• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The size of phase separation of the soluble polymer is controlled to less than 100 nm in the polymer alloy film of the at least one polymer which is slightly swelled in the organic electrolyte and the polymer alloy film of the polymer soluble in the organic electrolyte and the gel polymer electrolyte of the organic electrolyte. By using such a gel polymer electrolyte, generation of lithium dendritic crystals is suppressed, and thus a battery having high safety and reliability can be provided.
    公开号:KR19980070598A
    申请号:KR1019980001401
    申请日:1998-01-19
    公开日:1998-10-26
    发明作者:니시무라겐；오가와마사히코；사카이데쓰히사；이시다아키코；에다노부오
    申请人:모리시타요이찌；마쓰시타덴키산교가부시키가이샤；
    IPC主号:
    专利说明:

    Polymer Electrolyte and Lithium Battery Using the Same
    The present invention relates to a polymer electrolyte and a lithium battery using the polymer electrolyte.
    A lithium ion secondary battery is composed of, for example, LiCoO 2 as an anode, an organic solution containing natural graphite as an anode and ethylene carbonate as an electrolyte, and has a high energy density. By utilizing this feature, lithium ion secondary batteries are widely used as power sources, for example, portable personal computers (PCs) or portable telephones. In order to further increase the energy density of the battery, it is effective to use a metal lithium negative electrode.
    Compared with the negative electrode made of natural graphite, the metal lithium negative electrode has a discharge capacity of about 10 times per unit weight in theory and about 2.5 times per unit volume, which has a large discharge capacity. Even though the metal lithium anode has such an excellent capacity, it causes deformation and causes serious problems such as the generation of dendritic lithium crystals (hereinafter simply referred to as dendrite) generated by the charge-discharge cycle. Have.
    Dendritic crystals are easily released in the electrode plates. Free dendritic crystals cannot be used for charge and discharge reactions because they break electrical contact with the electrode plates. Moreover, lithium is a strong reducing agent, which reacts with the electrolyte to form a film. Therefore, if the surface area is increased by dendritic crystals, the volume of the film is also increased, and thus the amount of lithium used for charging and discharging is reduced. For these reasons, the formation of dendritic crystals significantly lowers the cycle efficiency of the negative electrode. In order to maintain a large number of cycles, an excessive amount of lithium must be packed relative to the capacity of the cathode, thereby reducing the energy density of the battery.
    Moreover, a significant increase in lithium surface area sometimes results in heat generation during use or storage of this battery at high temperatures. Proceedings of Seventh International Meeting on Lithium Batteries, p. 12 (1994) reported that when the lithium surface area of the negative electrode increased significantly due to the formation of dendritic crystals during charging and discharging, the self-heating rate rapidly increased, and in extreme cases, the reaction between the negative electrode and the electrolyte was caused. Thermal runaway occurs.
    Furthermore, dendritic crystals penetrate into porous separators made of polypropylene or polyethylene, causing internal short circuits of the cells or reducing cycle efficiency and safety.
    In order to prevent the formation of dendritic crystals, research and development on a solid electrolyte has been promoted as a substitute for a conventional organic electrolyte solution. Among the solid electrolytes, polymer electrolytes are particularly noticeable because they are flexible and easy to manufacture into thin films. The polymer electrolyte contains a solid solution of lithium salts. The inhibitory effect on dendritic crystal production is described in the Collection of the summaries of lectures to the 32th forum on batteries, p. 255 (1991). However, for the ionic conductivity of the polymer electrolyte, for example, the ionic conductivity of the poly (ethylene oxide) (hereinafter simply referred to as PEO) -LiClO 4 complex is about 10 −7 S / cm. This value is extremely lower than the ionic conductivity of the organic electrolyte solution 10 -3 ~10 -2 S / cm. Therefore, when the polymer electrolyte is used in the battery, the internal resistance increases, so that the discharge capacity of the battery is significantly reduced.
