SOLID STATE BATTERY

专利摘要:
solid-state battery, methods for fabricating an active electrode material and for fabricating an electrode, and, electrode one mode provides a solid-state battery that has a positive electrode layer; a negative electrode layer; and a solid electrolyte layer, which conducts lithium ions, disposed between the positive electrode layer and the negative electrode layer. the positive electrode layer contains a positive electrode active material and a solid electrolyte comprising a complex hydride. said positive electrode active material is sulfur based, and the solid electrolyte layer contains a solid electrolyte comprising a hydride of a complex.
公开号:BR112016004291B1
申请号:R112016004291-3
申请日:2014-08-27
公开日:2021-08-24
发明作者:Genki Nogami；Mitsugu Taniguchi；Masaru TAZAWA；Atsushi UNEMOTO；Motoaki Matsuo；Shinichi Orimo
申请人:Tohoku Techno Arch Co., Ltd.；Mitsubishi Gas Chemical Company, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a solid state battery, particularly a solid state battery, in which lithium ions are responsible for electrical conduction. Furthermore, the present invention further relates to a method for manufacturing an active electrode material. PRIOR TECHNIQUE
[002] In recent years, there has been an increasing demand for lithium-ion secondary batteries in applications such as portable information terminals, portable electronic devices, electric cars, hybrid electric cars, and other stationary electric storage systems. However, existing lithium-ion secondary batteries use flammable organic solvents such as liquid electrolytes, and require rigid exteriors in order to prevent leakage of organic solvents. Also, there are restrictions on the structure of devices, such as the need for portable personal computers or the like to have a risk-free structure in case of liquid electrolyte leakage.
[003] Furthermore, the applications extend even to mobile vehicles such as automobiles and aircraft, and large capacity is required in stationary lithium-ion secondary batteries. In addition, high energy density is required in smart phones, which have spread rapidly and widely in recent years. Given such a situation, there is a tendency that safety is considered to be more important than before, and the development of solid state lithium ion secondary batteries without the use of toxic materials such as organic solvents has been focused.
[004] As a solid electrolyte in solid-state lithium-ion secondary batteries, the use of oxides, phosphate compounds, organic polymers, sulfides, and the like, has been investigated. However, phosphate oxides and compounds have low redox resistance, and so it is difficult for them to exist stably in secondary lithium ion batteries. Yet, they also have a disadvantage that when materials such as lithium on metal, low crystallinity carbon, and graphite are used as a negative electrode, the solid electrolyte reacts with the negative electrode (Patent Literature 1).
[005] Furthermore, oxides and phosphate compounds have the characteristics that their particles are hard. Therefore, in order to form a solid electrolyte layer using these materials, sintering at a high temperature of 600°C or more is generally required, which is time-consuming. Furthermore, oxides and phosphate compounds, when used as a solid electrolyte layer material, have a disadvantage that the interfacial resistance with the active electrode material increases. Organic polymers have a disadvantage that the conductivity of lithium ions at room temperature is low, and the conductivity dramatically decreases when the temperature decreases.
[006] However, sulfides are known to have a high lithium ion conductivity of 1.0 x 10-3 S/cm or higher (Patent Literature 2) and 0.2 x 10-3 S/cm or highest (Patent Literature 3) at room temperature. Furthermore, its particles are soft, which allows a solid electrolyte layer to be produced by cold pressing, and can easily make its contact interface a good state. However, in the case of using Ge or Si containing materials as a sulfide solid electrolyte material (Patent Literature 2 and Patent Literature 4), these materials have a problem of being susceptible to reduction. In addition, there is also the following problem: when batteries are configured using negative electrode active materials having an electrode potential of about 0 V (with reference to the Li electrode), as typified by lithium metals or active electrode materials, which are able to ensure high voltage in a single cell (Patent Literature 4), the reduction reaction of the solid sulfide electrolyte takes place.
[007] In order to prevent the aforementioned problems, a method for providing a coating on the active material surface of the negative electrode (Patent Literature 5) and a method for engineering a solid electrolyte composition (Patent Literatures 6 to 10) , for example, were proposed. In particular, Patent Literature 10 uses a solid electrolyte containing P2S5, but a problem for a reaction with the active material of the negative electrode remains, even in the case of the use of such a solid sulfide electrolyte (Non-Patent Literature 1). Also, the stability of the negative electrode easily changes due to a small amount of impurities in the solid electrolyte layer, and its control is not easy. Under such circumstances, a solid electrolyte capable of forming a good interface with an adjacent material while having high lithium ion conductivity without adversely affecting the stability of the active electrode material was desired.
[008] With respect to new solid lithium ion conductive electrolytes it was reported in 2007 that the high temperature phase of LiBH4 had high lithium ion conductivity (Non-Patent Literature 2), and it was reported in 2009 that a solid solution obtained by adding LiI to LiBH4 could maintain the high temperature phase at room temperature (Non-Patent Literature 3 and Patent Literature 11; then, for example, an ion conductor containing a complex hydride, such as LiBH4, will also be referred to as a complex hydride solid electrolyte). Battery configurations that use such a complex hydride solid electrolyte have been studied, and it is reported that they exert effects particularly in the case of the use of lithium on metal as a negative electrode (Patent Literature 12 and Patent Literature 13).
[009] However, solid electrolyte containing LiBH4 has a disadvantage of reducing oxides that are generally used as an electrode positive active material, such as LiCoO2. As a technique to prevent this, it has been reported that charge/discharge cycles at 120°C could be achieved by coating with a LiCoO2 layer having 100 nm pulsed laser deposition (PLD) with about 10 nm Li3PO4 (Literature No Patent 4). However, this technique is not intended for bulk type batteries, but for thin film batteries, manufactured using vapor deposition, and therefore there are disadvantages that the capacity per cell may not be ensured as much as for bulk types , and productivity is also deficient.
[0010] Although a method to avoid complex hydride reduction using a positive electrode specific active material has been found, the active materials available for positive electrode are exceptionally limited (such as polycyclic aromatic hydrocarbons with a polyacene skeletal structure and fluoride fluorides. perovskite) (Patent Literature 12). Furthermore, these electrode positive active materials are not oxide positive electrode active materials which are commonly used for currently available commercially available lithium ion secondary batteries and thus have no current results concerning long term stability. Patent Literature 12 describes that active electrode positive oxide materials coated with conductors of specific ions or carbons are less likely to be reduced, but the data shown in their examples indicates only a reducing action during charging, and thus does not describe necessarily the effects when loading and unloading are repeated.
[0011] Non-Patent Literature 4 mentions that the reduction of LiCoO2 by LiBH4 occurs during charging, and figure 1 of Non-Patent Literature 4 clearly shows that battery resistance increases by repeating charge/discharge cycles. It can be said from this that there is a demand for effective means, capable of not only suppressing the reduction of active material from positive electrode due to complex hydride in the short term, but also suppressing the increase in battery resistance after charge repetition and discharge.
[0012] However, in the case of using sulfur as an active material, it has an exceptionally high theoretical capacity of 10 times or more, although it has a low operating voltage of 1.5 to 2.0 (with reference to the electrode of Li), compared to LiCoO2 (4.2 V with reference to the Li electrode) which is a positive electrode active material commonly used today for lithium ion batteries. Therefore, the development aimed at producing high-capacity batteries using various sulfur compounds has proceeded. However, when a sulfur-based active electrode material is used in the liquid electrolyte system, polysulfide is dissolved in the liquid electrolyte, and therefore there is a problem of a decrease in Coulomb efficiency (discharge capacity/capacity load) when loading and unloading are repeated (Non-Patent Literature 5). To solve this problem, a technique using a solid-state battery was devised, and the application of active sulfur-based electrode materials to solid-state batteries was expected.
[0013] Electrode materials also have the following problems. That is, the main current of currently used lithium ion secondary batteries is to use scarce resources, called rare metals, such as cobalt and nickel, as electrode materials, and therefore there is a demand for electrode materials with higher availability and lower cost.
[0014] As a cheap and abundant material, sulfur is exemplified. When sulfur is used as an active electrode material, it has an exceptionally high theoretical capacity of 10 times or more, although it has a low operating voltage of 1.5 to 2.5 V (with reference to the lithium electrode), in comparison with LiCoO2 (4.2 V with reference to Li electrode) which is a positive electrode active material commonly used for lithium ion secondary batteries today. Therefore, attempts to produce high quality batteries using various sulfur compounds as active electrode materials have been made.
[0015] Unlike LiCoO2, which is a common electrode positive active material for lithium ion secondary batteries, the sulfur-based electrode active materials do not contain lithium. Therefore, in order to operate them as batteries, an active material that contains lithium (eg, lithium in metal and lithium alloys such as Li-In alloy) is generally used in a negative electrode. However, since lithium on metal has exceptionally high reactivity and thus is dangerous, it is not easy to cause a large amount of active sulfur-based electrode material to react with lithium on metal. Also in the case of using a Li-In alloy, the alloy needs to be produced using lithium on metal, and so lithium on metal must be used after all.
[0016] Currently, the negative electrode active materials used in common secondary lithium ion batteries are carbon-based materials, which do not contain lithium. Furthermore, a material containing Si has been proposed as an active material of negative electrode, which may allow higher capacity batteries to be obtained, which also do not contain lithium. In the case where a battery is configured using such a lithium-free material as a negative electrode active material and a sulfur-based electrode active material as a positive electrode active material, the lithium insert (i.e., a doping with lithium) either on the positive electrode or on the negative electrode in advance is necessary (Patent Literatures 14 to 16).
[0017] Lithium doping is performed, for example, in lithium ion capacitors (Patent Literatures 17 and 18). Furthermore, a lithium doping method aimed at decreasing irreversible capacity is described for lithium ion secondary batteries (Patent Literature 19). These techniques are field doping methods for electrochemically doping lithium, which have a problem of needing replacement electrodes, or the need to insert a medium for doping into battery cells. Also, methods that use a liquid electrolyte are unsuitable as methods for doping solid-state battery electrodes.
[0018] A technique of reacting an active material with lithium in metal in advance before the electrodes are produced is also described (Patent Literatures 20 to 23). However, this method requires the use of lithium on metal with exceptionally high reactivity, and is unsuitable for mass production in view of both maintaining the quality of lithium on metal suitable for doping and safety.
[0019] Still, all of these methods aim to compensate for the irreversible capacity, and are unsuitable for doping in an amount equivalent to the theoretical capacity at which lithium can be inserted into an active material. This is because excess lithium remains as lithium in metal, which could possibly result in the generation of dendrite. Furthermore, it is highly possible that doping with a large amount of lithium in metal causes voids to be generated in portions where lithium in metal was originally present. In the case of batteries that use a liquid electrolyte, lithium ion conductivity can be ensured by the liquid electrolyte filling the voids that have been generated, whereas in the case of batteries that use a solid electrolyte, an increase in voids causes a decrease in the conductivity of lithium ions.
[0020] As a technique without the use of lithium on metal, a method for doping a silicon/silicon oxide composite with lithium using lithium hydride or lithium aluminum hydride is described (Patent Literature 24). However, this method also aims to compensate for the irreversible capacity, and it is described that the existence of unreacted lithium or lithium aluminum hydride causes unfavorable effects on the battery properties.
[0021] Therefore, there is a demand for a lithium doping method, which allows for safer and more convenient doping and which additionally is applicable to solid state batteries. Quote List Patent Literature
[0022] Patent Literature 1: Japanese Patent Open to Public Inspection No. 2000-223156; Patent Literature 2: International Publication No. WO 2011/118801; Patent Literature 3: Japanese Patent Open to Public Inspection No. 2012-43646; Patent Literature 4: Japanese Patent Open to Public Inspection No. 2006-277997; Literature Patent 5: Japanese Patent Open to Public Inspection No. 2011-150942; Patent Literature 6: Japanese Patent No. 3149524; Patent Literature 7: Japanese Patent No. 3163741; Patent Literature 8: Japanese Patent No. 3343934; Patent Literature 9: Japanese Patent No. 4165536; Literature Patent 10: Japanese Patent Open to Public Inspection No. 2003-68361; Patent Literature 11: Japanese Patent No. 5187703; Literature Patent 12: Japanese Patent Open to Public Inspection No. 2012-209106; Literature Patent 13: Japanese Patent Open to Public Inspection No. 2012-209104; Literature Patent 14: International Publication No. WO 2010/44437; Literature Patent 15: Japanese Patent Open to Public Inspection No. 2012-150934; Literature Patent 16: Japanese Patent Open to Public Inspection No. 2008-147015; Literature Patent 17: Japanese Patent Open to Public Inspection No. 2011 and 249517; Literature Patent 18: Japanese Patent Open to Public Inspection No. 2011 and 249507; Literature Patent 19: Japanese Patent No. 4779985 Literature Patent 20: Japanese Patent Open to Public Inspection No. 2012-204306; Literature Patent 21: Japanese Patent Open to Public Inspection No. 2012-204310; Literature Patent 22: Japanese Patent Open to Public Inspection No. 2012-209195; Literature Patent 23: Japanese Patent Open to Public Inspection No. 2012-38686 Literature Patent 24: Japanese Patent Open to Public Inspection No. 2011 and 222153. Non-Patent Literature Non-Patent Literature 1: SEI Technical Review, September 2005, vol . 167, pages 54 to 60; Non-Patent Literature 2: Applied Physics Letters (2007) 91, page 224103; Non-Patent Literature 3: JOURNAL OF THE AMERICAN CHEMICAL SOCIETI (2009), 131, pages 894 to 895; Non-Patent Literature 4: Journal of Power Sources (2013), 226, pages 61 to 64. Non-Patent Literature 5: Electrochemistry Communications, 31, pages 71-75 (2013). SUMMARY TECHNICAL PROBLEM
[0023] A first aspect of the present invention is intended to provide a solid state battery having high ion conductivity and excellent stability. Additionally, a second aspect of the present invention is intended to provide a method for doping a sulfur-based active electrode material with lithium, which allows for safe and convenient lithium doping. SOLUTION TO THE PROBLEM
[0024] The first aspect of the present invention, for example, is as follows: [1] A solid state battery comprising: a positive electrode layer; a negative electrode layer; and a solid electrolyte layer, which conducts lithium ions, disposed between the positive electrode layer and the negative electrode layer, wherein the positive electrode layer contains a positive electrode active material and a complex hydride solid electrolyte, the positive electrode active material is a sulfur-based electrode active material and the solid electrolyte layer contains a complex hydride solid electrolyte; [1 - 2] The solid state battery according to [1], wherein the complex hydride solid electrolyte contained in the positive electrode layer is the same as the complex hydride solid electrolyte contained in the solid electrolyte layer; [2] The solid state battery according to [1] or [1 - 2], wherein the active sulfur-based electrode material is an inorganic sulfur compound or a sulfur polyacrylonitrile; [3] The solid state battery according to [2], wherein the inorganic sulfur compound is selected from the group consisting of S, carbon-S composite, TiS2, TiS3, TiS4, NiS, FeS2, and MoS2 ; [4] The solid state battery according to any one of [1] to [3], wherein the complex hydride solid electrolyte is LiBH4 or a combination of LiBH4 and an alkali metal compound, represented by the formula (1) below: MX(1), wherein M represents an alkali metal atom selected from the group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or a group of NH2; [4-1] The solid state battery according to [4], wherein the complex hydride solid electrolyte has diffraction peaks of at least 2θ = 24.0 ± 1.0 degrees, 25.6 ± 1m2 degrees, 27.3 ± 1m2 degrees, 35.4 ± 1.5 degrees, and 42.2 ± 2.0 degrees in X-ray diffraction (CuKα: X = 1.5405 Â) at less than 115°C; [5] The solid state battery according to [4] or [4-1], wherein the alkali metal compound is selected from the group consisting of a rubidium halide, a lithium halide, a cesium halide , and a lithium amide; [5-1] The solid state battery according to any one of [1] to [5], wherein the negative electrode layer contains a negative electrode active material selected from the group consisting of Li, carbon, and Si; [5-2] The solid state battery according to any one of [1] to [5-1], wherein the negative electrode layer contains the same solid electrolyte as the complex hydride solid electrolyte contained in the electrode layer. solid electrolyte; [6] The solid-state battery according to any one of [1] to [5], in which the positive electrode layer is formed by pressing; and [7] The solid state battery according to [6], in which pressing is performed by applying a pressure of 114 to 500 MPa on a material of the positive electrode layer. The second aspect of the present invention, for example, is as follows: [8] A method for making a lithium-doped sulfur-based electrode active material comprising: doping a sulfur-based active electrode material, with lithium by mixing the sulfur-based active electrode material with a material containing a lithium-containing complex hydride; [9] The method for making a lithium-doped sulfur-based electrode active material according to [8], wherein the step of doping the sulfur-based active electrode material with lithium is performed by mixing the active sulfur-based electrode material with the material containing a lithium-containing complex hydride, followed by heating; [10] The method for fabricating a lithium-doped, sulfur-based active electrode material according to [9], wherein heating is carried out at a temperature of 60°C to 200°C; [10-1] The method of making a lithium-doped, sulfur-based active electrode material according to any one of [8] to [10], wherein the active electrode material mixture is based on the base. sulfur, with the material containing a complex hydride containing lithium is carried out under an inert gas atmosphere; [10-2] The method for manufacturing a lithium-doped, sulfur-based active electrode material according to any one of [8] to [10-1], wherein the active electrode material mixture, sulfur-based, with the material containing a lithium-containing complex hydride is carried out by a dry process; [11] The method of making a lithium-doped, sulfur-based electrode active material according to any one of [8] to [10-2], wherein the sulfur-based active electrode material , is selected from the group consisting of a sulfur polyacrylonitrile, a disulfide compound, TiS2, TiS3, TiS4, NiS, NiS2, CuS, FeS2, and MoS3; [12] The method for making a lithium-doped, sulfur-based electrode active material according to any one of [8] to [11], wherein the material containing a complex hydride containing lithium is an electrolyte solid that conducts lithium ions; [13] The method for making a lithium-doped, sulfur-based electrode active material according to any one of [8] to [12], wherein the material containing a complex hydride containing lithium is LiBH4 or a combination of LiBH4 and an alkali metal compound, represented by the formula (1) below: MX(1), wherein M represents an alkali metal atom selected from the group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or an NH2 group; [13-1] The method for fabricating a lithium-doped, sulfur-based active electrode material according to [13], wherein the material containing a complex hydride containing lithium