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    • 专利摘要:
    POSITIVE ELECTRODE COMPOSITION FOR SECONDARY NON-AQUEOUS ELECTROLYTE BATTERY. It is a positive electrode composition for a secondary battery of non-aqueous electrolyte comprising: a complex lithium transition metal oxide represented by a general formula LiaNia-x-yCoxMlyWzM2w02 (1.0, Lesser equal) to (Lesser equal ) 1.5, 0 (less than equal) x (less than equal) 0.5, 0 (less than equal) y (less than equal) 0.5, 0.002 (less than equal) z (less than equal) 0.03, 0 (less than equal) w (less than equal) 0.02, 0 (less than equal) x + y (less than equal) 0.7, M1 represents at least one element selected from the group consisting of Mn and Al, M2 represents at least one element selected from the group consisting of Zr, Ti, Mg, Ta, Nb, Mo); and a boron compound comprising at least the boron element and the oxygen element.
    公开号:BR102013009295B1
    申请号:R102013009295-9
    申请日:2013-04-16
    公开日:2020-06-30
    发明作者:Kousuke SHIMOKITA；Kenta Kawai；Kiyofumi INOUCHI
    申请人:Nichia Corporation；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a positive electrode composition for a secondary non-aqueous electrolyte battery such as a secondary lithium ion battery. In particular, the present invention relates to a positive electrode composition that can enhance a battery's output power characteristics, and can also enhance a battery's cyclization characteristics and viscosity stability of a positive electrode slurry. BACKGROUND OF THE TECHNIQUE
    [0002] [0002] With the progress of the dissemination and miniaturization of mobile devices such as VTR, mobile phone and PC type computer, a secondary non-aqueous electrolyte battery such as a secondary lithium ion battery has recently been used as a power source for the same. In addition, in order to overcome recent environmental problems, the secondary non-aqueous electrolyte battery has also attracted interest as a battery powered by an electric vehicle or the like.
    [0003] [0003] It was commonly used as a positive electrode active material for a secondary lithium ion battery, LiCoO 2 (lithium cobalt oxide) which can constitute a secondary class 4 V battery. When LiCoO 2 is used as the positive electrode active material, it is put to practical use in a discharge capacity of about 160 mA / g.
    [0004] [0004] Cobalt as a raw material for LiCoO 2 is a scarce resource, which leads to high costs, and cobalt is distributed unevenly, which can cause concern regarding the supply of a raw material.
    [0005] [0005] In response to these circumstances, the lithium transition metal complex oxide which has a layered structure, such as lithium oxide nickel cobalt manganese obtained by replacing Co in LiCoO 2 with one or more elements such as Ni and Mn was developed. In general, in relation to the lithium transition metal complex oxide which has a layered structure, its crystal structure becomes unstable when it has a higher nickel ratio, and thus, it tends to cause the precipitation of compound of lithium in a positive electrode slurry by making a positive electrode. In addition, when a cobalt ratio in the lithium transition metal complex oxide is decreased, the output power characteristics tend to be reduced.
    [0006] [0006] As an example, there are metal selection techniques (s) such as tungsten as a replacement element depending on the various purposes.
    [0007] [0007] Patent document 1 describes a technique for reducing a resistance of a positive electrode active material alone by adding one or more elements such as molybdenum and tungsten in lithium cobalt oxide and lithium nickel oxide.
    [0008] [0008] Patent document 2 describes lithium transition metal complex oxide in which up to about 20% nickel in lithium nickel oxide is replaced with manganese, cobalt and the like, and up to about 10% nickel is additionally replaced with tantalum, niobium, tungsten, molybdenum and the like. Patent document 2 describes that lithium nickel oxide has a specific composition replaced with at least two elements, thus presenting improved thermal stability under load, and enhanced safety through an internal short circuit due to its lower electrical conductivity in the form of powders. .
    [0009] [0009] Patent document 3 describes a technique for increasing an electrode plate density, as well as improved thermal stability and charging characteristics by the lithium transition metal complex oxide which has molybdenum, tungsten, boron and the like in it. surface. As a medium composition of the specific lithium transition metal oxide complex, lithium nickel cobalt manganese oxide comprising molybdenum is described.
    [0010] [00010] Patent document 4 describes a technique for improving the crystallinity of the lithium transition metal complex oxide by preventing sintering in a calcination stage through the involvement of boron and the like (additive element 1) and molybdenum, tungsten , niobium, tantalum and the like (additive element 2) in it, which leads to satisfying all of a cost, high voltage resistance, high safety rate characteristics and output power characteristics, and preventing a decrease in mass density and an increase in the specific surface area of the powders. Specifically, lithium nickel oxide cobalt manganese which comprises two additive elements mentioned above is described.
    [0011] [00011] On the other hand, there are techniques for mixing the boron compound such as boric acid with lithium transition metal complex oxide, or lithium transition metal complex oxide techniques that have boron compound on its surface.
    [0012] [00012] Patent document 5 describes a technique for suppressing a reaction of lithium manganese oxide that has a spinel structure with hydrohalic acid and enhancing cyclization characteristics due to a positive electrode that uses lithium manganese oxide which comprises a compound of boron soluble in an electrolyte, such as boron oxide, ortho-boric acid, metabolic acid and tetraboric acid.
    [0013] [00013] Patent document 6 describes a technique for increasing a discharge potential and improving life-long characteristics by forming on a complex lithium transition metal oxide surface, in which the treatment layer of The surface has excellent ion conductivity, the surface treatment layer comprising hydroxide, oxyhydroxide and the like of a coating element such as boron. As a specific coating method, it describes that the coating element dissolved in a solvent is precipitated on the surface of the lithium transition metal complex oxide followed by removal of the solvent.
    [0014] [00014] Patent document 7 describes a technique for preventing gelation of an electrode paste by involving boric acid and the like, such as inorganic acid in an electrode using lithium transition metal complex oxide and the like. As a specific example of the lithium transition metal complex oxide, lithium nickel oxide is described.
    [0015] [00015] Patent document 8 describes a technique for providing increased capacity of a secondary battery and improved charge-discharge efficiency of the secondary battery by trapping the borate beetle and the like, such as ammonium borate and lithium borate on a surface of the lithium transition metal complex oxide particles that comprise nickel or cobalt indispensably, and carrying out the treatment by heating under an oxidizing atmosphere. As a specific example of the lithium transition metal complex oxide, lithium nickel oxide in which a portion of nickel is replaced with cobalt and aluminum is described.
    [0016] [00016] In any of the patent documents 5 to 8 described above, a positive electrode and lithium transition metal oxide complex comprising tungsten is not described. TECHNICAL BACKGROUND DOCUMENT Patent Document
    [0017] [00017] Patent Document 1: JP 2000-113,884 A
    [0018] [00018] Patent Document 2: JP 2000-315,502 A
    [0019] [00019] Patent Document 3: JP 2005-251,716 A
    [0020] [00020] Patent Document 4: JP 2011 -108,554 A
    [0021] [00021] Patent Document 5: JP 2001-257,003 A
    [0022] [00022] Patent Document 6: JP 2002-124.262 A
    [0023] [00023] Patent Document 7: JP 10-079,244 A
    [0024] [00024] Patent Document 8: JP 2009-146,739 A SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [0025] [00025] As described in Patent Document 4, the output power characteristics of a battery can be enhanced by adding tungsten within the complex lithium transition metal oxide. However, the present inventors have found that the cyclization characteristics tend to degrade when the complex lithium transition metal oxide which has a layered structure and which comprises tungsten without its composition is used as a positive electrode active material.
    [0026] [00026] Under these circumstances, the present invention was made. An objective of the present invention is to improve output power characteristics and cyclization characteristics when the complex lithium transition metal oxide which is low in cobalt or does not comprise cobalt, and which comprises nickel and tungsten is used in a composition of positive electrode. In addition, an objective of the present invention is to provide a method for producing a positive electrode composition that achieves such an objective. SOLUTION TO THE PROBLEM
    [0027] [00027] In order to achieve the above objectives, the present inventors studied intensively, and thus, the present invention was completed. The present inventors have found that the output power characteristics and cycling characteristics can be improved in a positive electrode composition that uses lithium transition metal complex oxide that is low in cobalt or does not comprise cobalt, through the use of a positive electrode composition comprising a complex lithium transition metal oxide that essentially comprises nickel and tungsten and a particular boron compound. In addition, the present inventors have found that an increase in the viscosity of the positive electrode slurry is suppressed through the use of such a positive electrode composition.