    Therefore, in order to secure an ion conductivity substantially the same as the ionic conductivity of the electrolyte solution, a gel electrolyte obtained by blending a polymer matrix with the electrolyte solution has been developed. The polymers used in this gel are mainly polymers soluble in the electrolyte, such as PEO. Since ionic conduction occurs through the liquid phase of the gel, a high ionic conductivity substantially equal to that of the electrolyte can be obtained. However, since these polymers are dissolved in the electrolyte, their mechanical strength is reduced, for example, losing their function as a solid. Therefore, when the gel electrolyte is used in the battery, the dendritic crystal growth cannot be completely suppressed, which eventually causes an internal short circuit. The problem to be solved therefore is the improvement of the mechanical strength of the gel electrolyte.
    As a means for improving the mechanical strength of the gel electrolyte, there is a method for producing a crosslinked gel electrolyte disclosed in, for example, Japanese Patent Application Laid-Open No. 5-109310. According to this method, a mixture of a photocrosslinkable monomer and an electrolyte solution is an electron beam. Alternatively, the gel electrolyte is crosslinked by irradiation with ultraviolet rays or the like. However, this method does not significantly improve the mechanical strength. Furthermore, the crosslinked gel electrolyte is not suitable as an active material of a positive electrode for 4V batteries such as LiCoO 2 and is decomposed or converted in a short time.
    Therefore, although a method of coexisting a gel electrolyte and a polypropylene porous membrane has been developed, as disclosed in, for example, Japanese Patent Application Laid-open No. 61-183253, employing a polypropylene porous membrane cannot be the ultimate solution. As in the case of using a porous separator, internal short-circuiting occurs due to lithium dendritic crystals.
    As described above, the gel electrolyte needs to have safety for the active material in a 4V battery and, in particular, sufficient ionic conductivity and sufficient mechanical strength to prevent internal short circuit due to lithium dendritic crystals.
    The present invention aims to provide a novel gel electrolyte having the necessary characteristics as described above and a battery using the gel electrolyte.
    1 is a vertical cross-sectional view of a coin-shaped lithium battery using the gel electrolyte of the present invention.
    2 is a graph showing charge-discharge curves of lithium batteries using a gel electrolyte of the present invention and lithium batteries using a gel electrolyte as a control, respectively.
    3 is a graph showing discharge characteristics of a lithium battery using a gel electrolyte of the present invention and a lithium battery using a gel electrolyte as a control.
    4 is a graph showing cycle characteristics of a lithium battery using the gel electrolyte of the present invention and a lithium battery using the gel electrolyte as a control.
    In order to solve the above problems, the gel polymer alloy electrolyte of the present invention is a polymer alloy film having a phase separation property with an organic electrolyte solution, and the film is one or more polymers which swell to some extent in the organic electrolyte solution and the organic material. It is made of a polymer soluble in the electrolyte and the size of the separated micro-phase of the soluble polymer in the polymer alloy film is adjusted to less than 100 nm. Since this value is much smaller than the diameter of the dendritic crystals, the dendritic crystals cannot penetrate into the polymer alloy film.
    In a preferred embodiment, poly (vinylidene fluoride) s (hereinafter simply referred to as PVDF) or copolymers of vinylidene fluoride are used as polymers which swell to some extent in the electrolyte solution, and poly (methyl methacryl) as a soluble polymer. Rate) (hereinafter simply referred to as PMMA), poly (methyl acrylate) or poly (ethyl methacrylate), preferably PMMA.
    The lithium-polymer battery of the present invention is composed of the above-described gel polymer alloy electrolyte constituted between a negative electrode, a positive electrode and these electrodes. Employment of the electrolyte of the present invention prevents the formation of dendritic crystals, thereby providing a battery having no internal short circuit and high cycle efficiency and safety.
    In a preferred embodiment, using a negative electrode prepared from at least one selected from the group consisting of metal lithium, lithium alloys, inorganic compounds capable of absorbing and releasing lithium, and carbon materials capable of absorbing and releasing lithium, The containing transition metal oxide is used as the positive electrode active material.
    The gel polymer alloy electrolyte of the present invention is composed of one or more polymers slightly swelling in an organic electrolyte and a polymer soluble in the organic electrolyte and containing a phase-separable polymer alloy film and an organic electrolyte in which the phase separation size of the soluble polymer is less than 100 nm. It is a polymer electrolyte.