has diffraction peaks in at least 2θ = 24.0 ± 1.0 degrees, 25.6 ± 1m2 degrees, 27.3 ± 1m2 degrees, 35.4 ± 1.5 degrees, and 42.2 ± 2.0 degrees in X-ray diffraction (CuKα : X = 1.5405 Â) at less than 115 °C; [14] The method for fabricating a lithium-doped, sulfur-based electrode active material according to [13] or [13-1], wherein the alkali metal compound is selected from the group consisting of a rubidium halide, a lithium halide, a cesium halide, and a lithium amide; [15] An electrode comprising a lithium-doped, sulfur-based active electrode material manufactured by the method according to any one of [8] to [14]; [16] A method of making an electrode, comprising: preparing a mixture of a sulfur-based active electrode material and a material containing a complex hydride containing lithium; apply the mixture to a current collector; and doping the active sulfur-based electrode material with lithium by heating the current collector applied with the mixture; [16-1] The method for fabricating an electrode according to [16], wherein heating is carried out at a temperature of 60°C to 200°C; [16-2] The method for fabricating an electrode according to [16] or [16-1], wherein the preparation of a mixture of the active sulfur-based electrode material and the material containing a complex hydride containing lithium is carried out under an inert gas atmosphere; [16-3] The method for fabricating an electrode according to any one of [16] to [16-2], wherein the preparation of a mixture of the active sulfur-based electrode material and the material containing a Lithium-containing complex hydride is made by a dry process; [16-4] The method for fabricating an electrode according to any one of [16] to [16-3], wherein the active sulfur-based electrode material is selected from the group consisting of a polyacrylonitrile of sulfur, a disulfide compound, TiS2, TiS3, TiS4, NiS, NiS2, CuS, FeS2, and MoS3; [16-5] The method for fabricating an electrode according to any one of [16] to [16-4], wherein the material containing a complex hydride containing lithium is a solid electrolyte that conducts lithium ions; [16-6] The method for fabricating an electrode according to any one of [16] to [16-5], wherein the material containing a complex hydride containing lithium is LiBH4 or a combination of LiBH4 and a metal compound alkaline, represented by the formula (1) below: MX(1), wherein M represents an alkali metal atom selected from the group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or an NH2 group; [16-7] The method for fabricating an electrode according to [16-6], wherein the material containing a lithium-containing complex hydride has diffraction peaks of at least 2θ = 24.0 ± 1.0 degrees , 25.6 ± 1m2 degrees, 27.3 ± 1m2 degrees, 35.4 ± 1.5 degrees, and 42.2 ± 2.0 degrees in X-ray diffraction (CuKα: X = 1.5405 Â) in minus than 115 °C; [16-8] The method for fabricating an electrode according to [16-6], wherein the alkali metal compound is selected from the group consisting of a rubidium halide, a lithium halide, a cesium halide, and a lithium amide; [17] An electrode manufactured by the method according to any one of [16] to [16-8]; [18] A secondary lithium-ion battery comprising the electrode according to [15] or [17]; [19] The secondary lithium ion battery according to [18] being a solid state battery; [20] Li-ion secondary battery according to [18] or [19], where one electrode is the electrode according to [15] or [17], and the other electrode is a lithium-free electrode; and [21] A solid-state battery comprising: a positive electrode layer; a negative electrode layer; a solid electrolyte layer, which conducts lithium ions, disposed between the positive electrode layer and the negative electrode layer, where the positive electrode layer is the electrode according to [15] or [17], and the layer of solid electrolyte contains a complex hydride solid electrolyte. ADVANTAGEOUS EFFECTS OF THE INVENTION
[0025] The first aspect of the present invention can provide a solid state battery having high ion conductivity and excellent stability. In addition, the second aspect of the present invention can provide a method for making a lithium-doped, sulfur-based active electrode material that allows for safe and convenient lithium doping. Furthermore, the method according to the second aspect of the present invention can be applied also to solid state batteries. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 is a sectional view of a solid state battery according to the first aspect of the present invention.
[0027] Figure 2 is an SEM image showing a cross section of a positive electrode layer in a solid state battery, produced in Example A1.
[0028] Figure 3A is a graph showing the transition in discharge capacity of the solid state battery, produced in Example A1.
[0029] Figure 3B is a graph showing the transition in discharge capacity of a solid state battery, produced in Example A6.
[0030] Figure 3C is a graph showing the transition in discharge capacity of a solid state battery, produced in Example A7. [the 3D figure] The 3D figure is a graph showing the transition in discharge capacity of a solid state battery, produced in Example A8. [Figure 3E] Figure 3E is a graph showing the transition in discharge capacity of a solid-state battery produced in Example A9. [figure 3F] Figure 3F is a graph showing the transition in discharge capacity of a solid state battery produced in Example A10.
[0031] Figure 4A is a graph showing solid state battery charge-discharge curves, produced in Example A1, in the 1st, 2nd, and 45th cycles.
[0032] Figure 4B is a graph showing charge-discharge curves of the solid state battery, produced in Example A6, in the 2nd, 3rd, and 45th cycles.
[0033] Figure 4C is a graph showing charge-discharge curves of the solid state battery, produced in Example A7, in the 2nd, 3rd, and 20th cycles.
[0034] Figure 5 is a graph showing the results of thermal desorption mass spectroscopy for a mixture of TiS2 and LiBH4.
[0035] Figure 6A is a graph showing the X-ray Diffraction Measurement results for powders obtained in Example B1.
[0036] Figure 6B is a graph showing the X-ray diffraction measurement results for powders obtained in Example B2.
[0037] Figure 6C is a graph showing the X-ray diffraction measurement results for powders obtained in Example B3.
[0038] Figure 7 is a graph showing the correlation of lithium content with respect to the truss constants of the geometric axes a and c.
[0039] Figure 8 is a graph showing the transition in discharge capacity of a solid state battery, produced in Example B4.
[0040] Figure 9 is a graph showing solid state battery charge-discharge curves, produced in Example B4, at 1st, 2nd, and 20th cycles. DESCRIPTION OF MODALITIES
[0041] Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that components having the same or similar function in the drawings are represented by the same reference number, and the superimposed description will be omitted. Furthermore, the present invention is not limited to the materials, configurations, or the like, described below, and various modifications can be made within the scope of the spirit of the present invention. [First aspect]
[0042] Figure 1 is a sectional view of the solid state battery according to the first aspect of the present invention.
[0043] A solid state battery 10 is, for example, a solid state lithium ion secondary battery and can be used in various devices including mobile phones, personal computers, automobiles, and the like. The solid state battery 10 has a structure in which a solid electrolyte layer 2 is disposed between a positive electrode layer 1 and a negative electrode layer 3. In the present invention, the positive electrode layer 1 contains an active electrode material. positive and a complex hydride solid electrolyte, and the positive electrode active material is a sulfur-based electrode active material. In addition, solid electrolyte layer 2 contains a complex hydride solid electrolyte. Such a configuration allows for the suppression of an increase in battery resistance when the battery is operated. This effect is also obtained when charge/discharge cycles are repeated, and therefore it is possible to provide a solid state battery that operates stably over a long period of time, although it uses a complex hydride solid electrolyte with high ion conductivity .
[0044] As mentioned above, in the case of using a complex hydride as a solid electrolyte, the reduction of the active material of electrode positive is in question. The reason why the above-mentioned effect can be obtained in such a situation is unclear, but the state is thought to be less likely to lead to an increase in battery resistance and a decrease in battery capacity, even if the active material of positive electrode react with the complex hydride solid electrolyte. As a result, even if the complex hydride solid electrolyte is in contact with the positive electrode active material, the complex hydride with high lithium ion conductivity can be used as the solid electrolyte regardless of the reduction of the positive electrode active material by the complex hydride. Furthermore, it can be estimated that an increase in battery resistance is suppressed, as described above, as a result of which a solid state battery that operates stably over a long period of time, even if the charge/discharge cycles are repeated, can be provided.
[0045] Hereinafter, each element will be described in detail. 1. Positive electrode layer
[0046] The positive electrode layer 1 contains a sulfur-based electrode active material as a positive electrode active material and a complex hydride solid electrolyte. The positive electrode layer 1 may optionally further contain a conductive additive, a binder, or the like.
[0047] Any material can be used as the active electrode material, based on sulfur, as long as it is capable of releasing lithium ions during charging and absorbing lithium ions during discharge. Particles or a thin film of an organic sulfur compound or an inorganic sulfur compound can be used for this, both of which will carry out the charging and discharging using the sulfur oxidation-reduction reaction.
[0048] Examples of the organic sulfur compound include a disulfide compound, a sulfur polyacrylonitrile typified by a compound according to WO 2010-044437, a sulfur polyisoprene, rubeanic acid (dithiooxamide), and polysulfide carbon. Among them, a disulfide compound, a sulfur polyacrylonitrile, and rubeanic acid are preferable, and a sulfur polyacrylonitrile is particularly preferable. As a disulfide compound, a dithiobiurea derivative, and a disulfide compound having a thiourea, thioisocyanate group, or a thioamide group, they are more preferable.
[0049] Sulfur polyacrylonitrile is modified polyacrylonitrile containing sulfur atoms, which is obtained by mixing sulfur powder with polyacrylonitrile and heating the mixture under inert gas or reduced pressure. The estimated structure thereof is, for example, a structure in which polyacrylonitrile undergoes ring closure to be polycyclic, and at least a part of S binds to C, as shown in Chem. Mater. 2011, 23, 5024-5028. A compound described in this literature has strong peak signals at about 1330 cm-1 and 1560 cm-1, and still has peaks at about 307 cm-1, 379 cm-1, 472 cm-1, and 929 cm-1 in the Raman spectrum.
[0050] Here, a method for preparing sulfur polyacrylonitrile will be described.
[0051] Sulfur as a raw material is not specifically limited, but any of α-sulfur, β-sulfur, and Y—sulfur, each having a structure of S8 can be used for this. When the particle size of sulfur is too large, the mixing capacity decreases, and when it is too small, sulfur is in the form of nanoparticles, which are difficult to manipulate. Therefore, the particle size is preferably in the range of 1 to 300 µm, more preferably 10 to 200 µm, when viewed by an electron microscope.
[0052] Polyacrylonitrile is not specifically limited, but its molecular weight, average to weight, is preferably in the range of 10,000 to 300,000. The particle size of the polyacrylonitrile is preferably in the range 0.1 to 100 µm, particularly preferably 1 to 50 µm.
[0053] The method for mixing sulfur with polyacrylonitrile is not specifically limited, but examples of the same include methods using a grinding wheel, a ball mill, a planetary ball mill, a glass microsphere mill, a revolving mixer, a mixing device with high speed agitation, and a mixer with cleaning drum. However, if a method, in which high energy is supplied at the time of mixing, as typified by mixing through the use of a planetary ball mill, is used, not only the mixing, but also the reaction, can possibly proceed simultaneously. Therefore, a grinding wheel or cleaning drum mixer capable of gentle mixing is preferably used. In the case of small scale implementation, mixing the mortar by hand is preferable. Mixing is preferably carried out by a dry process, but it can also be carried out in the presence of a solvent. In the case of using a solvent, a solvent having a boiling point of 210°C or lower is preferably used, so that the solvent is volatilized and removed before the sulfur is reacted with polyacrylonitrile.
[0054] The mixing ratio between sulfur powder and polyacrylonitrile as raw materials is not specifically limited, but is preferably in the sulfur range: polyacrylonitrile = 0.3:1 to 10:1, more preferably 1:1 to 5:1, in a weight ratio.
[0055] Heating after mixing can be carried out under reduced pressure or inert gas. In the case of heating under reduced pressure, it is preferably carried out at a pressure in the range of 10 Pa to 70 kPa. In the case of heating under inert gas, it is preferably carried out at a pressure in the range of 0.1 kPa to 1 MPa, more preferably in the range of 1 kPa to 150 kPa. Examples of the inert gas can include helium, nitrogen, and argon. It should be noted that, in the case of heating under inert gas, the inert gas is preferably circulated. This is because the reaction proceeds well by removing hydrogen sulfide gas to be generated. In the case of heating under reduced pressure, the reactor is preferably replaced by the inert gas before heating. This is because an oxidation reaction, which is a side reaction, proceeds if oxygen remains. However, this does not apply in the case where the degree of vacuum is high, and oxygen can be almost removed from the system.
[0056] The heating temperature is preferably in the range 200 to 500°C, more preferably in the range 250 to 450°C. When the temperature is higher than this range, sulfur volatilization is improved, and therefore a greater amount of sulfur as a raw material is needed. When the temperature is low, the reaction proceeds slowly, which is not efficient.
[0057] The heating time is not specifically limited, but the above-mentioned temperature can be maintained, for example, for 1 to 12 hours. When the heating temperature is low, it takes time to obtain sulfur polyacrylonitrile, and when the heating temperature is high, sulfur polyacrylonitrile can be obtained within a short time. The temperature and time can be adjusted depending on the devices to be used or the scale.
[0058] Inorganic sulfur compound is preferable because of its excellent stability, and Specific examples thereof include sulfur(S), carbon-S composite, TiS2, TiS3, TiS4, NiS, NiS2, CuS, FeS2, Li2S , MoS2, and MoS3. Among them, S, carbon-S composite, TiS2, TiS3, TiS4, FeS2, and MoS2 are preferable, and carbon-S composite, TiS2, and FeS2 are most preferable.
[0059] The carbon-S composite contains sulfur dust and a carbon material, and is formed by heating or mechanically mixing them to form a composite state. More specifically, it is in a state in which sulfur is distributed over surfaces or in pores of the carbon material, in a state in which sulfur and carbon material are evenly dispersed at the nano level and are aggregated to form particles, in a state in which the carbon material is distributed over surfaces of or within the fine sulfur powder, or in a state in which a plurality of these states are combined.
[0060] Here, a method to prepare the carbon-S composite will be described.
[0061] Sulfur as a raw material is not specifically limited, but any of α-sulfur, β-sulfur, and Y—sulfur, either having a structure of S8, can be used for this. When the particle size of sulfur is too large, the mixing capacity decreases, and when it is too small, sulfur is in the form of nanoparticles, which are difficult to manipulate. Therefore, the particle size is preferably in the range of 1 to 300 µm, more preferably 10 to 200 µm.
[0062] Carbon material is not specifically limited, but examples thereof include carbon black, acetylene black, Ketjen black, Maxsorb(R), carbon fiber, and graphene. Also, these can be used in combination. In the case of using Maxsorb(R) and Ketjen Black in combination, the plateau region during loading and unloading expands, and the loading/unloading capacity retention rate is high, even after repeated cycles, which is more preferable.
[0063] The ratio of sulfur to carbon material is preferably in the range of sulfur: carbon material = 0.1:1 to 10:1, more preferably 0.5:1 to 3:1, in a ratio of Weight. When the amount of sulfur is large, an active material having high charge-discharge capacity per unit weight can be obtained, which is therefore preferable. When the amount of carbon material is excessively small, the electron conductivity decreases, and thus operation as a battery is made difficult. Therefore, the ratio of sulfur to carbon material is important. It should be noted that, in almost all of the preparation methods, the ratio of sulfur to carbon material as raw materials conforms to the ratio of sulfur to carbon material in the carbon-S composite as a product. .
[0064] The method of preparation is also not specifically limited, and Examples thereof include a method of mixing sulfur with the carbon material, followed by heating to the melting point of sulfur or higher, a method using a method of mechanochemical impact, high velocity air flow.
[0065] The method using mechanochemistry is a method to cause powerful grinding, mixing, and reaction by applying mechanical energy to a plurality of different materials. For example, the method is carried out using a ball mill, a glass microsphere mill, or a planetary ball mill, in which a solvent can also be used. The high velocity air flow impact method is an appropriate method for the case where preparation in a larger quantity is desired, which is carried out, for example, using a jet mill. As with these methods, in the case of using a method that has high grinding performance and is capable of very fine particle grinding, the sulfur and carbon material are evenly distributed at the nano level. When an S-carbon composite, obtained from particles formed by aggregating them, is used as an active material, the charge/discharge capacity retention rate is improved, which is therefore more preferable.
[0066] Also, a method to generate sulfur from thiosulfate, such as Na2S2O3, and insert sulfur into the inner space of a carbon material, is described (Japanese Patent Open to Public Inspection No. 2012204332), and a composite of carbon-S, prepared using the above-mentioned method can also be used.
[0067] The positive electrode layer 1 is of the putty type, containing both the active electrode material, based on sulfur, as the solid electrolyte of complex hydride. The battery can be operated by forming the positive electrode layer in a thin film with a thickness of 1 to 10 µm, even if the positive electrode layer does not contain a solid electrolyte, in which however, the amount of active material to be contained per cell decreases. Therefore, the above mentioned configuration is not preferable as a battery configuration that aims to ensure capacity.
[0068] As complex hydride solid electrolyte, the same material as that described in "2. Solid electrolyte layer" below can be used. In particular, it is preferable that the same complex hydride solid electrolyte is contained in the positive electrode layer 1 and the solid electrolyte layer 2. This is because, if layers containing solid electrolytes of different compositions are in contact with each other, it is highly possible that the constituent elements of solid electrolytes diffuse into the respective layers, which can result in a decrease in the conductivity of lithium ions.
[0069] As a result of repeating tests by the present inventors, it was found that a solid state battery with high positive electrode utilization (the ratio of discharge capacity to theoretical capacity) and low interfacial resistance can be obtained, in the case where a positive mass-type electrode layer is formed using a sulfur-based active electrode material together with a solid electrolyte. The sulfur-based electrode active material is softer than the oxide electrode active materials, which are commonly used in secondary lithium ion batteries. Therefore, it is considered that the sulfur-based electrode active material is crushed together with the solid electrolyte during the formation of the positive electrode layer so that a good interface is formed between the positive electrode active material and the solid electrolyte, thus leading to the aforementioned effect. In particular, the positive electrode layer 1 is preferably produced by pressing by applying a pressure of 50 to 800 MPa, more preferably 114 to 500 MPa, to the above-mentioned material of the positive electrode layer, in view of the above-mentioned effect. That is, a layer having good adhesion and less void spaces between particles can be obtained by pressing at a pressure in the aforementioned range.
[0070] The ratio of active electrode positive material to solid electrolyte in the positive electrode layer 1 is favorably higher within the range in which the positive electrode shape can be maintained, and the necessary ion conductivity can be ensured. For example, the ratio is preferably in the range of electrode positive active material: solid electrolyte = 9:1 to 1:9, more preferably 8:2 to 2:8, in a weight ratio.