    [0028] [00028] A positive electrode composition for a non-aqueous electrolyte secondary battery of the present invention comprises: a complex lithium transition metal oxide represented by a general formula Li a Ni 1-xy Co x M 1 y W z M 2 w O 2 (1.0≤a≤1.5, 0≤x≤0.5 , 0≤y≤0.5, 0.002≤z≤0.03, 0≤w≤0.02, 0≤x + y≤0.7, where M 1 represents at least one selected from the group consisting of Mn and Al, M 2 represents at least one selected from the group consisting of Zr, Ti, Mg, Ta, Nb and Mo); and a boron compound that comprises at least boron element and oxygen element.
    [0029] [00029] A method for producing a positive electrode composition for a non-aqueous electrolyte secondary battery of the present invention is a method for producing a positive electrode composition for a non-aqueous electrolyte secondary battery comprising a complex lithium transition metal oxide represented by a general formula Li a Ni 1-xy Co x M 1 y W z M 2 w O 2 (1.0≤a≤1.5, 0≤x≤0.5, 0≤y≤0.5, 0.002≤z≤0.03, 0≤w≤0.02, 0≤x + y≤0.7, where M 1 represents at least one selected from the group consisting of Mn and Al, M 2 represents at least one selected from the group consisting of Zr, Ti, Mg, Ta, Nb and Mo), and a boron compound comprising at least boron element and oxygen element, the method comprising at least: synthesize the lithium transition metal complex oxide; and mixing the lithium transition metal complex oxide obtained by synthesis and a raw material compound of the boron compound to obtain a mixture. ADVANTAGE EFFECTS OF THE INVENTION
    [0030] [00030] Since the positive electrode composition of the present invention has the features mentioned above, the output power characteristics and the cycling characteristics are improved. In addition, an increase in the viscosity of the positive electrode slurry can be suppressed by using the positive electrode composition of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
    [0031] [00031] Figure 1 shows a relationship between a boron compound content in positive electrode compositions and CC-IR (internal direct current resistances) at -25 ° C.
    [0032] [00032] Figure 2 shows a time-dependent change in the viscosity of positive electrode pastes prepared using positive electrode compositions that comprise a different amount of boron compound.
    [0033] [00033] Figure 3 shows a time-dependent change in viscosity of positive electrode pastes prepared using positive electrode compositions that comprise a different amount of boron compound.
    [0034] [00034] Figure 4 shows a relationship between a values in lithium transition metal complex oxide composition formulas and CC-IR at -25 ° C.
    [0035] [00035] Figure 5 shows a correlation between the levels of boron compound in positive electrode compositions and cycling characteristics. DESCRIPTION OF MODALITIES
    [0036] [00036] Hereinafter, a positive electrode composition of the present invention will be described in detail by reference to the modalities and Examples. However, the present invention is not limited to these modalities and Examples.
    [0037] [00037] A positive electrode composition of the present invention comprises a complex lithium transition metal oxide as described below and a boron compound comprising at least boron element and oxygen element. Complex lithium transition metal oxide
    [0038] [00038] The lithium transition metal complex oxide in the positive electrode composition of the present invention is represented by a general formula Li a Ni 1-xy Co x M 1 y W z M 2 w O 2 (1.0≤a ≤1.5, 0≤x≤0.5, 0≤y≤0.5, 0.002≤z≤0.03, 0≤w≤0.02, 0≤x + y≤0.7, where M 1 represents at least one selected from the group consisting of Mn and Al, M 2 represents at least one selected from the group consisting of Zr, Ti, Mg, Ta, Nb and Mo).
    [0039] [00039] The lithium transition metal complex oxide is essentially made up of nickel and additionally comprises tungsten. The lithium transition metal complex oxide in the positive electrode composition of the present invention can have a layered structure. In addition, a portion of nickel sites of the lithium transition metal complex oxide can be replaced with cobalt, manganese and / or aluminum. Alternatively, the lithium transition metal complex oxide may additionally comprise one or more elements other than tungsten.
    [0040] [00040] By replacing a portion of nickel locations with cobalt, output power characteristics can be improved. The value of x is from 0 to 0.5. When the value of x is in the range mentioned above, the cobalt ratio in the lithium transition metal complex oxide can be reduced or zero, and thus, the production cost can be reduced. Taking into account the balance with the various characteristics, the value of x is preferably from 0.05 to 0.35. In the lithium transition metal complex oxide composition formula, a, w, x, y and z signify a ratio of each element when the number of nickel sites is considered to be 1.
    [0041] [00041] By replacing a portion of nickel sites with at least one element (M 1 ) selected from the group consisting of manganese and aluminum, the stability of the crystal structure of the complex lithium transition metal oxide obtained can be improved. The y value is from 0 to 0.5. When the value of y is within the range mentioned above, excellent output power characteristics and load and discharge characteristics can be obtained. In addition, the value of x + y (total substitution quantity for nickel sites, that is, the sum of the substitution quantity with cobalt and that with the element M 1 ) is from 0 to 0.7. When the value of x + y is within the range mentioned above, excellent loading and unloading characteristics can be obtained. Taking into account the balance with the various characteristics, the value of x + y is preferably 0.2 to 0.6.
    [0042] [00042] The lithium transition metal complex oxide in the positive electrode composition of the present invention comprises tungsten. Since the lithium transition metal complex oxide comprises tungsten, the output power characteristics of the non-aqueous electrolyte secondary battery can be improved. The z value is from 0.002 to 0.03. When the z value is 0.002 or greater, excellent output power characteristics can be obtained. When the z value is 0.03 or less, excellent cycling characteristics can be obtained and, in addition, an effect on the improvement of the characteristics due to the other element (s) contained in the complex oxide of lithium transition metal are not prevented. The preferred range of the z value is 0.003 through 0.007.
    [0043] [00043] The lithium transition metal complex oxide may additionally comprise at least one element (M 2 ) selected from the group consisting of zirconium, titanium, magnesium, tantalum, niobium and molybdenum. The value of w is from 0 to 0.02. When the value of w is within the aforementioned range, several purposes can be achieved without impeding the effects on improving the characteristics due to the other element (s) contained in the complex transition metal oxide. lithium. For example, zirconium is suitable to improve storage characteristics, and titanium and magnesium are suitable to further improve cycling characteristics.
    [0044] [00044] In the lithium transition metal complex oxide of the present invention, the value of a (the ratio of the lithium element when the amount of nickel sites is considered to be 1) is 1.0 to 1.5. When the value of a is 1.0 or greater, excellent characteristics of output power can be obtained. When the value of a is 1.05 or greater, the effect on improving the output power characteristics is more significant. When the value of a is 1.5 or less, the lithium transition metal complex oxide can be readily synthesized. In addition, the positive electrode composition obtained can be readily manipulated since the progression of sintering in the synthesis process can be suppressed. Taking into account a balance of characteristics, a facility for synthesis and the like, the value of a is preferably from 1.05 to 1.25. Boron Compound
    [0045] [00045] The boron compound in the positive electrode composition of the present invention comprises at least boron element and oxygen element. In general, when a complex lithium transition metal oxide comprising tungsten is used as a positive electrode composition, tungsten tends to elute in an electrolyte in association with the charge and discharge reaction, and a portion of the eluted tungsten tends to elute. to be precipitated on a negative electrode, which is considered to cause the degradation of the cyclization characteristics. In contrast, in the positive electrode composition of the present invention, the aforementioned boron compound preferably reacts with tungsten which can be eluted from the lithium transition metal complex oxide. Therefore, tungsten precipitation on the negative electrode is suppressed, and as a result, degradation of the cyclization characteristic due to the tungsten elution can be suppressed. The positive electrode composition of the present invention can improve the output power characteristics as it comprises lithium transition metal complex oxide which comprises tungsten, and it can suppress the degradation of the cyclization characteristics due to the elution of the tungsten seen that it comprises the boron compound which comprises at least boron element and oxygen element.
    [0046] [00046] On the other hand, the increase in viscosity of the positive electrode slurry is considered to be caused by a lithium elution of a complex lithium transition metal oxide in a positive electrode slurry. Through the reaction of lithium eluted from the lithium transition metal complex oxide with a binder contained in the positive electrode slurry, gelation of the positive electrode slurry occurs, and as a result, the viscosity of the positive electrode slurry is increased. In contrast, in the positive electrode composition of the present invention, the aforementioned boron compound preferably reacts with lithium which can be eluted from the lithium transition metal complex oxide. Therefore, the reaction of lithium with the binder in the positive electrode slurry is suppressed, and as a result, the increase in viscosity of the positive electrode slurry can be suppressed. The present inventors have found that the effects mentioned above can be achieved when using the boron compound which comprises at least boron element and oxygen element.