    Phase separation of the polymer that swells to some extent in the organic electrolyte is not limited, but the preferred size is less than 100 nm.
    In the specification of the present invention, a slight swelling means that the polymer is insoluble but slightly swells in an organic electrolyte at room temperature so that the solubility cannot be measured using a conventional method. Means the average diameter of a domain of a polymer mainly composed of a slightly swollen polymer or the average diameter of a domain of a polymer mainly composed of a soluble polymer. It is preferable to measure the average diameter of the domain of the polymer containing the soluble polymer as the main component in terms of the contact of the soluble polymer with the negative electrode.
    The production of lithium dendritic crystals in this electrolyte is suppressed by controlling the size of the phase caused by phase separation of the polymer alloy film.
    The lithium polymer battery of the present invention is composed of the gel polymer alloy electrolyte of the present invention constituted between a negative electrode, a positive electrode and these electrodes. By employing the electrolyte of the present invention, a battery having no internal short circuit and high cycle efficiency and safety can be realized.
    Furthermore, in the lithium polymer battery, the gel polymer alloy electrolyte of the present invention is contained in at least one of the positive electrode and the negative electrode. By incorporating the polymer electrolyte of the present invention into the electrode (s), the supply of lithium ions or electrolyte to the active material is facilitated.
    As a polymer which swells to some extent in an organic electrolyte solution, it is preferable to use 1 or more types chosen from the group which consists of a copolymer of vinylidene fluoride and PVDF. Other monomers of the copolymer are not limited, but olefins such as ethylene, propylene and butene are preferred.
    As the polymer soluble in the organic electrolyte, PMMA is preferable to adjust the phase separation size of the soluble polymer to less than 100 nm.
    That is, the gel polymer electrolyte of the present invention is preferably composed of a polymer alloy film produced by mixing or mutual dissolving PMMA and at least one polymer selected from the group consisting of an organic electrolyte, a copolymer of vinylidene fluoride, and PVDF. Do.
    As the negative electrode, at least one selected from the group consisting of metal lithium, lithium alloys, inorganic compounds capable of absorbing and releasing lithium, and carbon materials capable of absorbing and releasing lithium is preferably used.
    It is preferable to use a lithium-containing transition metal oxide as the positive electrode active material.
    In the gel polymer alloy electrolyte of the present invention, the size of the phase separation is controlled to suppress the formation of lithium dendritic crystals.
    Depending on the combination of polymers, the structure of the polymer alloy is, for example, an archipelagic structure in which islands of polymer B are scattered in the sea of polymer A, or a modulation structure in which polymers A and B are continuously twisted with each other. In either case, the polymer alloy is formed by micro-phase separation into a phase containing a lot of (polymer A) and a phase containing a lot of (polymer B) and has a structure that can be designed to be smaller than several microns.
    The phase separation structure described above is a major factor for maintaining the mechanical strength of polymer alloy gels and achieving high ionic conductivity. When the polymer alloy film is immersed in the electrolyte solution, the electrolyte solution penetrates into the polymer soluble in the electrolyte solution, so that the polymer alloy film gels. However, because the slightly swelling polymers are microscopically twisted together to retain the soluble polymer, the soluble polymer remains stationary without flowing. The polymer alloy film thus functions as a gel with high mechanical strength and ionic conductivity.
    The lithium dendritic crystal has a diameter of 100 nm or more. This size is the basis for designing the polymer alloy of the present invention. Ionic conductivity through the electrolyte occurs through the phase of the soluble polymer in the organic electrolyte, so lithium precipitation occurs at the interface between the polymer phase and the lithium cathode.
    In this case, if the phase separation size of the soluble polymer is 100 nm or more, the dendritic crystal grows through this polymer phase. However, if this size is smaller than the diameter of the dendritic crystal, lithium cannot precipitate into the dendritic crystal and grows flat.
    Therefore, using the electrolyte of the present invention can realize a battery having no internal short circuit and high cycle efficiency and safety.
    In order to adjust the size of the phase separation to less than 100 nm, it is preferable to use at least one member selected from the group consisting of a copolymer of vinylidene fluoride and PVDF as a polymer that swells slightly in the organic electrolyte, and PMMA is preferable. Do.