[0071] The conductive additive to be used for the positive electrode layer 1 is not specifically limited as long as it has a desired conductivity, but examples thereof may include a conductive additive made of a carbon material. Specific examples thereof include carbon black, acetylene black, Ketjen black, and carbon fibers.
[0072] The content of the conductive additive in the positive electrode layer 1 is preferably lower within the range that allows a desired electron conductivity to be ensured. The content of the conductive additive with respect to the positive electrode layer forming materials is, for example, 0.1% by mass to 40% by mass, preferably 3% by mass to 30% by mass.
[0073] As the binder to be used for the positive electrode layer 1, the commonly used binders for the positive electrode layers of lithium ion secondary batteries can be used. For example, polysiloxane, polyalkylene glycol, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), and ethylene vinyl alcohol copolymer (EVOH) can be used. A thickener, such as carboxymethylcellulose (CMC), can also be used as needed.
[0074] The thickness of the positive electrode layer 1 is not specifically limited as long as the function as a positive electrode layer is exerted, but it is preferably 1 μm to 1000 μm, more preferably 10 μm to 200 μm. 2. Solid electrolyte layer
[0075] The solid electrolyte layer 2 is a conductive layer of lithium ions disposed between the positive electrode layer 1 and the negative electrode layer 3, and contains a complex hydride solid electrolyte.
[0076] The complex hydride solid electrolyte is not specifically limited as long as it is a material that contains a complex hydride conducting lithium ions. For example, the complex hydride solid electrolyte is LiBH4 or a combination of LiBH4 and an alkali metal compound, represented by formula (1) below: MX(1), where M represents an alkali metal atom, selected from group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or an NH2 group.
[0077] The halogen atom that serves as X in Formula (1) above, for example, may be an iodine atom, a bromine atom, a fluorine atom, or a chlorine atom. X is preferably an iodine atom, a bromine atom, or an NH2 group, more preferably an iodine atom or an NH2 group.
[0078] Specifically, the alkali metal compound is preferably a lithium halide (eg LiI, LiBr, LiF, or LiCl), a rubidium halide (eg RbI, RbBr, RbF, or RbCl), a halide of cesium (for example, CsI, CsBr, CsF, or CsCl), or a lithium amide (LiNH2), more preferably LiI, RbI, CsI, or LiNH2. As an alkali metal compound, one of these can be used alone, or two or more of these can be used in combination. Preferred combinations include the combination of LiI and RbI.
[0079] Known compounds can be used, respectively, as LiBH4 and the alkali metal compound. Furthermore, the purity of these compounds is preferably 80% or greater, more preferably 90% or greater. This is because compounds having a purity within the aforementioned range perform high as a solid electrolyte.
[0080] The molar ratio between LiBH4 and the alkali metal compound is preferably 1:1 to 20:1, more preferably 2:1 to 7:1. When the molar ratio falls within the aforementioned range, the amount of LiBH4 in the solid electrolyte can be sufficiently ensured, and high ion conductivity can be obtained. On the other hand, when the amount of LiBH4 is excessively large, the high temperature phase transition temperature (high ion conduction phase) is less likely to decrease, and so there is a tendency that sufficient ion conductivity cannot be obtained at a temperature lower than the high temperature phase transition temperature of LiBH4 (115°C).
[0081] In the case of using two or more types of alkali metal compounds in combination, their mixing ratio is not specifically limited. For example, in case of using LiI and another alkali metal compound (preferably RbI or CsI) in combination, the molar ratio between LiI and the other alkali metal compound is preferably 1:1 to 20:1, more preferably 5:1 to 20:1. When the molar ratio falls within the aforementioned range, the amount of LiI in the solid electrolyte can be sufficiently ensured, and a solid electrolyte layer having good thermal stability can be obtained. On the other hand, when the amount of LiI is excessively large, there is a tendency that the addition effect of the other alkali metal compound cannot be sufficiently obtained, as a result of which sufficient ion conductivity cannot be obtained.
[0082] The complex hydride solid electrolyte preferably has diffraction peaks of at least 2θ = 24.0 ± 1.0 degrees, 25.6 ± 1m2 degrees, 27.3 ± 1m2 degrees, 35.4 ± 1, 5 degrees, and 42.2 ± 2.0 degrees in X-ray diffraction (CuKα: X = 1.5405 Â) at less than 115°C. It has diffraction peaks most preferably at least 2θ = 23.7 ± 0.7 degrees, 25.2 ± 0.8 degrees, 26.9 ± 0.8 degrees, 35.0 ± 1.0 degrees, and 41.3 ± 1.0 degrees, still preferably at least 2θ = 23.6 ± 0.5 degrees, 24.9 ± 0.5 degrees, 26.7 ± 0.5 degrees, 34.6 ± 0.5 degrees, and 40.9 ± 0.5 degrees. Furthermore, it has diffraction peaks particularly preferably at least 2θ = 23.6 ± 0.3 degrees, 24.9 ± 0.3 degrees, 26.7 ± 0.3 degrees, 34.6 ± 0.3 degrees, and 40.9 ± 0.3 degrees. These diffraction peaks in the five regions correspond to the diffraction peaks of the high temperature phase of LiBH4. Solid electrolyte having diffraction peaks in the five regions, as described above, even at a temperature lower than the high-temperature phase transition temperature of LiBH4 tends to exhibit high ion conductivity even at a lower temperature than the aforementioned transition temperature.
[0083] The method for preparing the complex hydride solid electrolyte is not specifically limited, but preparation, for example, by mechanical grinding or melt mixing according to Japanese Patent No. 5187703 is preferable. Solid electrolyte layer 2 can contain different materials than above when necessary. For example, solid electrolyte layer 2 that is formed on a sheet using a binder can also be used.
[0084] The thickness of the solid electrolyte layer 2 is preferably smaller. Specifically, the thickness is preferably in the range 0.05 to 1000 µm, more preferably in the range 0.1 µm to 200 µm. 3. Negative electrode layer
[0085] The negative electrode layer 3 is a layer containing at least one active negative electrode material, and may optionally contain a solid electrolyte, a conductive additive, a binder, and the like.
[0086] As the active material of the negative electrode, an active material of metal and an active material of carbon, for example, can be used. Examples of the aforementioned metal active material include Li, In, Al, Si, and Sn, and alloys of these metals. However, examples of the above mentioned active carbon material include mesocarbon microgranules (MCMB), highly oriented pyrolytic graphite (HOPG), hard carbon, and soft carbon. In particular, the use of an active material having a lower electrode potential as a negative electrode improves battery energy density and improves operating voltage, which is therefore preferable. Examples of such a negative electrode active material include Li, In-Li alloy, a carbon active material, and Si. It should be noted that, in the case of using a lithium metal plate as a negative electrode, the battery solid state is preferably heated in advance (eg at 120°C for about 2 hours). The adhesion between the solid electrolyte layer and the lithium on metal is improved by heating, so that charging and discharging can be carried out more stably.
[0087] The solid electrolyte to be used for the negative electrode layer 3 is not specifically limited, as long as it has lithium ion conductivity and is stable with the active material of the negative electrode, but a complex hydride solid electrolyte, by example, can be used. The complex hydride solid electrolyte is comparatively soft, and therefore can form a good interface with the active material of the negative electrode, such as graphite. The negative electrode layer 3 is preferably of the mass type containing both the active material of the negative electrode and the solid electrolyte. As the complex hydride solid electrolyte to be contained in the negative electrode layer 3, the complex hydride solid electrolyte described above for the solid electrolyte layer 2 can be used. In particular, it is preferable that the same complex hydride solid electrolyte is contained in the negative electrode layer 3 and the solid electrolyte layer 2. This is because, if layers containing solid electrolytes of different compositions are in contact with each other, it is highly possible that the constituent elements of solid electrolytes diffuse into the respective layers, which can result in a decrease in the conductivity of lithium ions.
[0088] The ratio between the active material of the negative electrode and the solid electrolyte is favorably higher within the range in which the shape of the negative electrode can be maintained, and the necessary ion conductivity can be ensured. For example, the ratio is preferably in the range of electrode negative active material: solid electrolyte = 9:1 to 1:9, more preferably 8:2 to 2:8, in a weight ratio.
[0089] As the conductive additive, to be used for the negative electrode layer 3, the same conductive additive as that in the positive electrode layer 1 can be used. The content of the conductive additive with respect to the materials forming the negative electrode layer is, for example, 0.1% by mass to 20% by mass, preferably 3% by mass to 15% by mass.
[0090] As the binder to be used for the negative electrode layer 3, the commonly used binders for the negative electrode layer of secondary lithium batteries can be used. Examples thereof include polysiloxane, polyalkylene glycol, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyacrylic acid. A thickener, such as carboxymethylcellulose (CMC), can also be used as needed.
[0091] The thickness of the negative electrode layer 3 is not limited as long as the function as a negative electrode layer is exerted, but it is preferably 0.05 μm to 1000 μm, more preferably 0.1 μm to 200 μm. (Method to manufacture solid state battery)
[0092] Subsequently, a method for manufacturing the solid state battery, described above, will be described.
[0093] Solid state battery is manufactured by forming the aforementioned layers and laminating the same, but the method for forming and the laminating method for the layers are not specifically limited. Examples thereof include: a method of forming a film by forming a slurry by dispersing a solid electrolyte or electrode active material in a solvent and applying the slurry by scraping blade, spin coating, or the like, followed by lamination; a vapor-phase method, in which film formation and lamination are carried out by vacuum evaporation, ion coating, sputtering, laser ablation, or the like; and a pressing method, in which powder is formed and laminated by hot pressing or cold pressing, without heating. Since the complex hydride solid electrolyte is soft, it is particularly preferable for the battery to be produced by forming and laminating the layers by pressing. Examples of a pressing method include hot pressing, which is performed by heating, and cold pressing, which is performed without heating, but cold pressing is more preferable because the complex hydride has sufficiently good formability without heating. It is preferred that the layers are integrally formed by pressing at a pressure of preferably 50 to 800 MPa, more preferably 114 to 500 MPa. A layer having good adhesion and less voids between particles can be obtained by pressing at a pressure in the aforementioned range, which is therefore preferable in view of the ion conductivity. Increasing the pressure by more than necessary is not practical, because it requires the use of a pressing apparatus and a forming vessel made of expensive materials, and its service life is reduced. [Second aspect]
[0094] In the method described below, a lithium doping step can be performed during the manufacture of the sulfur-based electrode active material, which can be performed during the electrode production, or it can be performed during the battery production . Hereafter, each aspect will be described in detail. 1. The manufacture of active, sulfur-based, lithium-doped electrode material
[0095] A method for making a lithium-doped sulfur-based electrode active material in accordance with an embodiment of the present invention includes a step of doping a sulfur-based electrode active material with lithium by mixing the sulfur-based active electrode material with a material containing a complex hydride containing lithium. In this description, "doping" or "doping" means a phenomenon expressed in various terms, such as intercalation, insertion, absorption, and transport, and "lithium doping" or "lithium doping" means a lithium-sulfur compound it is formed as a result of the above mentioned phenomenon.
[0096] According to the embodiment of the present invention, lithium doping can be conveniently performed without the use of electrochemical techniques, which are safe, since there is no need to use lithium in metal. it is also advantageous that the active sulfur-based electrode material is uniformly doped with lithium. Furthermore, the embodiment of the present invention allows doping with the entire amount of lithium that is needed for electrode reactions. In addition, since the material containing the lithium-containing complex hydride, which is a doping agent, serves as a lithium ion conductor, adverse effects on the battery, due to the remaining, excess doping agent, are exceptionally diminished. .
[0097] The method of the present invention, for example, can be used electrode active materials for lithium ion secondary batteries using a non-aqueous liquid electrolyte and electrode active materials for solid state lithium ion secondary batteries. The lithium-doped sulfur-based electrode active material is preferably used as a positive electrode, but can also be used as a negative electrode active material by being combined with an active material (such as FePO4, FeF3, and VF3) having higher electrode potential than the active sulfur-based electrode material.
[0098] Hereinafter, each material will be described in detail. (1) active electrode material, based on sulfur,
[0099] Any sulfur compound can be used as the active sulfur-based electrode material provided it is capable of releasing lithium ions during charging and absorbing lithium ions during discharge. An organic sulfur compound or an inorganic sulfur compound can be used for this, and these compounds can be subjected to treatment such as carbon coating and carbon complexing to provide electron conductivity.
[00100] Examples of the organic sulfur compound include a disulfide compound, a sulfur polyacrylonitrile, typified by a compound according to International Publication No. WO 2010-044437, a sulfur polyisoprene, and polysulfide carbon. Among them, a disulfide compound and a sulfur polyacrylonitrile are preferable, and a disulfide compound having a dithiobiurea derivative, a thiourea, thioisocyanate group, or a thioamide group is more preferable.
[00101] Sulfur polyacrylonitrile is a modified polyacrylonitrile containing sulfur atoms, which is obtained by mixing sulfur powder with polyacrylonitrile and heating the same under inert gas or reduced pressure. The estimated structure thereof is a structure in which polyacrylonitrile undergoes ring closure to be polycyclic, and at least part of the S binds to C, as described, for example, in Chem. Mater. 2011, 23, 5024-5028. A compound described in this literature has strong peak signals around 1330 cm-1 and 1560 cm-1, and still has peaks at about 307 cm-1, 379 cm-1, 472 cm-1, and 929 cm-1 in the Raman spectrum.
[00102] Here, a method for preparing a sulfur polyacrylonitrile will be described.
[00103] Sulfur as a raw material is not specifically limited, but any of α-sulfur, β-sulfur, and Y—sulfur, either having a structure of S8, can be used for this. When the particle size of sulfur is too large, the mixing capacity decreases, and when it is too small, sulfur is in the form of nanoparticles, which are difficult to manipulate. Therefore, the particle size is preferably in the range of 1 to 300 µm, more preferably 10 to 200 µm, when viewed by an electron microscope.
[00104] Polyacrylonitrile is not specifically limited, but its molecular weight, average to weight, is preferably in the range of 10,000 to 300,000. The particle size of the polyacrylonitrile is preferably in the range 0.1 to 100 µm, particularly preferably 1 to 50 µm.
[00105] The method for mixing sulfur with polyacrylonitrile is not specifically limited, but examples of the same include methods using a grinding wheel, a ball mill, a planetary ball mill, a glass microsphere mill, a revolving mixer, a mixing device with high speed agitation, and a mixer with cleaning drum. However, if a method in which great energy is supplied at the time of mixing, as typified by mixing through the use of a planetary ball mill, is used, not only the mixing, but also the reaction, can possibly proceed simultaneously. Therefore, a grinding wheel or cleaning drum mixer, capable of gentle mixing, is preferably used. In the case of small scale implementation, mixing the mortar by hand is preferable. Mixing is preferably carried out by a dry process, but it can also be carried out in the presence of a solvent. In the case of using a solvent, a solvent having a boiling point of 210°C or lower is preferably used, so that the solvent is volatilized and removed before the sulfur is reacted with polyacrylonitrile.
[00106] The mixing ratio between sulfur powder and polyacrylonitrile as raw materials is not specifically limited, but is preferably in the sulfur range: polyacrylonitrile = 0.3:1 to 10:1, more preferably 1:1 to 5: 1, in a weight ratio.
[00107] Heating after mixing can be carried out under reduced pressure or inert gas. In the case of heating under reduced pressure, it is preferably carried out at a pressure in the range of 10 Pa to 70 kPa. In the case of heating under inert gas, it is preferably carried out at a pressure in the range of 0.1 kPa to 1 MPa, more preferably in the range of 1 kPa to 150 kPa. Examples of the inert gas can include helium, nitrogen, and argon. It should be noted that, in the case of heating under inert gas, the inert gas is preferably circulated. This is because the reaction proceeds well by removing the hydrogen sulfide gas to be generated. In the case of heating under reduced pressure, the reactor is preferably replaced by the inert gas before heating. This is because an oxidation reaction, which is a side reaction, proceeds if oxygen remains. However, it does not apply in the case where the degree of vacuum is high, and oxygen can be almost removed from the system.
[00108] The heating temperature is preferably in the range 200 to 500°C, more preferably in the range 250 to 450°C. When the temperature is higher than this range, sulfur volatilization is improved, and therefore a greater amount of sulfur as a raw material is needed. When the temperature is low, the reaction proceeds slowly, which is not efficient.
[00109] The heating time is not specifically limited, but the above mentioned temperature can be maintained, for example, for 1 to 12 hours. When the heating temperature is low, it takes time to obtain sulfur polyacrylonitrile, and when the heating temperature is high, sulfur polyacrylonitrile can be obtained within a short time. A temperature and time can be adjusted depending on the devices to be used or the scale.
[00110] The inorganic sulfur compound is preferable because of its excellent stability, and the Specific Examples thereof include TiS2, TiS3, TiS4, NiS, NiS2, CuS, FeS2, and MoS3. Among them, TiS2, TiS3, TiS4, NiS, NiS2, FeS2, and MoS3 are preferable, and TiS2 is more preferable. (2) Material containing a lithium-containing complex hydride (hereinafter, also referred to as the doping agent)
[00111] Lithium-containing complex hydride is not specifically limited, as long as it can cause the active sulfur-based electrode material to dope with lithium, but is preferably LiBH4, LiAlH4, LiH, LiNH2, LiNiH3, or a compound containing lithium, prepared using this. In particular, the material containing a lithium-containing complex hydride is preferably a solid electrolyte carrying lithium ions. This is because, even if the remaining unreacted doping agent is present in an electrode during battery production using the lithium-doped, sulfur-based electrode active material, the doping agent works as an electrolyte solid, which therefore does not cause great battery resistance. For example, the material containing a complex hydride containing lithium is LiBH4 or a combination of LiBH4 and an alkali metal compound, represented by formula (1) below: MX(1), where M represents an alkali metal atom, selected a from the group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or an NH2 group.
[00112] The halogen atom that serves as X in Formula (1) above, for example, may be an iodine atom, a bromine atom, a fluorine atom, or a chlorine atom. X is preferably an iodine atom, a bromine atom, or an NH2 group, more preferably an iodine atom or an NH2 group.
[00113] Specifically, the alkali metal compound is preferably a lithium halide (eg LiI, LiBr, LiF, or LiCl), a rubidium halide (eg RbI, RbBr, RbF, or RbCl), a halide of cesium (for example, CsI, CsBr, CsF, or CsCl), or a lithium amide (LiNH2), more preferably LiI, RbI, CsI, or LiNH2. As an alkali metal compound, one of these can be used alone, or two or more of these can be used in combination. Preferred combinations include the combination of LiI and RbI.
[00114] Known compounds can be used respectively for LiBH4 and the alkali metal compound. Furthermore, the purity of these compounds is preferably 80% or greater, more preferably 90% or greater. This is because compounds that have a purity within the aforementioned range perform high as a solid electrolyte.