    [0047] [00047] The aforementioned boron compound can be obtained at least by mixing the lithium transition metal complex oxide with a raw material compound of the boron compound. The raw material compound of the boron compound is described later. By obtaining the boron compound in this way, the reaction of tungsten and / or lithium that can be eluted from the lithium transition metal complex oxide with the boron compound readily occurs in addition, and as a result, the power characteristics of output can be further improved, and the increase in viscosity of the positive electrode slurry can be further suppressed.
    [0048] [00048] At least the portion of the boron compound preferably exists on or adjacent to the surface of the lithium transition metal complex oxide particles. In this case, it is considered that the reaction of tungsten and / or lithium that can be eluted from the lithium transition metal complex oxide with the boron compound readily occurs in addition, and as a result, the power characteristics of output can be further improved, and the increase in viscosity of the positive electrode slurry can be further suppressed. Furthermore, when at least a portion of the boron compound is physically bound to the lithium transition metal complex oxide by, for example, van der Waals forces, electrostatic force and the like, it is assumed that the elution of the tungsten itself and / or lithium is less likely to occur. At least a portion of the boron compound is preferably attached to the surface of the lithium transition metal complex oxide particles. Alternatively, at least a portion of the boron compound preferably covers at least partially the surface of the lithium transition metal complex oxide particles.
    [0049] [00049] Furthermore, it is preferred that at least a portion of the boron compound is chemically linked to one or more elements that make up the lithium transition metal complex oxide. This chemical bond is formed by reacting at least a portion of the raw material compound of the boron compound with one or more elements (such as lithium) that constitutes the lithium transition metal complex oxide. Although the detail of this chemical bond is unknown, it is assumed that, for example, at least a portion of the boron compound raw material will react with a portion of elements such as lithium in the complex metal oxide transition from lithium to form the complex oxide. When at least a portion of the boron compound forms the chemical bond with the elements that make up the lithium transition metal complex oxide, it is assumed that the elution of tungsten and / or lithium itself is less likely to occur.
    [0050] [00050] In addition, when the aforementioned physical and / or chemical bond is formed between the boron compound and the lithium transition metal complex oxide, the lithium ion conductivity of the entire positive electrode composition is considered to become become larger, and as a result, the output power characteristics can be further improved.
    [0051] [00051] Furthermore, in the positive electrode composition of the present invention, the boron compound is preferably obtained by mixing the lithium transition metal complex oxide with the raw material compound of the boron compound followed by calcination. Through calcination, the formation of the physical and / or chemical bond between the boron compound and the lithium transition metal complex oxide can be facilitated. In addition, through calcination, moisture and / or hydration water that may be present in the boron compound can be removed, and as a result, the degradation of characteristics due to moisture and / or hydration water can be suppressed. The calcination temperature in the calcination is preferably 450 ° C or less. The calcination conditions such as the calcination temperature are described later.
    [0052] [00052] In the positive electrode composition of the present invention, a ratio (molar percentage) of the boron element to the lithium transition metal complex oxide is preferably 2.0 mol% or less. When the boron element ratio is 2.0 mol% or less, excellent loading and unloading characteristics can be obtained. The boron element ratio is more preferably from 0.5 mol% to 1.5 mol%. When the boron element ratio is 0.5 mol% or May, the effect on suppression in the elution of tungsten and lithium is improved. In addition, when the boron element ratio is 1.5 mol% or less, the loading and unloading characteristics can be further improved. In this specification, the ratio of the boron element to the lithium transition metal complex oxide in the positive electrode composition is also referred to as “boron content”.
    [0053] [00053] The raw material compound of the aforementioned boron compound comprises at least boron element and oxygen element. The raw material compound of the boron compound is preferably at least one selected from the group consisting of boron oxide, boron oxy acids and boron oxy acid salts since the boron compounds finally obtained in the form suitable for the purposes of the present invention. Boron oxy acid and boron oxy acid salts include orthoboric acid, metabolic acid, polyboric acids such as diboric acid and triboric acid, and salts of such oxyacids. When the boron oxy acid salts are used as the raw material compound of the boron compound, lithium salt and / or ammonium salt of boron oxy acids is preferably used. Through the use of lithium salt and / or ammonium from boron oxyacids, the effects of the present invention can be achieved without impairing other battery properties. Specific examples of the boron compound raw material compound include lithium tetraborate (Li 2 B 4 O 7 ), ammonium pentaborate (NH 4 B 5 O 8 ) and the like. These boron compound feedstock compounds may contain hydration water. The raw material compound of the boron compound is preferably boron oxy acid in relation to its handling and the form of the boron compound finally obtained. Ortho-boric acid (hereinafter, it can be called merely "boric acid") is particularly preferred.
    [0054] [00054] In the positive electrode composition, according to the present invention, it is considered that the positive electrode composition does not change its composition before and after the mixing and calcination described above. In the positive electrode composition according to the present invention, it is assumed that at least a portion of the boron compound has the same composition as that of the raw material compound of the boron compound. In addition, at least a portion of the boron compound can be a compound obtained by chemical reaction of the raw material compound of the boron compound with one or more elements that make up the lithium transition metal complex oxide. The boron compound obtained through such a chemical reaction is considered to form a chemical bond to one or more elements that make up the lithium transition metal complex oxide. The presence of this chemical bond can be identified by, for example, X-ray excited photoelectron spectroscopy (XPS). Production of positive electrode composition
    [0055] [00055] In the following, a method for producing a positive electrode composition of the present invention is described. The method for producing a positive electrode composition comprises at least synthesizing a lithium transition metal complex oxide, and mixing the lithium transition metal complex oxide obtained through synthesis and a raw material compound of the boron compound. to get a mixture. Preferably, the method for producing the positive electrode composition further comprises calcining the mixture obtained by means of the mixture. Synthesis of lithium transition metal complex oxide
    [0056] [00056] The lithium transition metal complex oxide can be synthesized appropriately through the use of known methods. The lithium transition metal complex oxide can be obtained, for example, by mixing the respective raw material compounds, which are degraded into oxides at a higher temperature, to be a stoichiometric proportion of the composition of the complex metal oxide of transition of bleached lithium, and calcination of the mixed raw materials obtained at about 700 ° C to 1,100 ° C. Alternatively, the lithium transition metal complex oxide can be obtained by dissolving the respective raw material compounds, which are soluble in the solvent, to be a stoichiometric proportion of the transition metal complex oxide composition in a solvent. of bleached lithium, the temperature and / or pH is adjusted and / or a complexing agent is injected to generate a precipitation of the mixed raw materials, and calcination of the mixed raw materials at about 700 ° C to 1,100 ° C. Mixture
    [0057] [00057] Then, the lithium transition metal complex oxide obtained through synthesis is mixed with the raw material compound of the boron compound. This is sufficient to perform the mixing by using the existing and similar mixer, to the extent that both are mixed uniformly. The mixing is preferably carried out to the extent that a mechanochemical reaction occurs. The boron compound can be obtained in a more preferential way through the mechanochemical reaction of the lithium transition metal complex oxide with the raw material compound of the boron compound. For example, at least a portion of the boron compound may exist on the surface of the lithium transition metal complex oxide particles. In addition, at least a portion of the boron compound can be physically bound to the lithium transition metal complex oxide. Specifically, the boron compound can be trapped in or at least partially cover the surface of the lithium transition metal complex oxide particles. In addition, through the mechanochemical reaction of the lithium transition metal complex oxide with the raw material compound of the boron compound, at least a portion of the boron compound can form a chemical bond, for example, the complex oxide, with a or more elements (such as lithium) that make up the lithium transition metal complex oxide. The average composition of the lithium transition metal complex oxide is considered not to change before and after this reaction, even if at least a portion of the boron compound raw material reacts with one or more elements that make up the complex oxide of lithium transition metal. As the raw material compound of the boron compound, at least one selected from the group consisting of boron oxide, boron oxy acids and boron oxy acid salts is preferably used as described above. When boron oxyacid salts are used, lithium or ammonium salt is preferred. As described above, boron oxyacids are more preferred as the raw material compound of the boron compound, and ortho-boric acid is particularly preferred.
    [0058] [00058] The lithium transition metal complex oxide and the boron compound raw material compound are preferably mixed in such a way that the ratio of boron element to the lithium transition metal complex oxide is 2.0 mol% or less. By mixing in such a ratio, the ratio of boron element in the boron compound to the lithium transition metal complex oxide in the obtained positive electrode composition can be established at 2.0 mol% or less.