    Since PVDF and PMMA are suitable for positive electrode active materials for 4V batteries such as LiCoO 2 , the electrolyte of the present invention can be used in a 4-volt lithium secondary battery, which has been difficult to realize by using the aforementioned crosslinked gel electrolyte.
    In particular, the use of metallic lithium, which easily precipitates as a dendritic crystal, can be used as a negative electrode, but a remarkable effect can be obtained. For example, lithium alloys that generate and grow dendritic crystals in a smaller amount than metallic lithium, and inorganic compounds that can absorb and release lithium. Alternatively, when carbon is used, the use of the electrolyte of the present invention can improve safety and various properties.
    EXAMPLE
    Embodiments of the present invention will be described below with reference to the drawings.
    Example 1
    In this embodiment, a gel electrolyte of a polymer alloy film prepared by dissolving PVDF, which is a polymer slightly swelling in an organic solvent, and PMMA, which is a soluble polymer, was dissolved in each other. The production method of the polymer alloy film is as follows.
    First, a polymer solution prepared by dissolving PVDF in N-methyl-2-pyrrolidone (hereinafter simply referred to as NMP) to a concentration of 1 to 10 wt.%, And PMMA in NMP to a concentration of 1 to 10 wt. The polymer solution obtained by mixing the prepared polymer solution in a weight ratio of 50:50 was applied onto a smooth metal plate or a glass plate, and a thin polymer alloy film was prepared by evaporating the solvent at 80 ° C. in a dryer. The coating volume of this solution was adjusted so that it might be 20 micrometers in film thickness. The resulting film was dried in vacuo at 80 ° C. to sufficiently dry the remaining solvent and water.
    As a result of observing the prepared polymer alloy film with a transmission electron microscope, no obvious phase separation structure was found. Since the presence of a phase separation structure of 100 nm or more can be confirmed by transmission electron microscopy, it can be concluded that the polymer alloy film according to the present invention has a phase separation structure of less than 100 nm.
    Gel electrolyte was obtained by immersing the above polymer alloy film in the bath of organic electrolyte solution. As the organic electrolyte solution, a solution prepared by dissolving LiPF 6 as a solute in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (volume ratio 25:75) to a concentration of 1.5 mol / liter was used.
    A disk having a diameter of 17 mm was punched out of the gel electrolyte obtained above, and inserted between two disks having a diameter of 15 mm made of metallic lithium foil, and set in a coin-shaped battery case. The case was sealed to prepare a cell for measuring ion conductivity. The ion conductivity sigma was measured by a countercurrent impedance method and found to be 1.2 × 10 −3 S · cm −1 .
    The coin-shaped cell shown in FIG. 1 was prepared using a 15 mm diameter disk obtained by punching from the electrolyte shown above. The positive electrode layer 4 is a mixture of a positive electrode current collector 5 made of aluminum foil with an aqueous dispersion solution of LiCoO 2 as an active material, carbon black as a conductive material and poly (ethylene tetrafluoride) as a binder. It was prepared by applying and drying (weight ratio 100: 3: 10), then rolling the current collector portion 5 to punch a disk having a diameter of 12.5 mm therefrom. The negative electrode layer 2 was manufactured by directly pressure-bonding a metal lithium disk having a diameter of 14 mm to the lid 3 of the coin-shaped battery case. The battery of Example 1 was prepared by stacking the positive electrode, the disk of the polymer alloy gel electrolyte and the negative electrode as described above, and then setting them in a coin-shaped battery case 6 and sealing them with a gasket 7.
    Comparative Example 1
    Using a gel electrolyte prepared by inserting PVDF gelled with electrolyte into a polypropylene porous membrane, a cell for ion conductivity measurement and a coin-shaped battery having the same structure as in Example 1 were prepared.