[00115] The molar ratio between LiBH4 and the alkali metal compound is preferably 1:1 to 20:1, more preferably 2:1 to 7:1. When the molar ratio falls within the aforementioned range, the amount of LiBH4 can be sufficiently ensured, and high ion conductivity can be obtained. On the other hand, when the amount of LiBH4 is excessively large, the high temperature phase transition temperature (high ion conduction phase) is less likely to decrease, and so there is a tendency that sufficient ion conductivity cannot be obtained at a temperature lower than the high temperature phase transition temperature of LiBH4 (115°C).
[00116] In case of using two or more types of alkali metal compounds in combination, their mixing ratio is not specifically limited. For example, in case of using LiI and another alkali metal compound (preferably RbI or CsI) in combination, the molar ratio between LiI and the other alkali metal compound is preferably 1:1 to 20:1, more preferably 5:1 to 20:1. This is because such a mixing ratio allows, in the case where a material remains after doping with lithium, for the material to act favorably as a solid electrolyte.
[00117] Material containing a complex hydride containing lithium has diffraction peaks preferably at least 2θ = 24.0 ± 1.0 degrees, 25.6 ± 1m2 degrees, 27.3 ±1m2 degrees, 35.4 ± 1.5 degrees, and 42.2 ± 2.0 degrees in X-ray diffraction (CuKα: X = 1.5405 Â) at less than 115°C. It has diffraction peaks most preferably at least 2θ = 23.7 ± 0.7 degrees, 25.2 ± 0.8 degrees, 26.9 ± 0.8 degrees, 35.0 ± 1.0 degrees, and 41.3 ± 1.0 degrees, still preferably at least 2θ = 23.6 ± 0.5 degrees, 24.9 ± 0.5 degrees, 26.7 ± 0.5 degrees, 34.6 ± 0.5 degrees, and 40.9 ± 0.5 degrees. Furthermore, it has diffraction peaks particularly preferably at least 2θ = 23.6 ± 0.3 degrees, 24.9 ± 0.3 degrees, 26.7 ± 0.3 degrees, 34.6 ± 0.3 degrees, and 40.9 ± 0.3 degrees. These diffraction peaks in the five regions correspond to the diffraction peaks of the high temperature phase of LiBH4. the material having diffraction peaks in the five regions, as described above, even at a temperature lower than the high temperature phase transition temperature of LiBH4 tends to exhibit high ion conductivity even at a temperature lower than the above mentioned transition temperature.
[00118] The method for preparing the material containing a complex hydride containing lithium is not specifically limited, but it is preferably prepared, for example, by mechanical milling or melt mixing according to Japanese Patent No. 5187703.
[00119] Subsequently, each step of the method for fabricating a lithium-doped, sulfur-based active electrode material will be described. 1-1. mixing method
[00120] First, the active sulfur-based electrode material is mixed with the material containing a complex hydride containing lithium. Mixing is preferably carried out under an atmosphere of inert gas such as argon and helium. The mixing method is not specifically limited, but examples of it include methods using a grinding wheel, a ball mill, a planetary ball mill, a glass microsphere mill, a revolving mixer, a mixing device with agitation to high speed, and a drum cleaning mixer. However, if a method in which large energy is supplied at the time of mixing, as typified by mixing through the use of a planetary ball mill, is used, not only mixing but also lithium doping or side reaction may possibly proceed simultaneously. Therefore, in the case where the lithium doping reaction is not intended to proceed during mixing, as in the case where lithium doping is performed during electrode production or during battery production, which will be described below, a grinding wheel or cleaning drum mixer which is capable of gentle mixing is preferably used. In the case of small scale implementation, mixing the mortar by hand is preferable. Mixing is preferably carried out by a dry process, but it can also be carried out in the presence of a solvent having resistance to reduction. In the case of using a solvent, non-aqueous aprotic solvents are preferable, and more specific Examples thereof may include ether solvents such as tetrahydrofuran and diethyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide.
[00121] The mixing ratio between the sulfur-based electrode active material and the material containing a lithium-containing complex hydride is not specifically limited, but is preferably in the range of (amount of lithium in the lithium-containing complex hydride) /(amount of lithium doping) = 1 to 50, more preferably in the range of 2 to 20, particularly preferably in the range of 2 to 10, in a molar ratio, in order to sufficiently ensure the amount of lithium with which the material electrode active, based on sulfur, is doped. As described above, in the case where the material containing a complex hydride containing lithium is a solid electrolyte, as being different from the case of using lithium in alkyl or lithium in metal as a doping agent, the incorporation of excess rarely causes effects. adverse effects on the electrode reaction, and therefore not much attention needs to be paid to the mixing ratio. However, in the case of formation of an electrode without doping agent removal, when the doping agent ratio is increased too much, the active material ratio is decreased, resulting in a decrease in charge-discharge capacity by electrode density . Therefore, an appropriate mixing ratio is preferably selected. It should be noted that the "amount of lithium doping" means a theoretical amount of lithium that can be introduced into the sulfur-based active electrode material, which, however, can be adjusted to be a smaller amount, depending on the goal. 1. and 2. Lithium doping
[00122] Depending on the method of mixing, the active electrode material, based on sulfur, is doped with lithium during mixing. However, a lithium doping is preferably performed under heating for the purpose of conducting in a short time. In this case, lithium doping is performed by mixing the sulfur-based active electrode material with the material containing a lithium-containing complex hydride and then heating it.
[00123] The heating temperature varies depending on the combination of the active sulfur-based electrode material and the material containing a complex hydride containing lithium, but is, for example, in the range of 60 to 200°C, plus preferably 80 to 150 °C. A temperature range, as described above, is indicated to be preferable also in that hydrogen is generated at about 100°C or higher in thermal desorption mass spectroscopy results for a mixture of TiS2 and LiBH4 (figure 5). In figure 5, hydrogen release is detected at mass number = 2. It can be seen that the intensity starts to increase to the noise level or higher at about 100°C, which is surrounded by a circular dashed line. When the temperature is higher than the above mentioned range, by-product generation or material degradation tends to occur. On the other hand, when the temperature is lower than the above mentioned range, the fact that the reaction is slowed down is in question.
[00124] The lithium doping time is preferably 1 to 40 hours, more preferably 2 to 30 hours. When the time is less than above, a lithium doping may fail to proceed sufficiently in some cases. When the reaction time is longer than necessary, the productivity decreases, and in the case where the process is carried out at a high temperature for a long period of time, the occurrence of side reactions is in question. 1-3. Purification
[00125] After lithium doping, purification can be carried out. For purification, a solvent, in which used material containing a lithium-containing complex hydride is dissolved, for example, ether solvents such as tetrahydrofuran and diethyl ether, and non-aqueous aprotic solvents such as N,N- dimethylformamide and N,N-dimethylacetamide can be used. However, the purification step is not necessarily necessary, and particularly in the case of using lithium-doped sulfur-based electrode active material in a solid-state lithium-ion secondary battery, the steps can be simplified. by omitting the purification step almost without deteriorating performance like a battery. 2. Electrode
[00126] The active, sulfur-based, lithium-doped electrode material obtained by the above-mentioned method can be used effectively in an electrode of a secondary lithium-ion battery. Accordingly, an embodiment of the present invention provides an electrode containing a lithium-doped, sulfur-based electrode active material manufactured by the above-mentioned method. In this case, the structure and manufacturing method for the electrode are the same as those for electrodes in common secondary lithium ion batteries. That is, the electrode can be manufactured by mixing the active, sulfur-based, lithium-doped electrode material with other electrode materials and combining the mixture with a current collector. "Other electrode materials" here means other materials that can be used as electrode materials, such as a binder and conductive additive, and the detailed description will be given below.
[00127] Also, a lithium doping can also be performed during electrode production, instead of using the active sulfur-based electrode material, which was doped with lithium. That is, an embodiment of the present invention provides a method of making an electrode, including: preparing a mixture of a sulfur-based active electrode material and a material containing a complex hydride containing lithium; apply the mixture to a current collector; and doping the active sulfur-based electrode material with lithium by heating the current collector applied with the mixture.
[00128] Still, an embodiment of the present invention provides an electrode that can be manufactured by the method mentioned above.
[00129] Also in the case of performing lithium doping during electrode production, the same effects as in the case of using the active sulfur-based electrode material, which was doped with lithium, in advance, can be obtained. In addition, lithium doping during electrode production, under heating, eg by hot pressing, is preferable since a good dense electrode is formed and production time can be reduced.
[00130] The details of the material mixing method, the heating temperature, the materials to be used in each case are as described above in "1. The manufacture of active electrode material, based on sulfur, doped with lithium" . Further, in the above-mentioned step of "preparing a mixture of a sulfur-based active electrode material and a material containing a complex hydride containing lithium", other electrode materials, as described below, may be included. , the "mixture" in the step of "applying the mix to a current collector" can also contain the other electrode materials. Hereinafter, the sulfur-based active electrode material, the material containing a complex hydride containing lithium, and the other electrode materials may also be collectively referred to as "electrode materials".
[00131] The current collector that can be used is not specifically limited, and materials conventionally used as current collectors for secondary lithium ion batteries, such as thin plates or meshes of aluminum, stainless steel, copper, nickel, or your leagues, can be used for this. Also, non-woven carbon cloths, woven carbon cloths, or similar, can also be used as a current collector.
[00132] Electrode materials may include a binder. As the binder, binders commonly used for lithium-ion secondary battery electrodes can be used. For example, polysiloxane, polyalkylene glycol, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene vinyl alcohol copolymer (EVOH), or the like can be used.
[00133] A thickener, such as carboxymethylcellulose (CMC), can also be used when needed.
[00134] Further, a conductive polymer having electron conductivity or a conductive polymer having ion conductivity can be used as the binder. Examples of the conductive polymer having electron conductivity include polyacetylene. In this case, the binder o Exercises a function also as conductive additive particles, and therefore there is no need to add a conductive additive.
[00135] The content of the binder is not specifically limited, but is preferably 0.1 to 10% by mass, more preferably 0.1 to 4% by mass, with reference to the sum of the masses of the active electrode material, based on sulfur, the lithium-containing complex hydride, the conductive additive, and the binder. When the amount of ligand is excessive, the ratio of active material in the electrode decreases, and the energy density decreases. Therefore, the minimum amount, which allows the formation of the electrode resistance to be sufficiently ensured, is preferable. It should be noted that the lithium-containing complex hydride and the sulfur-based electrode active material play a role as a binder to a not small extent, and therefore it is also possible to produce the electrode without the use of the binder. .
[00136] Electrode materials may include a conductive additive. The conductive additive is not specifically limited as long as it has a desired conductivity, but examples thereof may include a conductive additive made of a carbon material. Specific examples thereof include carbon black, acetylene black, Ketjen black, and carbon fibers. It should be noted that some sulfur-based active electrode materials, such as TiS2, have high electron conductivity, and in the case of using such a sulfur-based active electrode material, there is no need to use the conductive additive.
[00137] The content of the conductive additive varies in relation to the electron conductivity or the weight density between the active, sulfur-based electrode material and to be used, but the content of the conductive additive is often in the range of 1 to 200 parts by weight, more preferably in the range of 10 to 100 parts by weight, with respect to 100 parts by weight of the sulfur-based active electrode material.
[00138] The electrode can be produced by a commonly used method. For example, it can be manufactured by applying electrode materials to the current collector, and removing a solvent from the coating materials applied over the current collector.
[00139] Examples of the solvent to be used when applying the electrode materials onto the current collector include ether solvents such as tetrahydrofuran and diethyl ether, and non-aqueous aprotic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide.
[00140] The application method is not particularly limited, and a method that is commonly employed to produce electrodes can be used. Examples thereof include split die coating and scraper blade.
[00141] The method for removing the solvent in the coating materials applied on the current collector is not specifically limited, and the current collector coated with the coating materials can be dried, for example, under an atmosphere at 80 to 150° Ç. It should be noted that, in the case of carrying out lithium doping during electrode fabrication, the heating temperature during lithium doping and the solvent removal temperature are in the same temperature range, and therefore the required time to manufacture the electrode can be reduced by simultaneous lithium doping and solvent removal.
[00142] Then, the electrode thus produced can be pressed, for example, using a roller pressing device, when necessary. Linear pressure in roller pressing, for example, can be 10 to 50 kgf/cm.
[00143] It should be noted that the electrode can also be produced without the use of solvent by a method to form the mixed powders of the electrode materials by pressing, a method to vibrate the mixed powders after placing them on the current collector , and a method of filling porous portions of the current collector with the electrode materials, for example, by pushing them into the porous portions with a spatula or the like.
[00144] An electrode thickness is not specifically limited, as long as the function as an electrode is exerted, but it is preferably 1 µm to 1000 µm, more preferably 10 µm to 200 µm. 3. Li-ion secondary battery
[00145] The electrode thus produced can be used in a secondary lithium ion battery. That is, an embodiment of the present invention provides a secondary lithium ion battery including the aforementioned electrode is provided.
[00146] The secondary lithium ion battery can be manufactured by a known method. The electrode of the present invention can be used for either a positive electrode layer or a negative electrode layer, but it is preferable that the electrode be the electrode according to the present invention, and the other electrode be a lithium-free electrode. For example, in the case of using the electrode of the present invention as a positive electrode layer, a carbon material such as known graphite, a silicon material, or an alloy material such as Cu-Sn and Co-Sn, it is preferably used as a negative electrode active material.
[00147] Examples of liquid electrolytes, which can be used, include aprotic high dielectric constant solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, and Y-butyrolactone; and aprotic low viscosity solvents such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propyl methyl carbonate, dipropyl carbonate, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1 ,3-dioxolane, sulfolane, methyl sulfolane, acetonitrile, propionitrile, anisoles, acetic acid esters such as methyl acetate, or propionic acid esters. As the electrolyte, a solution in which a lithium salt such as lithium perchlorate, LiPF6, LiBF4, and LiCF3SO3 is dissolved at a concentration of about 0.5 mol/l to 1.7 mol/l can be used. In addition, a secondary lithium-ion battery can be assembled by a conventional method that uses other known battery components.
[00148] The present invention can also be used for solid state batteries. That is, according to an embodiment of the present invention, the aforementioned lithium ion secondary battery is a solid state battery. Hereinafter, the solid state battery will be described.
[00149] The solid state battery has a structure, in which a solid electrolyte layer is disposed between a positive electrode layer and a negative electrode layer. The solid state lithium ion secondary battery has a following problem: most solid electrolytes react with lithium on metal, and therefore the method of the present invention that does not use lithium on metal is particularly useful. In the case of using lithium-doped sulfur-based electrode active material as a positive electrode, a lithium-free active material such as an indium plate, a carbon electrode active material, and an active material Si electrode, can be used as a negative electrode, and therefore the above mentioned problem of solid electrolyte degradation and the problems described in the prior art can be solved.
[00150] Hereinafter, each element that constitutes the solid state battery will be described by way of an example, in the case of the use of the present invention in a positive electrode layer. However, there is no limitation regarding this aspect. (1) Positive electrode layer
[00151] The configuration and production method for the positive electrode layer are as described in the above mentioned section "2. Electrode". However, in the case where the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are integrally formed in "(4) Method for producing the solid state battery", which will be described below, it is also possible dispose the current collector after it is fully formed.
[00152] The thickness of the positive electrode layer is not specifically limited as long as the function as a positive electrode layer is exerted, but it is preferably from 1 μm to 1000 μm, more preferably from 10 μm to 200 μm. (2) Solid electrolyte layer
[00153] The solid electrolyte layer is a conductive layer of lithium ions, disposed between the positive electrode layer and the negative electrode layer, and is formed by using a solid electrolyte that conducts lithium ions. As a solid electrolyte, solid electrolytes of complex hydrides, oxide materials, sulfide materials, polymer materials, Li3N, or the like can be used. More specifically, examples thereof include oxide glasses such as Li3PO4-Li4SiO4 and Li3BO4-Li4SiO4; perovskite oxides such as La0.5Li0.5TiO3; NASICON oxides, such as Li1,3Al0,3Ti1,7 (PO4)3 and Li1,5Al0,5Ge1,5 (PO4)3; LISICON oxides, such as Li14Zn(GeO4)4, Li3PO4, and Li4SiO4; garnet oxides, such as Li7La3Zr2O12, Li5La3Ta2O12, and Li5La3Nb2O12; sulfide glass or sulfide glass ceramics, such as Li2S-P2S5, 80Li2S-20P2S5, 70Li2S-27P2S5-3P2O5, and Li2S-SiS2; thio-LISICON materials such as Li3.25Ge0.25P0.75S4, Li4SiS4, Li4GeS4, and Li3PS4; Li10GeP2S 12 having high lithium ion conductivity; materials, called LIPON, obtained by partial nitriding of Li3PO4 (examples of their composition include Li3,3PO3,8N0,22 and Li2,9PO3,3N0,46); and polymer materials such as polyethylene oxide, polyacrylonitrile, and poly(cyano ethoxy vinyl) (CNPVA) derivatives. Among them, a complex hydride solid electrolyte is preferable as it forms good interface with the above-mentioned positive electrode layer. As the complex hydride solid electrolyte, the same material as described above as the material containing a complex hydride containing lithium can be used.
[00154] The solid electrolyte layer may contain different materials than the above when necessary. For example, the solid electrolyte layer formed on a sheet using a binder can also be used.
[00155] The thickness of the solid electrolyte layer is preferably smaller. Specifically, the thickness is preferably in the range 0.05 µm to 1000 µm, more preferably in the range 0.1 µm to 200 µm. (3) Negative electrode layer
[00156] The negative electrode layer is a layer containing at least one active material of negative electrode, and may contain a solid electrolyte, a conductive additive, a binder, and the like, when necessary.
[00157] As the active material of the negative electrode, an active material of metal and an active material of carbon, for example, can be used. Examples of the aforementioned metal active material include In, Al, Si, and Sn, and alloys of these metals. However, examples of the above mentioned active carbon material include mesocarbon microgranules (MCMB), highly oriented pyrolytic graphite (HOPG), hard carbon, and soft carbon. In particular, the use of an active material having a lower electrode potential as a negative electrode improves the battery's energy density and improves the operating voltage, which is therefore preferable. Examples of such a negative electrode active material include an active material of carbon and Si.