    [0059] [00059] The mixture obtained by mixing as described above can be used as the positive electrode composition of the present invention. The positive electrode composition obtained by the method of the present invention has excellent characteristics of output power and cycling characteristics. In addition, the increase in viscosity of the positive electrode slurry can be suppressed by using the positive electrode composition obtained by the method of the present invention. Calcination
    [0060] [00060] The formation of the physical and / or chemical bond between the boron compound and the lithium transition metal complex oxide can be facilitated by additional calcination of the mixture obtained through the mixture mentioned above. As a result, the elution of tungsten and / or lithium from the lithium transition metal complex oxide is less likely to happen. In addition, the lithium ion conductivity of the entire positive electrode composition is increased, and the output power characteristics are further enhanced. In addition, moisture and / or hydration water that may be present in the boron compound can be removed by means of calcination, and as a result, the degradation of characteristics due to moisture and / or hydration water can be suppressed.
    [0061] [00061] The calcination temperature is preferably 450 ° C or less, and more preferably 400 ° C or less, and 200 ° C or greater. When the calcination temperature is 450 ° C or less, or more preferably 400 ° C or less, the lithium transition metal complex oxide can react with the raw material compound of the boron compound to an extent that the innate characteristics of the lithium transition metal complex oxide can be sufficiently presented. When the calcination temperature is 200 ° C or higher, the effects such as suppression of tungsten and lithium elution can be further improved. Secondary non-aqueous electrolyte battery
    [0062] [00062] A secondary non-aqueous electrolyte battery, according to the present invention, uses the above-mentioned positive electrode composition for its positive electrode. The components of the secondary non-aqueous electrolyte battery according to the present invention are not specifically limited, and the components known as those for the secondary non-aqueous electrolyte batteries can be used appropriately. The secondary non-aqueous electrolyte battery, according to the present invention, can be suitably prepared according to known methods. An example of a non-aqueous electrolyte secondary battery configuration according to the present invention is described below; however, the present invention is not limited to the following configuration example.
    [0063] [00063] In one example, the secondary non-aqueous electrolyte battery comprises a positive electrode, a negative electrode and a non-aqueous electrolyte.
    [0064] [00064] The positive electrode is not specifically limited as long as it can be used in the secondary non-aqueous electrolyte battery. In one example, the positive electrode can be obtained by preparing a positive electrode slurry comprising at least the positive electrode composition of the present invention, applying the positive electrode slurry to at least one side of an electrode collector positive, and drying the applied positive electrode slurry. The positive electrode slurry mentioned above can additionally comprise a conductive agent, a binder, a dispersion medium and the like. The conducting agent, the binder, the dispersion medium and the like can be appropriately selected depending on the purposes. The obtained positive electrode can be formed by compression appropriately and cut to a given size.
    [0065] [00065] The negative electrode is not specifically limited as long as it can be used in the secondary non-aqueous electrolyte battery. In one example, the negative electrode can be obtained by preparing a negative electrode slurry comprising at least one negative electrode active material, applying the negative electrode slurry obtained on at least one side of an electrode collector negative, and drying of the negative electrode slurry. The aforementioned negative electrode slurry may further comprise a thickening agent, a binder, a dispersion medium and the like. The thickening agent, the binder, the dispersion medium and the like can be appropriately selected depending on the purposes. The obtained negative electrode can be properly formed by compression and cut to a given size. The negative electrode active material is not specifically limited as long as it can be used as a negative electrode active material from non-aqueous electrolyte secondary batteries and, for example, carbon materials such as artificial graphite can be used.
    [0066] [00066] Non-aqueous electrolyte is not specifically limited as long as it can be used for secondary non-aqueous electrolyte batteries. The non-aqueous electrolyte generally comprises a support electrolyte and a solvent. As the supporting electrolyte, for example, UBF4, LiPF 6 and the like can be used. As the solvent, carbonate based solvents such as ethylene carbonate, methyl ethyl carbonate and the like can be used. For example, a mixed solvent obtained by mixing EC (ethylene carbonate) and MEC (methyl ethyl carbonate) in a volume ratio of 3: 7. The concentration of the supporting electrolyte is not specifically limited, and can be from about 0.5 mol / l to about 1.5 mol / l.
    [0067] [00067] A secondary non-aqueous electrolyte battery can be manufactured using known methods. In one example, the secondary non-aqueous electrolyte battery can be obtained by placing the positive and negative electrodes mentioned above opposite each other by means of a separator, and encapsulating them together with the non-aqueous electrolyte in a set external. The secondary non-aqueous electrolyte battery, according to the present invention, has excellent output power characteristics and cycling characteristics. Examples Example 1
    [0068] [00068] In a reaction vessel, pure water is prepared with stirring, and aqueous solutions of nickel sulphate, cobalt sulphate and manganese sulphate are added by dripping in a flow rate ratio such that a molar ratio of nickel, cobalt and manganese are Ni: Co: Mn = 4: 3: 3. After the drip addition is complete, a liquid temperature is adjusted to 50 ° C and a given amount of an aqueous sodium hydroxide solution is added by dripping in order to obtain a precipitation of complex nickel-cobalt-manganese hydroxide . The obtained precipitation is washed with water, filtered, separated and then mixed with lithium carbonate, tungsten oxide (VI) and zirconium oxide (IV) so that Li: (Ni + Co + Mn): W: Zr become 1.07: 1: 0.004: 0.005 (a molar ratio) in order to obtain a raw material. The mixed raw material obtained is calcined under the atmosphere at 885 ° C for 15 hours in order to obtain a sintered body. The sintered body obtained is ground and subjected to dry sieving to obtain a complex lithium transition metal oxide represented by a composition formula Li 1.07 Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O 2 .
    [0069] [00069] The complex transition metal oxide of lithium and boric acid (orthoboric acid, H 3 BO 3 ) as the raw material compound of the boron compound is mixed by means of a high speed shear type mixer of so that a ratio of boron element to lithium transition metal complex oxide is 0.5 mol% to obtain a mixture. The obtained mixture is calcined under the atmosphere at 250 ° C for 10 hours to obtain a positive electrode composition from Example 1. Example 2
    [0070] [00070] A positive electrode composition of Example 2 is obtained in the same way as in Example 1, except by mixing the lithium transition metal complex oxide and boric acid (orthoboric acid) so that a boron element ratio for the lithium transition metal complex oxide is 1.0 mol%. Example 3
    [0071] [00071] A positive electrode composition of Example 3 is obtained in the same manner as in Example 1, except by mixing the precipitation of nickel-cobalt-manganese hydroxide with lithium carbonate, tungsten oxide (VI) and oxide (IV ) of zirconium so that Li: (Ni + Co + Mn): W: Zr becomes 1.21: 1: 0.004: 0.005 (a molar ratio) and obtain a complex lithium transition metal oxide represented by of a formula of composition Li 1.21 Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O2. Example 4
    [0072] [00072] A positive electrode composition of Example 4 is obtained in the same manner as in Example 1, except by mixing the precipitation of nickel-cobalt-manganese hydroxide with lithium carbonate, tungsten oxide (VI) and oxide (IV ) of zirconium so that Li: (Ni + Co + Mn): W: Zr becomes 1.00: 1: 0.004: 0.005 (a molar ratio) and obtain a complex lithium transition metal oxide represented by of a formula of composition Li 1.00 Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O2. Example 5
    [0073] [00073] In a reaction vessel, pure water is prepared with stirring, and aqueous solutions of nickel sulphate, cobalt sulphate and manganese sulphate are added by dripping in a flow rate ratio such that a molar ratio of nickel, cobalt and manganese are Ni: Co: Mn = 5: 1: 4. After the drip addition is complete, a liquid temperature is adjusted to 50 ° C and a given amount of an aqueous sodium hydroxide solution is added by dripping in order to obtain a precipitation of complex nickel-cobalt-manganese hydroxide . The obtained precipitation is washed with water, filtered, separated and then mixed with lithium carbonate, tungsten oxide (VI) and zirconium oxide (IV) so that Li: (Ni + Co + Mn): W: Zr become 1.21: 1: 0.005: 0.005 (a molar ratio) in order to obtain a raw material. The mixed raw material obtained is calcined under the atmosphere at 885 ° C for 15 hours in order to obtain a sintered body. The sintered body obtained is milled and subjected to dry sieving to obtain a complex lithium transition metal oxide represented by a composition formula Li 1.21 Ni 0.5 Co 0.1 Mn 0.4 W 0.005 Zr 0.005 O2.