    A cell for measuring ion conductivity was prepared as follows. 1.5 g of PVDF powder was sufficiently dispersed in 8.5 g of an electrolyte solution prepared by dissolving LiPF 6 as a solute in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (volume ratio 25:75) to a concentration of 1.5 mol / liter. A polypropylene porous membrane separator (porosity: 38%) having a diameter of 17 mm was applied with the PVDF dispersion described above, and inserted between two disks having a diameter of 15 mm of metal lithium foil, and set in a coin-shaped battery case. . This case was sealed to manufacture a battery for measuring ion conductivity. The desired coin-shaped battery was heated at 90 ° C. for 5 minutes to gel the PVDF dispersion to prepare a desired polymer gel electrolyte. After completion of the heating, the coin-shaped battery was cooled to room temperature, and the ion conductivity σ of the gel electrolyte was measured by the reverse current impedance method. As a result, σ was 8.1 × 10 −4 S · cm −1 .
    A coin-shaped battery having the same structure as in Example 1 was manufactured in the same manner as in the case of a battery for measuring ion conductivity. This battery is referred to as the battery of Comparative Example 1.
    Comparative Example 2
    A coin-shaped battery having the same structure as in Example 1 was prepared using a crosslinked gel electrolyte.
    A coin-shaped battery was prepared as follows. An electrolyte solution prepared by dissolving LiPF 6 in a weight ratio of 20: 0.1: Mix by 80 to prepare a solution. This solution was applied onto the cathode metal lithium to have a thickness of 50 µm, irradiated with ultraviolet rays having a maximum output wavelength of 365 nm for 3 minutes to crosslink and cure the above polymer to form a gel electrolyte containing a nonaqueous electrolyte on the cathode metal lithium. The same positive electrode as in Example 1 was laminated on the gel electrolyte, and the obtained laminate was set in a battery case to prepare a battery of Comparative Example 2.
    2 shows the charge-discharge curves at the first cycle of each cell of Example 1 and Comparative Examples 1 and 2. FIG. Each cell was tested on a 0.56 mA / cm 2 constant ammeter and the measurements were measured at a voltage of 4.2 V to 3.0 V at room temperature.
    As can be seen from FIG. 2, the lithium-polymer batteries of Example 1 and Comparative Example 1 have sufficient performance characteristics as batteries operating at normal temperatures because the discharge capacity is 2.0 mA / cm 2 or more. On the other hand, the battery of Comparative Example 2 is not charged to 4.2V. The battery voltage during charging was a constant voltage near 4.1V. The reason is considered that the crosslinked gel electrolyte is decomposed by LiPF 6 having a strong oxidizing effect.
    Then the first embodiment and the comparative charge current of 0.2C (0.56mA / cm 2) for each cell of Example 1, each of 0.2C (0.56mA / cm 2), 0.5C (1.4mA / cm 2), 1.0C ( 2.8 mA / cm 2 ) and 2.0 C (5.6 mA / cm 2 ) were tested at discharge currents to determine their discharge capacity. 3 shows the results obtained.
    As can be seen from FIG. 3, the battery of Example 1 is superior to the battery of Comparative Example 1 in all discharge current values. The reason is that since the gel electrolyte of the battery of Example 1 is a substantially uniform polyelectrolyte due to the mutual dissolution of PVDF and PMMA, ion migration easily occurs in the whole separator. In the cell of Comparative Example 1, the porosity of the polypropylene porous membrane was low as 38%. Furthermore, since the cell had a structure in which the pore velocity of the porous membrane was filled with the gel electrolyte, ion transport was not observed throughout the separator. It does not happen easily, but only partially in the pore area. As can be seen from FIG. 3, the above difference becomes remarkable as the discharge rate is increased, that is, as the discharge current is increased.
    4 shows cycle characteristics of each battery of Example 1 and Comparative Example 1. FIG. The batteries of Example 1 and Comparative Example 1 were both charged and discharged stably until the end of the 300th cycle. When the battery of Example 1 was disassembled after the end of the 300th cycle, no penetration of dendritic crystals was found, and only a small amount of dendritic crystals accumulated at the interface between the lithium negative electrode and the electrolyte. When the battery of Comparative Example 1 was dismantled and observed in the same manner as above, no penetration of dendritic crystals was found, but gel electrolyte was formed in the pores of the polypropylene porous membrane. These facts show that the battery of Example 1 suppresses the growth of dendritic crystals and provides a lithium secondary battery having high safety and reliability.