[00158] The solid electrolyte to be used for the negative electrode layer is not specifically limited, as long as it has lithium ion conductivity and is stable with the active material of the negative electrode, but a complex hydride solid electrolyte, for example , can be used. The complex hydride solid electrolyte is comparatively soft, and therefore can form a good interface with the active material of the negative electrode, such as graphite, while being stable to reduction, which is therefore preferable. The negative electrode layer is preferably of the mass type containing both the active material from the negative electrode and the solid electrolyte. As the complex hydride solid electrolyte to be contained in the negative electrode layer, the same material as described above as the material containing a lithium-containing complex hydride can be used. In particular, it is preferable that the same complex hydride solid electrolyte is contained in the negative electrode layer and the solid electrolyte layer. This is because, if layers containing solid electrolytes with different compositions are in contact with each other, it is highly possible that the solid electrolytes will react with each other, or the constituent elements of the solid electrolytes will diffuse into the respective layers, which can result in a decrease in lithium ion conductivity.
[00159] The ratio between the active material of the negative electrode and the solid electrolyte is favorably higher within the range in which the shape of the negative electrode can be maintained, and the necessary ion conductivity can be ensured. For example, the ratio is preferably in the range of electrode negative active material: solid electrolyte = 9:1 to 1:9, more preferably 8:2 to 2:8, in a weight ratio.
[00160] As the conductive additive to be used for the negative electrode layer, the same conductive additive as in the positive electrode layer can be used. The percentage of the conductive additive with respect to the total mass of the materials forming the negative electrode layer is, for example, 0.1% by mass to 20% by mass, preferably 3% by mass to 15% by mass. The materials that form the negative electrode layer here include the active material of the negative electrode, and optionally include the solid electrolyte, the conductive additive, and the binder, for example.
[00161] As the binder to be used for the negative electrode layer, the commonly used binders for the negative electrode layer of lithium ion secondary batteries can be used. Examples thereof include polysiloxane, polyalkylene glycol, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), and polyacrylic acid. A thickener, such as carboxymethylcellulose (CMC), can also be used as needed.
[00162] The thickness of the negative electrode layer is not limited as long as the function as the negative electrode layer is exerted, but it is preferably 0.05 μm to 1000 μm, more preferably 0.1 μm to 200 μm. (4) Method to produce solid state battery
[00163] A solid state battery is manufactured by producing the above-mentioned layers and laminating the same, but the production method and laminating method for each layer are not specifically limited. Examples thereof include: a method of forming a film by forming a slurry by dispersing a solid electrolyte or electrode active material in a solvent and applying the slurry by scraping blade, spin coating, or the like, followed by lamination; a vapor-phase method, in which film formation and lamination are performed by vacuum evaporation, ion coating, sputtering, laser ablation, or the like; and a pressing method, in which powder is formed and laminated by hot pressing or cold pressing, without heating. In the case of using complex hydride solid electrolyte or sulphide solid electrolyte, which is comparatively soft, it is particularly preferable that the battery is produced by forming and laminating each layer by pressing. Examples of a pressing method include hot pressing, which is performed under heating, and cold pressing, which is performed without heating, either of which can be appropriately selected depending on the combination of solid electrolyte and material active. It is preferred that the layers are integrally formed by pressing at a pressure of preferably 50 to 800 MPa, more preferably 114 to 500 MPa. A layer having good adhesion and less void spaces between particles can be obtained by pressing with pressure in the aforementioned range, which is therefore preferable in view of the ion conductivity. Increasing the pressure by more than necessary is not practical, because it requires the use of a pressing apparatus and a forming vessel made of expensive materials, and its service life is reduced.
[00164] Doping with lithium in the active sulfur-based electrode material can also be performed after battery formation. In this case, the electrode is produced in the same way as in the case of performing lithium doping during electrode production, but heating is not performed at this time, and heating is performed after the battery is formed. The heating temperature is the same as in the case of doping the active sulfur-based electrode material with lithium in advance, or in the case of carrying out lithium doping during electrode production. Even in the case of carrying out lithium doping during battery production, the same effects described above as in the case of manufacturing the sulfur-based active electrode material, doped with lithium, in advance, can be obtained. EXAMPLES [Example A]
[00165] Hereinafter, the first aspect of the present invention will be described in detail by way of the Examples, but the contents of the present invention are not limited by these examples. <Example A1> (Preparation of complex hydride solid electrolyte)
[00166] Within a glove box under an argon atmosphere, LiBH4 (with a purity of 90%, manufactured by Sigma-Aldrich Co. LLC.) was weighed, and ground in an agate mortar, to obtain a solid electrolyte of complex hydride (LiBH4). (Preparation of positive electrode layer powder)
[00167] Powders were weighed into a glove box in a weight ratio of the positive electrode active material TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.): complex hydride solid electrolyte (LiBH4) = 2:3, and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00168] The complex hydride solid electrolyte powder, prepared above, was placed in a powder tabletting machine having a diameter of 8 mm and was formed by compression at a pressure of 143 MPa to a disk shape (forming of the complex hydride solid electrolyte layer). Without removing the formed product, the positive electrode layer powder, prepared above, was placed in a powder tabletting machine having a diameter of 8 mm to produce tablets and was integrally formed at a pressure of 285 MPa. Thus, a disk-shaped globule, in which the positive electrode layer (75 μm) and the complex hydride solid electrolyte layer (300 μm) were laminated together was obtained. On the surface of the globule, opposite the positive electrode layer, a lithium metal sheet with a thickness of 200 µm and a diameter of 8 mm (manufactured by Honjo Metal Co. Ltd.) was affixed to form a negative electrode layer of Li, and the resultant was placed in a battery test cell made of SUS304 to form a solid-state secondary battery. (Observation SEM)
[00169] The globule thus produced, composed of the positive electrode layer and the solid electrolyte layer of the solid state battery, was shaped into a thin film using a FIB apparatus (FB2200, manufactured by Hitachi High-Technologies Corporation), and the Cross section of the positive electrode layer was observed using an FE-SEM (SU9000, manufactured by Hitachi High-Technologies Corporation). The cross-sectional appearance is shown in Figure 2. In Figure 2, the portion that appears to be black is the complex hydride solid electrolyte (LiBH4), and the portion that appears to be white is the electrode positive active material (TiS2). It can be seen from Figure 2 that the complex hydride solid electrolyte (LiBH4) and the electrode positive active material (TiS2) crush each other, and a good interface is formed between them. As mentioned above, this is because both LiBH4 and TiS2 are soft. (Load-unload test)
[00170] The solid-state battery thus produced was subjected first to discharge, followed by charging and discharging, at a constant current under the conditions of a test temperature of 120°C, a cut-off voltage of 1.6 to 2.7 V, and a 0.1 C rating, using a potentiostat/galvanostat (VMP3, manufactured by Bio-Logic Science Instruments), to determine charge-discharge capability. It should be noted that a 3 minute break was provided after each loading and unloading. <Example A2>
[00171] Powders of a complex hydride solid electrolyte and a positive electrode layer were prepared in the same manner as in Example A1. (Solid state battery production)
[00172] The complex hydride solid electrolyte powder was placed in a powder tabletting machine having a diameter of 8 mm and was formed by compression at a pressure of 143 MPa to a disk shape. Without removing the formed product, the positive electrode layer powder was placed in it and was integrally shaped at a pressure of 285 MPa. Thus, a disk-shaped globule, in which the positive electrode layer (75 μm) and the complex hydride solid electrolyte layer (300 μm) were laminated together, was obtained. To this globule, an indium plate having a thickness of 250 µm and a diameter of 8 mm was affixed, and a lithium metal plate having a thickness of 200 µm and a diameter of 8 mm was further affixed thereon to form a negative electrode layer to form the Li-In alloy, and the resultant was placed in a battery test cell made of SUS304 to form a solid state secondary battery. (Load-unload test)
[00173] The solid state electrolyte battery thus produced was heated to 120°C, and was allowed to stand for about 2 hours, thus forming the Li-In alloy. This generated an electromotive force. Thereafter, it was subjected first to discharge, followed by charge and discharge, at a constant current under the conditions of a test temperature of 120°C, a cut-off voltage of 1.15 to 2.25 V (1.77 at 2.87 V with reference to Li), and a rate of 0.1 C, to determine the charge-discharge capacity. <Example A3> (Preparation of positive electrode active material)
[00174] Inside a glove box under an atmosphere of argon, TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.) and sulfur (S) (with a purity of 99.98% , manufactured by Sigma-Aldrich Co. LLC.) were weighed at a molar ratio of TiS2:S = 1:2 and mixed in an agate mortar. Next, the mixed starting materials were placed in a 45 ml pot made of SUJ-2, and spheres made of SUJ-2 (20 spheres with a diameter of 7 mm) were further placed into it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 400 rpm for 10 hours to obtain an electrode positive active material (TiS4 ). (Preparation of positive electrode layer powder)
The positive electrode layer materials were weighed into a glove box in a weight ratio of TiS4, prepared above: complex hydride solid electrolyte (LiBH4): carbon black (with a purity of 99.9% , manufactured by Sigma-Aldrich Co. LLC.) = 40:60:6 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00176] A solid state battery was produced in the same manner as in Example A1, except that the above-mentioned positive electrode layer powder was used. The charge-discharge test was carried out in the same manner as in Example A1 except that the test was carried out under the conditions of a cutoff voltage of 1.9 to 3.0 V and a rating of 0.05 C. <Example A4> (Preparation of complex hydride solid electrolyte)
[00177] Within a glove box under an argon atmosphere, LiBH4 (90% pure, manufactured by Sigma-Aldrich Co. LLC.) and LiI (99.999% pure, manufactured by Sigma-Aldrich Co.) . LLC.) were mixed in an agate mortar at a molar ratio of LiBH4:LiI = 3:1. Next, the mixed starting materials were placed in a 45 ml pot made of SUJ-2, and spheres made of SUJ-2 (20 spheres with a diameter of 7 mm) were further placed into it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 400 rpm for 5 hours to obtain a complex hydride solid electrolyte (3LiBH4 -LiI). (Preparation of positive electrode layer powder)
[00178] Powders were weighed into a glove box in a weight ratio of the positive electrode active material TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.): complex hydride solid electrolyte (3LiBH4-LiI) = 2:3 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00179] A solid state battery was produced in the same manner as in Example A1 except that the solid electrolyte powders and positive electrode layer, prepared as above, were used. (Load-unload test)
[00180] The solid state battery thus produced was heated to 120°C for 2 hours, thus allowing the solid electrolyte layer to adhere to the lithium metal sheet. Thereafter, the battery was subjected first to discharge, followed by charge and discharge, at a constant current under the conditions of a test temperature of 60°C, a cut-off voltage of 1.75 to 2.85 V, and a 0.1 C rate, using a potentiostat/galvanostat (VMP3, manufactured by Bio-Logic Science Instruments), to determine charge-discharge capacity. It should be noted that a 3 minute break was provided after each loading and unloading. <Example A5> (Load-unload test)
[00181] The charge-discharge test was carried out in the same manner as in Example A4, except that the solid state battery, after the test of Example A4, was used, and the test temperature was changed to 120°C. <Example A6> (Preparation of positive electrode active material)
Sulfur (S) (99.98% pure, manufactured by Sigma-Aldrich Co. LLC.), Ketjen Black (EC600JD, manufactured by Lion Corporation), and Maxsorb (R) (MSC30, manufactured by Kansai Coke and Chemicals Company, Limited) were placed in a 45 ml pot made of SUJ-2 in a weight ratio of S: Ketjen black: Maxsorb (R) = 50:25:25. Spheres made of SUJ-2 (20 spheres with a diameter of 7 mm) were further placed inside it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 400 rpm for 20 hours to obtain a composite positive electrode active material of carbon-S. (Preparation of positive electrode layer powder)
[00183] Powders were weighed into a glove box in a weight ratio of the S-carbon composite positive electrode active material prepared above: complex hydride solid electrolyte (LiBH4) = 1:1 and mixed in a mortar , to provide a positive electrode layer powder. (Solid state battery production)
[00184] A solid state battery was produced in the same manner as in Example A1 except that the positive electrode layer powder, prepared above, was used. (Load-unload test)
[00185] The solid-state battery thus produced was subjected first to discharge, followed by charge and discharge, at a constant current under the conditions of a test temperature of 120°C, a discharge cut-off capacity of 789 mAh /g (by sulfur) or a discharge cut-off voltage of 1.0 V, a charge cut-off voltage of 2.5 V, and a rate of 0.05 C, using a potentiostat/galvanostat (VMP3, manufactured by BioLogic Science Instruments) to determine load-discharge capability. <Example A7> (Preparation of positive electrode active material)
[00186] Sulfur (S) (with a purity of 99.98%, manufactured by Sigma-Aldrich Co. LLC. powder) and polyacrylonitrile (with a weight-average molecular weight of 150,000, manufactured by Sigma- Aldrich Co. LLC.) were mixed in an agate mortar at a weight ratio of S : polyacrylonitrile = 3:1.2 g of the milky mixture was placed on a boat made of quartz, and the boat was enclosed in an electric oven tubular (alumina tube: with an outer diameter of 42 mm, an inner diameter of 35 mm, and a length of 600 mm; and heater length: 250 mm). An argon gas was exhausted at a flow rate of 50 mL/minute, to sufficiently replace the internal air with the argon gas, the temperature of which was then raised to 400°C/hour to 450°C. The boat was kept as it was at 450°C for 8 hours, followed by natural cooling to obtain 0.7 g of black sulfur-polyacrylonitrile. As a result of CHNS analysis (FLASH EA1112, manufactured by Thermo Fisher Scientific Inc.), the sulfur polyacrylonitrile (Sulphur-PAN) obtained above had a composition of 41.6% by weight of carbon, 15.6% by weight of nitrogen, 40.8% by weight of sulfur, and less than 1% by weight of hydrogen. (Preparation of positive electrode layer powder)
[00187] Powders were weighed into a glove box in a weight ratio of sulfur-polyacrylonitrile, prepared above: complex hydride (LiBH4) solid electrolyte: carbon black (manufactured by Sigma-Aldrich Co. LLC.) = 16 :76:8 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00188] A solid state battery was produced in the same manner as in Example A1 except that the positive electrode layer powder, prepared above, was used. (Load-unload test)
[00189] The charge-discharge test was performed in the same manner as in Example A1, except that the solid state battery, produced above, was used, and the cut-off voltage was changed to 1.0 to 3.0 V. <Example A8> (Preparation of positive electrode active material)
[00190] Sulfur (S) (with a purity of 99.98%, manufactured by Sigma-Aldrich Co. LLC.) and nickel (Ni) (NIE10PB fine Ni powder, manufactured by Kojundo Chemical Laboratory Co. Ltd.) were placed in a 45 ml pot made of zirconia at a molar ratio of S : Ni = 1:1. Beads made of zirconia (62 g, with a diameter of 5 mm) were further placed inside it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 370 rpm for 24 hours to obtain NiS. (Preparation of positive electrode layer powder)
[00191] Powders were weighed into a glove box in a weight ratio of NiS, prepared above: complex hydride solid electrolyte (LiBH4): carbon black (manufactured by Sigma-Aldrich Co. LLC.) = 60:40 :6 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00192] A solid state battery was produced in the same manner as in Example A1 except that the positive electrode layer powder, prepared above, was used. (Load-unload test)
[00193] The solid-state battery thus produced was subjected first to discharge, followed by charging and discharging, at a constant current under the conditions of a test temperature of 120°C, a discharge cut-off voltage of 1, 0 V, a charge cut-off voltage of 3.0 V, and a rate of 0.1 C, using a potentiostat/galvanostat (VMP3, manufactured by Bio-Logic Science Instruments), to determine charge-discharge capability. <Example A9> (Preparation of positive electrode active material)
[00194] Sulfur (S) (with a purity of 99.98%, manufactured by Sigma-Aldrich Co. LLC.) and iron (Fe) (FEE12PB Fe fine powder, manufactured by Kojundo Chemical Laboratory Co. Ltd.) were placed in a 45 ml pot made of zirconia in a molar ratio of S : Fe = 2:1. Beads made of zirconia (62 g, with a diameter of 5 mm) were further placed inside it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 370 rpm for 24 hours to obtain FeS2. (Preparation of positive electrode layer powder)
[00195] Powders were weighed into a glove box in a weight ratio of FeS2, prepared above: complex hydride solid electrolyte (LiBH4): carbon black (manufactured by Sigma-Aldrich Co. LLC.) = 60:40 :6 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00196] A solid state battery was produced in the same manner as in Example A1 except that the positive electrode layer powder, prepared above, was used. (Load-unload test)
[00197] The charge-discharge test was performed on the solid-state battery thus produced, in the same manner as in Example A8. <Example A10> (Preparation of positive electrode layer powder)
[00198] Powders were weighed into a glove box in a weight ratio of MoS2 (with a purity of 99%, manufactured by Sigma-Aldrich Co. LLC.): complex hydride solid electrolyte (LiBH4) = 60:40 and mixed in a mortar to provide a positive electrode layer powder. (Solid state battery production)
[00199] A solid state battery was produced in the same manner as in Example A1 except that the positive electrode layer powder, prepared above, was used. (Load-unload test)
[00200] The charge-discharge test was performed on the solid-state battery thus produced, in the same manner as in Example A8, except that the charge-cut voltage was changed to 2.1 V. <Comparative example A1> (Preparation of positive electrode layer powder)
[00201] Powders were weighed into a glove box in a weight ratio of LiCoO2 positive electrode active material (CELLSEED C-5H, manufactured by NIPPON CHEMICAL INDUSTRIAL CO. LTD.): complex hydride solid electrolyte (LiBH4): carbon black (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.) = 40:60:6 and mixed in a mortar to provide a positive electrode layer powder.
[00202] A solid state battery was produced in the same manner as in Example A1, except that the above-mentioned positive electrode layer powder was used, and the cut-off voltage was changed to 3.2 to 4.2 V. The load-unload test was carried out in the same manner as in Example A1, except that the test was started with load. <Comparative example A2> (Preparation of positive electrode layer powder)
[00203] Powders were weighed into a glove box in a weight ratio of positive electrode active material LiFePO4 (SLFP-ES01): complex hydride solid electrolyte (LiBH4): carbon black (with a purity of 99.9 %, manufactured by Sigma-Aldrich Co. LLC.) = 40:60:6 and mixed in a mortar to provide a positive electrode layer powder.
[00204] A solid state battery was produced in the same manner as in Example A1, except that the above-mentioned positive electrode layer powder was used, and the cut-off voltage was changed to 2.5 to 3.8 V. The load-unload test was carried out in the same manner as in Example A1, except that the test was started with load.
[00205] The battery configurations of Examples A1 to A10 and Comparative Examples A1 and A2 described above are collectively shown in Table 1 below. [Table 1] Table 1: Bacteria configuration