    [0074] [00074] The lithium transition metal oxide complex and boric acid (ortho-boric acid) as the raw material compound of the boron compound is mixed by means of a high speed shear type mixer so that a ratio of boron element for the lithium transition metal complex oxide is 0.5 mol% to obtain a mixture. The obtained mixture is calcined under the atmosphere at 250 ° C for 10 hours to obtain a positive electrode composition from Example 5. Example 6
    [0075] [00075] A positive electrode composition of Example 6 is obtained in the same way as in Example 5, except by mixing the lithium transition metal complex oxide and boric acid (orthoboric acid) so that a ratio of the boron element to the lithium transition metal complex oxide is 1.0 mol%. Example 7
    [0076] [00076] A positive electrode composition of Example 7 is obtained in the same way as in Example 5, except by mixing the lithium transition metal complex oxide and boric acid (orthoboric acid) so that a ratio of the boron element to the lithium transition metal complex oxide is 0.25 mol%. Example 8
    [0077] [00077] A positive electrode composition of Example 8 is obtained in the same manner as in Example 5, except by mixing the precipitation of nickel-cobalt-manganese hydroxide with lithium carbonate, tungsten oxide (VI) and oxide (IV ) of zirconium so that Li: (Ni + Co + Mn): W: Zr becomes 1.07: 1: 0.005: 0.005 (a molar ratio) and obtain a complex lithium transition metal oxide represented by of a formula of composition Li 1.07 Ni 0.5 Co 0.1 Mn 0.4 W 0.005 Zr 0.005 O2. Example 9
    [0078] [00078] A positive electrode composition from Example 9 is obtained in the same way as in Example 5, except by using LiBO 2 in place of boric acid (ortho-boric acid). Example 10
    [0079] [00079] The lithium transition metal complex oxide is obtained in the same manner as in Example 5. The lithium transition metal complex oxide and boric acid obtained as the raw material compound of the boron compound are mixed by means of a high speed shear-type mixer so that a ratio of the boron element to the lithium transition metal complex oxide is 0.5 mol% to obtain a positive electrode composition of Example 10. Example 11
    [0080] [00080] In a reaction vessel, pure water is prepared with stirring, and aqueous solutions of nickel sulphate, cobalt sulphate and aluminum sulphate are added by dripping in a flow rate ratio such that a molar ratio of nickel, cobalt and aluminum are Ni: Co: AI = 8.15: 1.55: 0.30. After the drip addition is complete, a liquid temperature is adjusted to 50 ° C and a given amount of an aqueous sodium hydroxide solution is added by dripping in order to obtain a precipitation of complex nickel-cobalt-aluminum hydroxide . The obtained precipitation is washed with water, filtered, separated and then mixed with lithium carbonate, tungsten oxide (VI) and zirconium oxide (IV) so that Li: (Ni + Co + AI): W: Zr become 1.10: 1: 0.004: 0.005 (a molar ratio) in order to obtain a raw material. The mixed raw material obtained is calcined under the atmosphere at 885 ° C for 15 hours in order to obtain a sintered body. The sintered body obtained is milled and subjected to dry sieving to obtain a complex lithium transition metal oxide represented by a formula of composition Li 1.10 Ni 0.815 Co 0.155 Mn 0.030 W 0.004 Zr 0.005 O2.
    [0081] [00081] The complex lithium transition metal oxide and the boric acid obtained (ortho-boric acid) are mixed using a high-speed shear-type mixer so that a ratio of the boron element to the complex metal oxide lithium transition is 1.0 mol% to obtain a mixture. The obtained mixture is calcined under the atmosphere at 250 ° C for 10 hours to obtain a positive electrode composition from Example 11. Comparative Example 1
    [0082] [00082] The lithium transition metal complex oxide is obtained by the same way as in Example 1 and is used with a positive electrode composition from Comparative Example 1. Comparative Example 2
    [0083] [00083] The lithium transition metal complex oxide is obtained by the same way as in Example 3 and is used with a positive electrode composition from Comparative Example 2. Comparative Example 3
    [0084] [00084] The lithium transition metal complex oxide is obtained by the same way as in Example 4 and is used with a positive electrode composition from Comparative Example 3. Comparative Example 4
    [0085] [00085] The lithium transition metal complex oxide is obtained by the same way as in Example 5 and is used with a positive electrode composition from Comparative Example 4. Comparative Example 5
    [0086] [00086] The lithium transition metal complex oxide is obtained by the same way as in Example 8 and is used with a positive electrode composition from Comparative Example 5. Comparative Example 6
    [0087] [00087] The lithium transition metal complex oxide is obtained by the same way as in Example 11 and is used with a positive electrode composition from Comparative Example 6. Comparative Example 7
    [0088] [00088] Precipitation of nickel-cobalt-manganese hydroxide is obtained in the same way as in Example 1. The obtained precipitation is washed with water, filtered, separated and then mixed with lithium carbonate and (IV) oxide. zirconium so that Li: (Ni + Co + Mn): Zr becomes 1.07: 1: 0.005 (a molar ratio) in order to obtain a raw material. The mixed raw material obtained is calcined under the atmosphere at 885 ° C for 15 hours in order to obtain a sintered body. The sintered body obtained is ground and subjected to dry sieving to obtain a complex lithium transition metal oxide represented by a composition formula Li 1.07 Ni 0.4 Co 0.3 Mn 0.3 Zr 0.005 O2 . This lithium transition metal complex oxide is used with a positive electrode composition from Comparative Example 7. Comparative Example 8
    [0089] [00089] A positive electrode composition of Comparative Example 8 is obtained in the same way as in Example 1, except by using TiB 2 in place of boric acid (ortho-boric acid) so that a ratio of the boron element to the complex oxide of lithium transition metal is 0.5 mol%. Comparative Example 9
    [0090] [00090] A positive electrode composition from Comparative Example 9 is obtained in the same way as in Example 1, except by using ZrB 2 in place of boric acid (ortho-boric acid) so that a ratio of the boron element to the complex oxide of lithium transition metal is 0.5 mol%. Evaluation of output power characteristics
    [0091] [00091] Using the positive electrode compositions of Examples 1 through 11 and Comparative Examples 1 through 9, the batteries for evaluation are prepared according to the following procedures, and CC-IR (internal direct current resistances) of the batteries is measured in a manner as described below. 1. Preparation of positive electrode
    [0092] [00092] A positive electrode slurry is prepared by dispersing 85 parts by weight of the positive electrode composition, 10 parts by weight of carbon black as a conductive agent and 5.0 parts by weight of PVDF (polyvinylidene fluoride) ) as a binder in NMP as a dispersion medium. The obtained positive electrode slurry is applied to a dry aluminum sheet, formed by compression using a roller press and then cut to a given size to obtain a positive electrode. 2. Preparation of negative electrode
    [0093] [00093] A negative electrode slurry is prepared by dispersing 97.5 parts by weight of artificial graphite, 1.5 parts by weight of CMC (carboxymethylcellulose) as a thickening agent and 1.0 parts by weight of SBR (styrene-butadiene rubber) as a binder in water as a dispersion medium. The obtained negative electrode slurry is applied to a dry copper sheet, formed by compression using a roller press and then cut to a given size to obtain a negative electrode. 3. Preparation of electrolyte
    [0094] [00094] EC (ethylene carbonate) and MEC (methyl ethyl carbonate) are mixed with each other in a volume ratio of 3: 7 to obtain a solvent. Lithium hexafluorophosphate (LiPF 6 ) is dissolved in the mixed solvent obtained so that the concentration becomes 1 mol / l to obtain a non-aqueous electrolyte. 4. Battery manufacturing for evaluation
    [0095] [00095] The lead electrodes are respectively attached to current collectors of the positive and negative electrodes mentioned above, followed by vacuum drying at 120 ° C. Then, a separator made of porous polyethylene is provided between the positive electrode and the negative electrode, and they are placed in a laminated pouch-shaped assembly. After that, the moisture absorbed by each member is removed by vacuum drying at 60 ° C. After vacuum drying, the non-aqueous electrolyte mentioned above is injected into the laminated assembly, followed by sealing to obtain a secondary battery of laminated non-aqueous electrolyte for evaluation. 5. CC-IR measurement
    [0096] [00096] The battery obtained is aged with the application of a micro current, thus allowing the electrolyte to permeate the positive and negative electrodes sufficiently. Then, the discharge with high current and charge with micro current are repeatedly alternated. The charging capacity at 10 ạ charge is considered as a full battery charging capacity. After 10 ạ discharge, the battery is charged to 40% of the full charge capacity. After charging, the battery is placed in a constant temperature bath set at -25 ° C. After leaving for six hours, the battery is discharged with 0.02 A, 0.04 A and 0.06 A, and the voltage is measured in relation to each current. The points at the intersections of the currents in the abscissa and the voltages in the ordinate are plotted, and a slope of a straight line that connects the points is considered to be CC-IR. Lower CC-IR means good output power characteristics.