    Example 2
    A polymer secondary battery was prepared by containing the polymer alloy gel electrolyte of the present invention in both the positive electrode and the negative electrode.
    The positive electrode was made up of 5 wt% lithium cobalt oxide, 0.15 g carbon black, and a 12 wt% solution with PVDF in N-methyl-pyrrolidone (hereinafter simply referred to as NMP) and a 12 wt% solution with PMMA in NMP. 4 g of the mixed solution was mixed, and the obtained paste was applied to an aluminum current collector, dried, rolled, and prepared by punching a contact with a diameter of 15 mm. The obtained positive electrode was then immersed in the same electrolyte solution as in Example 1 and treated under a vacuum of -50 cmHg.
    The negative electrode comprises 8.4 g of a mixture of 10 g of spherical graphite, 0.53 g of carbon fiber, a 12 wt% solution containing PVDF in NMP, and a 12 wt% solution containing PMMA in NMP, 4.2 g of NMP, and 4.2 g of acetonitrile. After mixing, the obtained paste was applied to a copper current collector, dried and rolled, and then prepared by punching a contact having a diameter of 15 mm. The obtained negative electrode was then immersed in the same electrolytic solution as in Example 1 and treated under vacuum of -50 cmHg.
    A polymer alloy gel electrolyte was prepared in the same manner as in Example 1 and a 16 mm diameter disk was punched out of this electrolyte.
    The positive electrode, the disc of the gel electrolyte, and the negative electrode were stacked, set in a coin-shaped battery case, and the case was sealed. In this way the obtained battery 0.2C (0.56mA / cm 2) and the charging current, respectively, of 0.2C (0.56mA / cm 2), 0.5C (1.4mA / cm 2), 1.0C (2.8mA / cm 2) And a discharge current of 2.0 C (5.6 mA / cm 2 ) to measure the discharge capacity. 3 shows the results obtained.
    As is apparent from FIG. 3, a battery prepared by containing the gel electrolyte of the present invention in the positive electrode and the negative electrode shows extremely good discharge characteristics even at a high discharge rate. There are two reasons for this. That is, the first reason is that the carbon anode has a much larger reaction area than the lithium metal electrode, and the second reason is that the active materials of the electrode plates used in Examples 1 and 1 are densified by rolling, This is because the movement of lithium ions or the electrolyte solution is somewhat suppressed during the discharge. Therefore, in each of the electrode plates of Example 2 prepared by containing the gel electrolyte in the electrode, since the polymer alloy is present around the active material, the polymer alloy absorbs the electrolyte even when the rolled electrode is used together with the electrolyte. Therefore, lithium ions or electrolytes can be smoothly supplied to the active material. It is considered that the battery of Example 2 can exhibit good characteristics even at a high discharge rate due to the above reasons.
    In each example, PVDF is used as a polymer that swells slightly in the electrolyte, but a copolymer of vinylidene fluoride or other polymer may be used instead of PVDF.
    In each example, PMMA was used as a polymer soluble in the electrolyte, but other polymers such as poly (methyl acrylate) and poly (ethyl methacrylate) may be used instead of PMMA.
    Proper mixing ratios of PVDF used as poorly soluble polymers in electrolytes and PMMA used as soluble polymers in electrolytes, although described in Example 2, were used to prepare electrolytes with small separation phases, high mechanical strength and high ion conductivity. The blending ratio of each material depends on the material.
    In the embodiment, LiPF 6 was used as the solute of the organic electrolyte, but other lithium salts such as LiCF 3 SO 3 , LiClO 4 , LiN (CF 3 SO 2 ) 2 , LiAsF 6 , and LiBF 4 may be used instead of LiPF 6 .
    In each embodiment, a mixed solvent (volume ratio 25:75) of ethyl carbonate and ethyl methyl carbonate was used as a solvent of the organic electrolyte, but other organic solvents or mixed solvents of the same amount of propylene carbonate and ethylene carbonate instead of the above-described mixed solvents A mixed solvent of may be used.