[00206] The transitions in the discharge capacity of the batteries produced in Examples A1 and A6 to A10 are respectively shown in figure 3A to figure 3F (figure 3A: Example A1, figure 3B: Example A6, figure 3C: Example A7, Figure 3D: Example A8, Figure 3E: Example A9, and Figure 3F: Example A10). In addition, the charge-discharge curves of Example A1 in the 1st, 2nd, and 45th cycles are shown in Figure 4A. The charge-discharge curves from Example A6 at the 2nd, 3rd, and 45th cycles are shown in Figure 4B. The charge-discharge curves from Example A7 in the 2nd, 3rd, and 20th cycles are shown in figure 4C. In addition, the battery resistance, Coulomb efficiency, and discharge capacity of the batteries produced in Examples A1 to A10 in the 2nd cycle and the 20th cycle are shown in Table 2 below. It should be noted that the charge-discharge capacity was calculated by taking the charge-discharge capacity obtained for the battery tested as a value per gram of active electrode positive material. However, the charge-discharge capacity of Examples A6, A8, and A9 was calculated by taking it as a value per gram of sulfur. Battery resistance was calculated from the IR drop in one second after charging pause. Coulomb efficiency was calculated from the load capacity/discharge capacity. The phrase "No discharge capacity obtained" indicates that the discharge capacity per gram of active material was less than 5 mAh. [Table 2] Table 2: Test Results