    [0097] [00097] Regarding the batteries for evaluation obtained by using the positive electrode compositions of Comparative Examples 8 using TiB 2 as the raw material compound of the boron compound and Comparative Example 9 using ZrB 2 as the material compound of the boron compound, the evaluation of the output power characteristics could not be performed since a behavior that appears to be a short circuit was observed under load. The cause of the behavior that appears to be a short circuit is considered that titanium or zirconium contained in the boron compound is eluted in the electrolyte, and the eluted titanium or zirconium is reprecipitated in the negative electrode, and the reprecipitated titanium or zirconium causes the short circuit. . Positive electrode slurry viscosity measurement
    [0098] [00098] With respect to the positive electrode compositions of Examples 1 to 11 and Comparative Examples 1 to 7, a viscosity of the positive electrode slurry is measured as follows. 1. Measurement of initial viscosity
    [0099] [00099] 30 g of a positive electrode composition, 1.57 g of PVDF and 12.48 g of NMP are placed in a 150 ml polyethylene container and kneaded at a normal temperature (about 25 ° C) for 5 minutes. After kneading, the viscosity of the slurry obtained is immediately measured by an E type viscometer. The measurement is carried out using a cone-plate blade at a rotor speed of 5 rpm. Thus, a measured value of an initial viscosity is obtained. 2. Viscosity change assessment
    [0100] [000100] Next, the slurry in the polyethylene container is left in a constant temperature bath at 60 ° C, and the viscosity is measured after 24 hours and 48 hours. Before the respective measurements, the slurry is kneaded at a normal temperature for 2 minutes. Assessment of cycling characteristics
    [0101] [000101] With respect to the positive electrode compositions of Examples 1 through 11 and Comparative Examples 1 through 9, the cycling characteristics are measured as follows.
    [0102] [000102] A secondary battery for evaluation prepared in the same way as the battery for evaluation of the output power characteristics is aged with a microcurrent, thus allowing the electrolyte to permeate sufficiently in the positive and negative electrodes. After aging, the battery is placed in a constant temperature bath set at 20 ° C, and the charge-discharge is carried out repeatedly in which the charge has a charging potential of 4.2 V and a charging current of 1.0 C (1 C is defined as a current with which the discharge is completed in one hour) and the discharge with a discharge potential of 2.75 V and a discharge current of 1.0 C is related to a cycle. A value (%) of discharge capacity at the nth cycle divided by the discharge capacity in the first cycle is listed as a discharge capacity retention (QSR) in the nth cycle. The retention of greater discharge capacity means good cycling characteristics.
    [0103] [000103] With respect to the positive electrode compositions of Comparative Examples 8 and 9, the evaluation of the cycling characteristics could not be performed since a behavior that appears to be a short circuit was observed under load.
    [0104] [000104] The composition formulas (shown as "Composition A" in Table 1) of the lithium transition metal complex oxide of Examples 1 to 11 and Comparative Examples 1 to 9, compound composition formulas of compound raw materials boron levels (shown as “Composition B” in Table 1) and boron levels in positive electrode compositions (shown as “B content” in Table 1 and Figure 1) are shown in Table 1, and CC-IR (R ), viscosity (v) of the positive electrode slurry and the retention of discharge capacity (QsR) after the 100th cycle shown in Table 2.
    [0105] [000105] As is evident from Tables 1 and 2, the positive electrode composition of Comparative Example 7 comprising the lithium transition metal complex oxide does not comprise tungsten and the boron compound comprising at least boron element and oxygen element has lower output power characteristics when compared to the positive electrode composition of Example 1 which comprises the lithium transition metal complex oxide comprising tungsten and the boron compound comprising at least boron element and oxygen element . On the other hand, the positive electrode composition of Comparative Example 1 which comprises only the complex lithium transition metal oxide which comprises tungsten has improved output power characteristics, but reduced cyclization characteristics when compared to the positive electrode composition of the Comparative Example 7. In contrast, it can be seen that the positive electrode composition of Example 1 which comprises the lithium transition metal complex oxide comprising tungsten and the boron compound comprising at least boron element and oxygen element has improved output power characteristics, as well as improved cycling characteristics when compared to the positive electrode composition of Comparative Example 7. In addition, as is evident from Tables 1 and 2, the positive electrode composition of Example 1 can suppress the increase in viscosity of the positive electrode slurry compared to co positive electrode arrangements of Comparative Examples 1 and 7.
    [0106] [000106] Figure 1 shows a relationship between the boron content in the positive electrode and CC-IR (R) compositions in relation to Examples 1 and 2 and Comparative Example 1 using the lithium transition metal complex oxide represented by the formula of composition Li 1.07 Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O2. as well as Examples 5 to 7 and Comparative Example 4 using the lithium transition metal complex oxide represented by the composition formula Li 1.21 Ni 0.5 Co 0.1 Mn 0.4 W 0.005 Zr 0.005 O2. As is evident from Figure 1, the output power characteristics are enhanced through the use of a positive electrode composition that comprises a boron compound that comprises at least boron element and oxygen element, compared to the use case. the lithium transition metal complex oxide alone. The output power characteristics are further improved as the boron content is increased, and the output power characteristics become constant when the boron content is about 0.5 mol% or more. Therefore, it can be seen that the sufficient effect can be achieved when the boron content is about 0.5 mol% or more.
    [0107] [000107] With respect to the results of the CC-IR measurements shown in Table 2, the effect on improving the output power characteristics due to the positive electrode composition comprising the boron compound will also be confirmed in other modalities of complex oxide. lithium transition metal, from the comparisons between Example 3 and Comparative Example 2, between Example 4 and Comparative Example 3, between Example 8 and Comparative Example 5 and between Example 11 and Comparative Example 6.
    [0108] [000108] In addition, as is evident from Table 1, the lithium transition metal complex oxide represented by the composition formula Li 1.21 Ni 0.5 Co 0.1 Mn 0.4 W 0.005 Zr 0.005 O2 . (Comparative Example 4) has lower output power characteristics compared to the lithium transition metal complex oxide represented by the composition formula Li 1.07 Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O2. (Comparative Example 1). It can be seen from Figure 1 that Example 5 through the use of the lithium transition metal complex oxide which represents relatively lower output power characteristics has a greater effect on improving the output power characteristics due to the addition of the compound boron, compared to the lithium transition metal complex oxide which represents relatively higher output power characteristics, when the boron content is the same.
    [0109] [000109] Figure 2 shows a time-dependent change in the viscosity of the positive electrode slurries of Examples 1 and 2 and Comparative Example 1, and Figure 3 shows a time-dependent change in the viscosity of the positive electrode slurries of the Examples 5 to 7 and Comparative Example 4. As is evident from Figures 2 and 3, the increase in viscosity can be suppressed by using the positive electrode composition comprising the boron compound comprising at least boron element and oxygen element in the positive electrode slurry, compared to the case of the use of lithium transition metal complex oxide alone according to the positive electrode composition.
    [0110] [000110] Figure 4 shows a relationship between the value of a and CC-IR (R) in relation to the positive electrode compositions of Examples 1, 3 and 4 comprising the complex lithium transition metal oxide represented by the composition formula Li a Ni 0.4 Co 0.3 Mn 0.3 W 0.004 Zr 0.005 O2, as well as the positive electrode compositions of Examples 5 and 8 comprising the lithium transition metal complex oxide represented by the Li a composition formula Ni 0.5 Co 0.1 Mn 0.4 W 0.005 Zr 0.005 O2. As can be seen from Figure 4, the output power characteristics are further improved as the value of a is increased in both lithium transition metal complex oxide compositions. In addition, it can be seen from Figure 4 that the output power characteristics are significantly improved when the value of a exceeds about 1.05.
    [0111] [000111] Figure 5 shows the cycling characteristics in relation to Examples 1 and 2 and Comparative Example 1. As is evident from Figure 5, the cycling characteristics are improved through the use of the positive electrode composition comprising the boron compound comprising at least boron element and oxygen element, compared to the use of lithium transition metal complex oxide alone as per the positive electrode composition. In addition, it can be seen that such an effect becomes greater as the boron content is increased.
