WO2002078114A1 - Batterie lithium polymere et procede de production correspondant - Google Patents

Batterie lithium polymere et procede de production correspondant Download PDF

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Publication number
WO2002078114A1
WO2002078114A1 PCT/JP2002/002872 JP0202872W WO02078114A1 WO 2002078114 A1 WO2002078114 A1 WO 2002078114A1 JP 0202872 W JP0202872 W JP 0202872W WO 02078114 A1 WO02078114 A1 WO 02078114A1
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WIPO (PCT)
Prior art keywords
solid electrolyte
secondary battery
negative electrode
lithium polymer
polymer secondary
Prior art date
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PCT/JP2002/002872
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English (en)
Japanese (ja)
Inventor
Motoaki Nishijima
Naoto Torata
Naoto Nishimura
Takehito Mitate
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Sharp Kabushiki Kaisha
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Priority to JP2002576043A priority Critical patent/JP4365098B2/ja
Publication of WO2002078114A1 publication Critical patent/WO2002078114A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/188—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Lithium polymer secondary battery and method of manufacturing the same Lithium polymer secondary battery and method of manufacturing the same
  • the present invention relates to a lithium polymer secondary battery having a solid electrolyte having excellent safety and cycle characteristics, and has excellent battery characteristics and high load characteristics, particularly has excellent cycle characteristics, and has excellent stability in battery characteristics.
  • the present invention relates to an excellent lithium polymer secondary battery and a method for producing the same. Background art
  • Secondary batteries are often used as power supplies for portable devices from the viewpoint of economy.
  • nickel-cadmium batteries are currently most commonly used, and nickel-metal hydride batteries have recently become widespread.
  • lithium secondary batteries are becoming the mainstay of secondary batteries because of their higher output voltage and higher energy density than nickel-cadmium batteries and nickel-metal hydride batteries.
  • the lithium secondary battery lithium cobalt acid L i C o 0 2, lithium, nickel L i N i 0 2, have a solid solutions thereof L i (C o!
  • This battery has a solid electrolyte, and can be easily sealed with a resin film or the like without the risk of liquid leakage, even if it is not completely sealed with a metal can or the like as in current lithium secondary batteries. It has features such as the ability to make batteries thinner.
  • the gel-like solid electrolyte is made of a polymer obtained by dissolving a high molecular compound such as fluoropolymer represented by polyvinylidene fluoride (PVdF) or polyacrylonitrile (PAN), and a lithium salt in an organic solvent.
  • PVdF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • the resulting solution is classified into two types: polymerized by applying energy such as heat or light (chemical gel).
  • These lithium polymer secondary batteries have the feature that they can be made thinner and larger in area.
  • a lithium polymer secondary battery is usually manufactured by laminating several combinations of a positive electrode and a negative electrode.
  • the method of impregnation with an organic electrolyte is the most problematic.
  • the electrodes are stacked and the organic electrolyte is impregnated between them, and then the organic electrolyte is solidified.
  • it is very difficult to impregnate the organic electrolyte into the electrodes it is difficult to manufacture a large-area battery.
  • a battery is manufactured by laminating electrodes with solid electrolytes that are individually polymerized (cured) by heat or light, so that the electrodes do not adhere firmly to each other, and the physical strength of the battery cannot be secured. There is a problem in that the performance is degraded when is repeatedly used.
  • an electrolyte layer for transferring lithium ions between the positive electrode and the negative electrode is required.
  • the electrolyte layer needs to have a certain thickness and strength in order to prevent an internal short circuit of the battery, and a porous material is usually used as a structural material in the electrolyte layer.
  • Such a lithium polymer primary battery has a porous body as a structural material and a solid body. It can be manufactured by forming in advance a solid electrolyte layer composed of a solidified solid electrolyte and sandwiching this between a positive electrode and a negative electrode. However, even in this case, the problem that the performance deteriorates when the battery is used repeatedly cannot be solved.
  • a porous body serving as a structural material is disposed on an electrode surface, and the porous body and the electrode are impregnated with an organic electrolyte.
  • the degree of curing of the electrode gel is not sufficient.
  • the gel is physically isolated by the structural material, there is a problem that the strength of the interface between the electrode and the electrolyte layer cannot be sufficiently secured.
  • Japanese Patent Application Laid-Open No. Hei 11-2603336 discloses a technique using a nonwoven fabric having a specific fiber system, porosity and thickness.
  • Japanese Patent Application Laid-Open No. 2000-220228 discloses a technology using a nonwoven fabric having a specific vicat softening temperature.
  • No. 5,274,42 discloses a technique using a nonwoven fabric having a specific thickness, basis weight, and weight.
  • lithium secondary batteries have a much higher theoretical energy density than other batteries, and can be made smaller and lighter. Therefore, they have been actively researched and developed as power sources for portable electronic devices. However, with the advancement of portable electronic devices, further weight reduction and thickness reduction are required. In addition, devices such as mobile phones are required to have reliability and safety against a large number of repeated charge / discharge cycles.
  • lithium secondary batteries use an organic electrolyte in which a lithium salt is dissolved in an organic solvent as the electrolyte between the positive electrode and the negative electrode.
  • Iron and aluminum cans are used as exterior materials to maintain reliability. For this reason, the weight and thickness of the lithium secondary battery are limited to the weight and thickness of the metal can, which is an exterior material thereof.