[00207] For Comparative Examples A1 and A2, no discharge capacity was obtained, and the function as a battery was not exercised. It can be seen from the above-mentioned test results that, in solid-state batteries according to the embodiments of the present invention, the battery resistance is less likely to increase, and therefore the discharge capacity is less likely to decrease even if the charge/discharge cycles are repeated. Therefore, it can be said that solid state batteries according to the embodiments of the present invention are capable of stably operating over a long period of time. Furthermore, solid-state batteries in accordance with embodiments of the present invention stand out as having another advantage: that Coulomb efficiency is less likely to decrease, even after repeated charge/discharge cycles.
[00208] Still, as described above, according to the modalities of the present invention, the complex hydride with high conductivity of lithium ions can be used as a solid electrolyte without concern about the reduction of the positive electrode active material by the hydride complex. Furthermore, a good interface is formed between the positive electrode active material and the solid electrolyte, as a result of which the interfacial resistance is lowered, and the lithium ion conductivity of the battery, as a whole, can also be improved. [Example B]
Hereinafter, the second aspect of the present invention will be described in detail by way of the Examples, but the contents of the present invention are not limited by these examples. <Example B1> (1) The mixture of active electrode material, based on sulfur, with complex hydride containing lithium
[00210] Powders were weighed into a glove box in a weight ratio of sulfur-based electrode active material, TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.): Lithium-containing complex hydride (LiBH4, 90% purity, manufactured by Sigma-Aldrich Co. LLC.) = 2:3 and mixed in a mortar. (2) Thermal desorption mass spectroscopy
[00211] The powder obtained above was subjected to thermal desorption mass spectroscopy (detector: M-200QA, manufactured by CANON ANELVA CORPORATION) in an argon stream at a rate of temperature rise of 5°C/minute. The results are shown in figure 5. It can be seen from this that lithium doping starts at about 100°C. (3) Lithium doping
[00212] Lithium doping was performed by heating the obtained mixture in (1) to 120°C for 2 hours, under an argon atmosphere. (4) Measurement by X-ray diffraction
[00213] The powder obtained in (3) was subjected to measurement by X-ray diffraction (X'Pert Pro, manufactured by PANalytical B.V. CuKα: X = 1.5405 Â) at room temperature. The results are shown in Figure 6A. in figures 6A to 6C, the X-ray diffraction spectrum of the low temperature phase of LiBH4, the X-ray diffraction spectrum of TiS2, and the X-ray diffraction spectrum of the mixture obtained in (1) are also shown. It can be seen from Figure 6A that the TiS2 peaks are displaced by lithium doping.
[00214] Also, the truss constants of the geometric axes a and c of the powder obtained in (3), described above, were determined (space group P-3m1 (164)), using an analysis software program (HighScore Plus, manufactured by PANalytical BV). As a result, the a axis was 0.3436 nm, and the c axis was 0.6190 nm. These values were applied to a previously reported graph (Solid State Comm. 40 (1981) 245-248) indicating the relationship of lithium content with respect to the truss constants of the geometric a and c axes (figure 7). It was verified from the lithium content read in Figure 7 that the composition formula of the powder obtained in (3), described above, was Li0.80TiS2. It should be noted that the lithium content in the composition formula is shown as an average of a value derived from the axis truss constant a and a value derived from the axis truss constant c. <Example B2>
[00215] Lithium doping was performed in the same manner as in Example B1 except that Lithium doping time was changed by 20 hours. The results of the X-ray diffraction measurement are shown in Figure 6B. As a result of determining the lithium content in the same way as in Example B1, it was found that the composition formula of the obtained powder was Li0.95TiS2. <Example B3> (1) Preparation of material containing a complex hydride containing lithium
[00216] Within a glove box under an argon atmosphere, LiBH4 (90% pure, manufactured by Sigma-Aldrich Co. LLC.) and LiI (99.999% pure, manufactured by Sigma-Aldrich Co.) . LLC.) were mixed in an agate mortar at a molar ratio of LiBH4:LiI = 3:1. Next, the mixed starting materials were placed in a 45 ml pot made of SUJ-2, and spheres made of SUJ-2 (20 spheres with a diameter of 7 mm) were further placed into it. Then, the pot was completely sealed. This pot was mounted on a planetary ball mill (P7, manufactured by Fritsch Japan Co. Ltd.), and mechanical grinding was performed at a rotation rate of 400 rpm for 5 hours, to obtain a material containing a complex hydride containing lithium (3LiBH4-LiI). (2) Lithium doping and X-ray diffraction measurement
[00217] Mixing and doping with lithium was carried out in the same manner as in Example B1, except that 3LiBH4-LiI was used in place of LiBH4. The X-ray diffraction measurement was also carried out in the same manner as in Example B1, and the results are shown in Figure 6C. In addition, the truss constants of the a and c axes were also determined in the same manner as in Example B1 to obtain the lithium content using Figure 7, as a result of which the compositional formula was found to be Li0.66TiS2. <Example B4>
[00218] Lithium doping was carried out in the same manner as in Example B1, except that the raw material ratio was changed to a TiS2 weight ratio (with a purity of 99.9%, manufactured by Sigma-Aldrich Co . LLC.): lithium-containing complex hydride (LiBH4, 90% purity, manufactured by Sigma-Aldrich Co. LLC.) = 3:1. As a result of determining the lithium content in the same manner as in Example B1, it was found that the composition formula of the obtained powder was Li0.05TiS2. <Example B5>
[00219] Lithium doping was performed in the same manner as in Example B4, except that Lithium doping time was changed by 20 hours. As a result of determining the lithium content in the same way as in Example B1, it was found that the composition formula of the obtained powder was Li0.51TiS2. <Example B6>
[00220] Lithium doping was carried out in the same manner as in Example B1, except that the raw material ratio was changed to a weight ratio of TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co . LLC.): lithium-containing complex hydride (LiBH4, 90% purity, manufactured by Sigma-Aldrich Co. LLC.) = 4:1. As a result of determining the lithium content in the same way as in Example B1, it was found that the composition formula of the obtained powder was Li0.35TiS2. Despite the fact that the LiBH4 ratio was lower in Example B6 than in Example B4, the amount of lithium doping was higher in Example B6 than in Example B4 in the result. Since the production batches of LiBH4 used for the reaction were different, a slight difference in LiBH4 particle size between Example B4 and Example B6 could possibly have affected the results. That is, it is inferred that a difference in particle size of LiBH4 can cause a difference in reaction rate. <Example B7>
[00221] Lithium doping was carried out in the same manner as in Example B2, except that the raw material ratio was changed to a weight ratio of TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co LLC.): lithium-containing complex hydride (LiBH4, 90% purity, manufactured by Sigma-Aldrich Co. LLC.) = 5:1. As a result of determining the lithium content in the same way as in Example B1, it was found that the composition formula of the obtained powder was Li0.02TiS2. <Example B8> (1) Solid state battery production before lithium doping
The powders were weighed into a glove box in a weight ratio of sulfur-based electrode active material TiS2 (with a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.) :complex hydride containing lithium (LiBH4) = 2:3 and mixed in a mortar. The mixture was placed into a powder tabletting machine having a diameter of 10 mm and was formed by compression at a pressure of 28 MPa to a disk shape (positive electrode layer formation). Without removing the formed product, the complex hydride solid electrolyte powder (LiBH4) was subsequently placed in the tabletting machine and was formed by compression again at a pressure of 28 MPa (formation of solid electrolyte layer). To the surface of the solid electrolyte layer, opposite the positive electrode layer, an indium plate with a thickness of 100 µm and a diameter of 8 mm was affixed, and was integrally formed at a pressure of 285 MPa. Thus, a disc-shaped globule, in which 75 μm from the positive electrode layer, 500 μm from the complex hydride solid electrolyte layer, and 70 μm from the negative electrode layer (in the indium plate was spread to a 9 mm diameter ) were sequentially laminated together, was obtained. The globule was placed in a battery test cell, made of SUS304, to produce a solid-state battery prior to lithium doping (with neither the positive electrode nor the negative electrode retaining the amount of lithium needed for charging and discharging). (2) Lithium doping
[00223] The above-mentioned solid state battery, prior to lithium doping, was subjected to lithium doping by heating at 120°C for 2 hours. The active sulfur-based electrode material was doped with lithium by this operation, so charging and discharging were allowed. (3) Load-unload test
[00224] The charge-discharge test for the solid-state battery, produced as above, was started with charging at a constant current, a measurement temperature of 120°C, a cut-off voltage of 1.15 to 2.25 V, and a rate of 0.1 C, using a potentiostat/galvanostat (VMP3, manufactured by Bio-Logic Science Instruments). The transition in discharge capacity to the 20° cycle is shown in figure 8, and the load-discharge curves in the 1st, 2nd and 20th cycles are shown in figure 9. It should be noted that the discharge capacity was expressed by taking the discharge capacity obtained in the tested battery as a value per gram of active electrode material, based on sulfur. A sulfur-based active electrode material composition after lithium doping, as determined from the Coulomb force during discharge in the 1st cycle, was Li0.84TiS2 (where the theoretical capacity per gram of TiS2 was assumed be 239 mAh).
[00225] For examples B1 to B7, lithium doping conditions; the truss constants of geometric axes a and c, determined from X-ray diffraction; the lithium insertion quantities determined, respectively, from the lattice constants of the geometric axes a and c using Figure 7; and the average of the aforementioned lithium insertion amounts, are collectively shown in Table 3 below.
In addition, the truss constants of the lithium-free TiS2 geometry a and c axes are shown as Reference B1, and the truss constants of the lithium-containing LiTiS2 geometry a and c axes from the beginning are shown as the Reference B2. [Table 3] Table 3: Variation of the truss constants of the geometric axes and the amount of Li inserted in lithium doping