    [0112] [000112] As can be seen from Tables 1 and 2, the positive electrode composition of Example 9 through the use of LiBO 2 as the raw material compound of the boron compound has characteristics of output power and characteristics of improved cycling when compared to the positive electrode composition of Comparative Example 4 that does not comprise the boron compound. In addition, it can be seen that the positive electrode composition of Example 9 has lower output power characteristics and cyclization characteristics when compared to the positive electrode composition of Example 5 through the use of boric acid (orthoboric acid) as the compound of raw material of the boron compound. On the other hand, it can be seen that the effect in suppressing the increase in viscosity of the positive electrode slurry is slightly greater in the positive electrode composition of Example 9 than that of Example 5. Therefore, it can be seen that boric acid is more preferable for the raw material compound of the boron compound.
    [0113] [000113] As is evident from Tables 1 and 2, the positive electrode composition of Example 10 in which calcination is not performed after mixing the lithium transition metal complex oxide and the raw material compound of the compound boron has improved output power characteristics and improved cycling characteristics, as well as the greater effect in suppressing the increase in viscosity of the positive electrode slurry compared to the positive electrode composition of Comparative Example 4 that does not comprise the boron compound. This describes that the effects of the present invention can be achieved even when calcination is not carried out. INDUSTRIAL APPLICABILITY
    [0114] [000114] By using the positive electrode composition of the present invention, the secondary non-aqueous electrolyte battery can achieve both greater output power characteristics and greater cycling characteristics. In addition, performance and operability are improved as the increase in viscosity of the positive electrode slurry is suppressed. Therefore, the secondary non-aqueous electrolyte battery through the use of the positive electrode composition of the present invention can achieve low cost as well as high output power characteristics and high cycling characteristics, and thus, may be particularly suitable for use not only in mobile devices such as a mobile phone, a PC-type computer and a digital camera, but also on a high-output power supply for large applications such as a battery for an electric vehicle.
    权利要求:
    Claims (13)
    [0001]
    Positive electrode composition for non-aqueous electrolyte secondary battery, characterized by the fact that it comprises:a complex lithium transition metal oxide represented by a general formula LiTheNi1-xyCoxM1 yWzM2 wTHE2 (on what 1.0≤a≤1.5, 0≤x≤0.5, 0 <y≤0.5, 0.002≤z≤0.03, 0≤w≤0.02, 0≤x + y≤0, 7, M1 comprises Mn and Al, and M2 comprises Zr); anda boron compound comprising at least the boron element and the oxygen element,wherein the boron compound is obtained at least by mixing the lithium transition metal complex oxide and boron compound raw material compound,wherein the raw material compound of the boron compound is at least one element selected from the group consisting of orthoboric acid and boron oxy acid salts, andwherein a ratio of the boron element to the lithium transition metal complex oxide is in the range 0.5 mol% to 1.5 mol%.
    [0002]
    Positive electrode composition for secondary non-aqueous electrolyte battery, according to claim 1, characterized by the fact that the boron compound is obtained by mixing the lithium transition metal complex oxide and the raw material compound boron compound followed by calcination.
    [0003]
    Positive electrode composition for secondary non-aqueous electrolyte battery, according to claim 2, characterized by the fact that a calcination temperature in the calcination is 450 ° C or less.
    [0004]
    Positive electrode composition for secondary non-aqueous electrolyte battery, according to claim 1, 2 or 3, characterized by the fact that the raw material compound of the boron compound is ortho-boric acid.
    [0005]
    Positive electrode composition for non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, characterized in that the lithium transition metal complex oxide is in the form of particles, and at least a portion of the compound boron exists on a surface of lithium transition metal complex oxide particles.
    [0006]
    Positive electrode composition for secondary non-aqueous electrolyte battery according to claim 5, characterized in that at least a portion of the boron compound covers at least partially the surface of the lithium transition metal complex oxide particles.
    [0007]
    Positive electrode composition for non-aqueous electrolyte secondary battery according to any one of claims 1 to 6, characterized in that at least a portion of the boron compound is chemically linked to one or more elements that make up the complex oxide of lithium transition metal.
    [0008]
    Positive electrode composition for non-aqueous electrolyte secondary battery according to claim 7, characterized by the fact that at least a portion of the boron compound forms a complex oxide with one or more elements that constitute the complex transition metal oxide of lithium.
    [0009]
    Secondary non-aqueous electrolyte battery, characterized by the fact that it uses, for a positive electrode, the positive electrode composition as defined in any one of claims 1 to 8.
    [0010]
    Method for producing a positive electrode composition for a non-aqueous electrolyte secondary battery comprising a complex lithium transition metal oxide represented by a general formula LiTheNi1-xyCoxM1 yWzM2 wTHE2 (on what 1.0≤a≤1.5, 0≤x≤0.5, 0 <y≤0.5, 0.002≤z≤0.03, 0≤w≤0.02, 0≤x + y≤0, 7, M1comprises Mn and Al, and M2 comprises Zr), and a boron compound comprising at least the boron element and the oxygen element, characterized by the fact that it comprises at least:synthesize the lithium transition metal complex oxide; andmixing the lithium transition metal complex oxide obtained by the synthesis and a raw material compound of the boron compound to obtain a mixture,wherein the raw material compound of the boron compound is at least one element selected from the group consisting of orthoboric acid and boron oxy acid salts, andwherein the lithium transition metal complex oxide and the boron compound raw material compound are mixed in the mixture so that a ratio of the boron element to the lithium transition metal oxide complex is in a 0 range, 5 mol% to 1.5 mol%.
    [0011]
    Method according to claim 10, characterized by the fact that it further comprises calcining the mixture.
    [0012]
    Method according to claim 11, characterized by the fact that a calcination temperature in the calcination is 450 ° C or less.
    [0013]
    Method according to claim 10, 11 or 12, characterized by the fact that the raw material compound of the boron compound is ortho-boric acid.
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    同族专利:
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    EP2654109B1|2018-11-28|
    JP2013239434A|2013-11-28|
    BR102013009295A2|2015-06-23|
    CN103456916B|2017-06-30|
    RU2618229C2|2017-05-03|
    US20130277604A1|2013-10-24|
    JP6286855B2|2018-03-07|
    HUE041410T2|2019-05-28|
    KR20130117340A|2013-10-25|
    US20170317339A1|2017-11-02|
    RU2013117850A|2014-10-27|
    US9742002B2|2017-08-22|
    EP2654109A1|2013-10-23|
    KR102021151B1|2019-09-11|
    PL2654109T3|2019-05-31|
    US10454097B2|2019-10-22|
    CN103456916A|2013-12-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    AT295619B|1969-04-02|1972-01-10|Varta Gmbh|Rechargeable mercury / mercury oxide electrode for galvanic elements|
    JPH1079244A|1996-09-04|1998-03-24|Toray Ind Inc|Electrode and nonaqueous electrolyte second battery using it|
    JP3566106B2|1998-10-01|2004-09-15|日本碍子株式会社|Lithium secondary battery|
    JP3088716B1|1999-04-30|2000-09-18|同和鉱業株式会社|Positive electrode active material and lithium secondary battery using the positive electrode active material|
    JP2001257003A|2000-03-13|2001-09-21|Yuasa Corp|Lithium secondary battery|
    US7138209B2|2000-10-09|2006-11-21|Samsung Sdi Co., Ltd.|Positive active material for rechargeable lithium battery and method of preparing same|
    JP2005251716A|2004-02-05|2005-09-15|Nichia Chem Ind Ltd|Cathode active substance for nonaqueous electrolyte secondary battery, cathode mixture for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery|
    CN101536220B|2006-12-26|2013-07-10|三菱化学株式会社|Lithium transition metal compound powder, process for production thereof, lithium secondary battery|
    JP5515211B2|2007-12-14|2014-06-11|ソニー株式会社|Method for producing positive electrode active material|
    JP2010040383A|2008-08-06|2010-02-18|Sony Corp|Method of manufacturing positive electrode active material, and positive electrode active material|
    KR20110019574A|2009-08-20|2011-02-28|삼성에스디아이 주식회사|Cathode active material, cathode and lithium battery containing the material and preparation method thereof|
    US8609284B2|2009-10-27|2013-12-17|Farasis Energy, Inc.|Composite for cathode of Li-ion battery, its preparation process and the Li-ion battery|