    Metal lithium, and a carbon material capable of absorbing and releasing lithium were used as the negative electrode in each embodiment, but the present invention can be applied to a lithium ion battery, and also a lithium alloy or a lithium compound capable of absorbing and releasing lithium. You may use it.
    In each example, LiCoO 2 was used as the positive electrode active material, but other lithium transition metal oxides (eg, LiNiO 2 , LiMn 2 O 4 , LiMnO 2, etc.) or metal compounds containing no lithium at all (eg, MnO 2 , V 2 O 5, etc.) may be used.
    Gel polymer according to the present invention comprising a polymer alloy film and an organic electrolyte comprising one or more polymers slightly swelling in the organic electrolyte and a polymer soluble in the organic electrolyte and having a phase separation of less than 100 nm in phase separation of the soluble polymer. The electrolyte and the lithium-polymer battery using the same have high cycle efficiency with high safety, high reliability, and no internal short circuit since the formation of lithium dendritic crystals is suppressed. Therefore, it is expected that the contribution to the related industries will be very large.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] It comprises an organic electrolyte and a polymer alloy film, which is composed of at least one polymer that swells slightly in the organic electrolyte and a polymer soluble in the organic electrolyte and having phase separation of less than 100 nm in the size of the phase separation of the soluble polymer. Gel polymer electrolyte.
    [2" claim-type="Currently amended] The polymer electrolyte according to claim 1, wherein the polymer which swells slightly in the organic electrolyte is selected from the group consisting of copolymers of vinylidene fluoride and poly (vinylidene fluoride) s.
    [3" claim-type="Currently amended] The polymer electrolyte of Claim 1 wherein the polymer soluble in the organic electrolyte is poly (methyl methacrylate).
    [4" claim-type="Currently amended] The polymer alloy film of claim 1, wherein the polymer alloy film comprises at least one polymer selected from the group consisting of copolymers of vinylidene fluoride and poly (vinylidene fluoride) and poly (methyl). Gel polymer electrolyte prepared by mixing methacrylate or dissolving each other and having phase separation of less than 100 nm in size of phase separation of the soluble polymer.
    [5" claim-type="Currently amended] In a lithium-polymer battery composed of a negative electrode, a positive electrode, and a polymer electrolyte composed between these electrodes, the polymer electrolyte is composed of at least one polymer that swells slightly in the organic electrolyte and a polymer soluble in the organic electrolyte, and phase separation of the soluble polymer. Lithium-polymer battery, characterized in that the gel polymer electrolyte containing a polymer alloy film and an organic electrolyte having a phase separation of less than 100nm in size.
    [6" claim-type="Currently amended] The lithium polymer battery of claim 5, wherein the polymer electrolyte is contained in a negative electrode, a positive electrode, or two of them.
    [7" claim-type="Currently amended] The negative electrode of claim 5 or 6, wherein the negative electrode is selected from at least one selected from the group consisting of metal lithium, lithium alloys, inorganic compounds capable of absorbing and releasing lithium, and carbon materials capable of absorbing and releasing lithium. Lithium-polymer battery produced.
    [8" claim-type="Currently amended] The lithium-polymer battery according to claim 5 or 6, wherein the active material of the positive electrode is a lithium-containing transition metal oxide.
    [9" claim-type="Currently amended] The lithium-polymer battery according to claim 5 or 6, wherein the polymer which swells to some extent in the organic electrolyte is selected from the group consisting of copolymers of vinylidene fluoride and poly (vinylidene fluoride) s.
    [10" claim-type="Currently amended] The lithium-polymer battery according to claim 5 or 6, wherein the polymer soluble in the organic electrolyte is poly (methyl methacrylate).
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    同族专利:
    公开号 | 公开日
    ID19572A|1998-07-23|
    EP0858119A3|2006-02-01|
    EP0858119A2|1998-08-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-01-20|Priority to JP97-007285
    1997-01-20|Priority to JP728597
    1998-01-19|Application filed by 모리시타요이찌, 마쓰시타덴키산교가부시키가이샤
    1998-10-26|Publication of KR19980070598A
    2001-10-19|Application granted
    2001-10-19|Publication of KR100306870B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP97-007285|1997-01-20|
    JP728597|1997-01-20|
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