[00227] It can be seen from Table 3 above that the active sulfur-based electrode materials of the Examples were doped with lithium in an amount sufficient for the electrode reaction. LIST OF REFERENCE SIGNALS 1: Positive electrode layer, 2: Solid electrolyte layer, 3: Negative electrode layer, 10: Solid state battery.

权利要求:
Claims (4)
[0001]
1. Solid state battery (10), characterized in that it comprises: a positive electrode layer (1); a negative electrode layer (3); and a solid electrolyte layer, which conducts lithium ions (2), disposed between the positive electrode layer (1) and the negative electrode layer (3), wherein the positive electrode layer (1) contains an active material of positive electrode and a complex hydride solid electrolyte, the positive electrode active material is a sulfur-based electrode active material selected from the group consisting of a sulfur polyacrylonitrile, carbon-S and NiS composite, and the solid electrolyte layer (2) contains a complex hydride solid electrolyte.
[0002]
2. Solid state battery (10) according to claim 1, characterized in that the complex hydride solid electrolyte is LiBH4 or a combination of LiBH4 and an alkali metal compound, represented by formula (1) below: MX ( 1), wherein M represents an alkali metal atom selected from the group consisting of a lithium atom, a rubidium atom, and a cesium atom, and X represents a halogen atom or an NH2 group.
[0003]
3. Solid state battery (10) according to claim 2, characterized in that the alkali metal compound is selected from the group consisting of a rubidium halide, a lithium halide, a cesium halide, and a lithium amide.
[0004]
4. Solid state battery (10) according to any one of claims 1 to 3, characterized in that the positive electrode layer (1) is formed by pressing.

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法律状态:
2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-04-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2013-181579|2013-09-02|

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JP2013181579|2013-09-02|

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JP2013-191048|2013-09-13|

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JP2013191048|2013-09-13|

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JP2014067825|2014-03-28|

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JP2014-067826|2014-03-28|

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JP2014-067825|2014-03-28|

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JP2014067826|2014-03-28|

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PCT/JP2014/072439|WO2015030053A1|2013-09-02|2014-08-27|Solid-state battery and method for manufacturing electrode active material|

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