    JP2011108554A|2009-11-19|2011-06-02|Mitsubishi Chemicals Corp|Lithium transition metal based compound powder, its manufacturing method, and positive electrode material for lithium secondary battery and lithium secondary battery using it|
    JP5382061B2|2010-06-22|2014-01-08|日亜化学工業株式会社|Positive electrode composition for non-aqueous electrolyte secondary battery and positive electrode slurry using the positive electrode composition|
    CN103069623B|2010-08-09|2015-07-22|株式会社村田制作所|Electrode active material and non-aqueous electrolyte secondary battery provided with same|
    CN103548186B|2011-05-23|2017-04-26|丰田自动车株式会社|Positive electrode active material particles, and positive electrode and all-solid-state battery using same|TWI609519B|2013-10-29|2017-12-21|Ｌｇ化學股份有限公司|Manufacturing method of cathode active material, and cathode active material for lithium secondary battery manufactured thereby|
    JP6554780B2|2013-10-29|2019-08-07|日亜化学工業株式会社|Positive electrode composition for non-aqueous electrolyte secondary battery and method for producing the same|
    KR101589296B1|2013-12-10|2016-01-28|주식회사 포스코|Positive electrode active material for rechargable lithium battery, method for synthesis the same, and rechargable lithium battery including the same|
    KR101977995B1|2013-12-24|2019-05-13|경북대학교 산학협력단|Positive electrode active material coated with boron compounds for lithium secondary battery and preparation method thereof|
    KR101589294B1|2014-01-29|2016-01-28|주식회사 포스코|Positive electrode active material for rechargable lithium battery, method for synthesis the same, and rechargable lithium battery including the same|
    US20170077492A1|2014-02-28|2017-03-16|Sanyo Electric Co., Ltd.|Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same|
    JP6119641B2|2014-02-28|2017-04-26|三洋電機株式会社|Cylindrical non-aqueous electrolyte secondary battery|
    CN106104860B|2014-03-20|2018-11-30|三洋电机株式会社|Positive electrode for nonaqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery|
    JP6065874B2|2014-05-27|2017-01-25|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery using the positive electrode active material|
    JP6685640B2|2014-07-31|2020-04-22|日亜化学工業株式会社|Non-aqueous electrolyte Positive electrode active material for secondary battery|
    EP3353835B1|2015-09-23|2020-06-10|Umicore|Lithium-rich nickel-manganese-cobalt cathode powders for lithium-ion batteries|
    US10411259B2|2015-10-21|2019-09-10|Nichia Corporation|Positive electrode composition for non-aqueous secondary battery and method of producing the same|
    KR101927295B1|2015-11-30|2018-12-10|주식회사 엘지화학|Positive electrode active material for secondary battery and secondary battery comprising the same|
    JP2017130409A|2016-01-22|2017-07-27|Ｃｓエナジーマテリアルズ株式会社|Doped and coated positive electrode active material for composite lithium ion battery, and lithium ion battery arranged by use thereof|
    DE102017207683A1|2016-05-09|2017-11-09|Nichia Corporation|A process for producing a nickel-cobalt composite hydroxide and a process for producing an active material of a positive electrode for an anhydrous electrolyte secondary battery|
    CN109155412A|2016-05-16|2019-01-04|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery|
    CN109891643A|2016-08-29|2019-06-14|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery|
    JPWO2018043669A1|2016-08-31|2019-06-24|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery|
    JP6862727B2|2016-09-13|2021-04-21|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery and its manufacturing method, and non-aqueous electrolyte secondary battery using the positive electrode active material|
    JP6637873B2|2016-11-02|2020-01-29|Ｊｘ金属株式会社|Positive active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery|
    KR20190086692A|2016-12-07|2019-07-23|스미또모 가가꾸 가부시끼가이샤|Method for producing positive electrode active material for lithium secondary battery|
    KR101918719B1|2016-12-12|2018-11-14|주식회사 포스코|Positive electrode active material for rechargeable lithium battery, method for manufacturing the same, and rechargeable lithium battery including the same|
    JP6222337B2|2016-12-19|2017-11-01|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery using the positive electrode active material|
    CN110392950A|2016-12-26|2019-10-29|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method and non-aqueous electrolyte secondary battery|
    JP6583254B2|2016-12-27|2019-10-02|日亜化学工業株式会社|Non-aqueous secondary battery positive electrode material, non-aqueous secondary battery and method for producing positive electrode material for non-aqueous secondary battery|
    KR102133916B1|2016-12-28|2020-07-15|주식회사 엘지화학|Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same|
    KR102176633B1|2017-02-28|2020-11-09|주식회사 엘지화학|Positive electrode active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising the same|
    WO2018160023A1|2017-02-28|2018-09-07|주식회사 엘지화학|Cathode active material for lithium secondary battery, production method therefor, and lithium secondary battery comprising same|
    CN106876686B|2017-04-14|2020-04-21|中南大学|Method for surface modification of positive electrode active material for lithium ion battery|
    JPWO2019039567A1|2017-08-25|2020-10-01|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary batteries and its manufacturing method, positive electrode mixture paste for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary batteries|
    JPWO2019044204A1|2017-08-30|2020-08-20|パナソニックＩｐマネジメント株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery|
    EP3567661B1|2017-09-19|2021-08-04|LG Chem, Ltd.|Cathode active material for secondary battery, and lithium secondary battery comprising same|
    CN107681140A|2017-09-25|2018-02-09|江苏奔拓电气科技有限公司|A kind of composite anode material for lithium ion battery and preparation method thereof|
    US11024850B2|2017-09-27|2021-06-01|Xilectric, Inc.|Li-ion batteries with improved abuse tolerance and performance|
    JP6996198B2|2017-09-28|2022-01-17|住友金属鉱山株式会社|Manufacturing method of positive electrode active material for lithium ion secondary battery, positive electrode active material for lithium ion secondary battery and lithium ion secondary battery|
    KR102132878B1|2017-10-20|2020-07-10|주식회사 엘지화학|Positive electrode active material for lithium secondary battery, preparing method of the same, positive electrode and lithium secondary battery including the same|
    KR20190103955A|2018-02-28|2019-09-05|주식회사 엘지화학|Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same|
    KR101918723B1|2018-06-12|2018-11-14|주식회사 포스코|Positive electrode active material for rechargeable lithium battery, method for manufacturing the same, and rechargeable lithium battery including the same|
    WO2020003848A1|2018-06-29|2020-01-02|株式会社豊田自動織機|Lithium nickel cobalt tungsten oxide having layered rock salt structure|
    KR20210016026A|2018-07-25|2021-02-10|미쓰이금속광업주식회사|Positive electrode active material|
    WO2020027158A1|2018-07-31|2020-02-06|住友金属鉱山株式会社|Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery|
    CN112514119A|2018-08-03|2021-03-16|住友金属矿山株式会社|Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery|
    US11063247B2|2018-08-22|2021-07-13|Ecopro Bm Co., Ltd.|Positive electrode active material and lithium secondary battery comprising the same|
    KR102225892B1|2018-08-22|2021-03-11|주식회사 에코프로비엠|Lithium composite oxide, positive electrode active material and lithium secondary battery comprising the same|
    US11078089B2|2018-08-22|2021-08-03|Ecopro Bm Co., Ltd.|Lithium composite oxide, positive electrode active material and lithium secondary battery comprising the same|
    KR102195178B1|2018-09-18|2020-12-28|주식회사 에코프로비엠|Positive electrode active material and lithium secondary battery comprising the same|
    KR20200047116A|2018-10-26|2020-05-07|주식회사 엘지화학|Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same|
    WO2020195431A1|2019-03-27|2020-10-01|住友金属鉱山株式会社|Positive electrode active material for lithium ion secondary batteries, method for producing same, and lithium ion secondary battery|
    EP3951947A1|2019-03-27|2022-02-09|Sumitomo Metal Mining Co., Ltd.|Positive-electrode active material for lithium-ion secondary cell, method for manufacturing positive-electrode active material, and lithium-ion secondary cell|
    JP2021005474A|2019-06-25|2021-01-14|住友金属鉱山株式会社|Cathode active material for lithium ion secondary battery, manufacturing method of the same, and the lithium ion secondary battery|
    CN112993239A|2019-12-17|2021-06-18|天津国安盟固利新材料科技股份有限公司|High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof|
    US11233239B2|2020-03-27|2022-01-25|Board Of Regents, The University Of Texas System|Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries|
    CN112331844A|2020-11-03|2021-02-05|中信大锰矿业有限责任公司|Preparation method of modified nickel cobalt lithium manganate ternary positive electrode material|
    法律状态:
    2015-06-23| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-094305|2012-04-18|
    JP2012094305|2012-04-18|
    JP2013-079800|2013-04-05|
    JP2013079800A|JP6286855B2|2012-04-18|2013-04-05|Positive electrode composition for non-aqueous electrolyte secondary battery|
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