  • a lithium polymer secondary battery is a battery using a solid electrolyte, that is, a solid electrolyte such as a lithium ion conductive polymer or a lithium ion conductive gel. Since the electrolyte is solid, the battery can be easily sealed, and very light and thin materials such as aluminum laminate resin film can be used for the exterior material, further reducing the weight and thickness of the battery Becomes possible.
  • the above-mentioned lithium ion conductive polymer or lithium ion conductive gel is often obtained by three-dimensionally polymerizing (crosslinking) a polymerizable monomer by adding a lithium salt and, in some cases, an organic solvent.
  • a polymerization reaction by irradiation with light such as radiation or ultraviolet light, a polymerization reaction by heat, and the like are used.
  • JP-A-5-290885 discloses a method of forming an electrode and an electrolyte by using ionizing radiation such as an electron beam. Since the electron beam has good transparency, an excellent polymer solid electrolyte can be formed inside the composite electrode. However, there is a problem that a portion having a different polymerization state easily occurs in the electrode thickness direction, and it is difficult to sufficiently crosslink. There is also a problem that a device for generating ionizing radiation is expensive.
  • Japanese Patent Application Laid-Open No. H10-209409 discloses that an actinic ray-polymerizable compound having a specific structure and an actinic ray polymerization initiator having a specific structure are combined by actinic rays such as ultraviolet rays and visible rays.
  • a method for forming a polymer solid electrolyte by using the method is disclosed. According to this method, the polymerizability is good, the polymerization reaction proceeds even with a small amount of the polymerization initiator added, and a stable polymer solid electrolyte with few residual double bonds and residual by-products can be obtained. Batteries with excellent reliability have been obtained.
  • the formation of each electrode and electrolyte layer is a one-step polymerization reaction, and ultraviolet rays penetrate inside the electrodes. However, there is a problem that sufficient crosslinking is difficult.
  • Japanese Patent Application Laid-Open No. H11-1497989 discloses that a combination of a thermal polymerization initiator and a polymerizable compound, which are susceptible to a polymerization reaction due to heat, is excellent in the inside of a composite electrode where actinic rays cannot reach.
  • a method for forming a solid polymer electrolyte gel has been disclosed. According to this method, a battery having a long life and excellent reliability is obtained.
  • the formation of each electrode and electrolyte layer is a one-step polymerization method, and the polymerization by heat is more difficult than the polymerization by ultraviolet irradiation, especially in the case of solid electrolyte polymer gel when the battery is assembled.
  • the occurrence rate of short-circuit becomes high in the inside.
  • Japanese Patent Application Laid-Open No. 11-185584 discloses a polymer solid electrolyte formed by radical polymerization by ionizing radiation, and a lithium battery comprising a power generation element, in which a thermal polymerization initiator is contained in the electrolyte. It is stated that it should be included.
  • the polymerizable monomer near the surface is polymerized and fixed by ionizing radiation, and then the unreacted polymerizable monomer away from the surface is polymerized by heat. Less unreacted polymerizable monomers.
  • Japanese Patent Application Laid-Open No. 9-129249 discloses that a mixture of a polymerizable monomer and a lithium salt to which a photopolymerization initiator and a thermal polymerization initiator are added is cast on a positive electrode and irradiated with ultraviolet light for several minutes.
  • a method of forming a solid electrolyte battery in which a polymer solid electrolyte is provided between a positive electrode and a negative electrode by a two-stage polymerization method in which thermal polymerization is performed after photopolymerization by the method described above.
  • An object of the present invention is to provide a lithium polymer secondary battery having a solid electrolyte having excellent safety and cycle characteristics.
  • an object of the present invention is to reduce the amount of unreacted polymerizable monomer and unreacted polymerization initiator that become a solid electrolyte inside the composite electrode, and at the same time, to improve the adhesiveness at each interface of the positive electrode layer Z
  • An object of the present invention is to provide a lithium polymer secondary battery having excellent battery characteristics and high load characteristics, particularly excellent cycle characteristics, and excellent stability of battery characteristics.
  • a lithium polymer secondary battery having a solid electrolyte between a positive electrode and a negative electrode, wherein the solid electrolyte is formed integrally with the positive electrode or the negative electrode, and has a light transmittance of 5%.
  • a lithium polymer secondary battery (Invention 1) comprising 0% or more of a porous material, an organic electrolyte, and a polymer is provided.
  • a lithium polymer primary battery in which a solid electrolyte layer supported by a porous material having a light transmittance of 50% or more is interposed between a positive electrode and a negative electrode, and the molded positive electrode material And at least one electrode material of the anode material and the porous material for the solid electrolyte layer include at least a polymerizable monomer, a lithium salt, a photopolymerization initiator, and a thermal polymerization initiator having the same or different compositions. Impregnated with a mixed precursor solution for forming a solid electrolyte, and integrating the porous material with the positive electrode material or the negative electrode material, and irradiating light in a temperature range of 30 to 100 to carry out the first polymerization.
  • the positive electrode material and the negative electrode material are bonded so that the solid electrolyte is interposed between the positive electrode material and the negative electrode material, and then heated in a temperature range of 30 to 100 t: for the second time.
  • Lithium polymer obtained by polymerizing Secondary batteries, and
  • a lithium polymer secondary battery in which a solid electrolyte layer supported by a porous material having a light transmittance of 50% or more is interposed between a positive electrode and a negative electrode.
  • One of the electrode materials of the negative electrode material and A porous material for a solid electrolyte layer is impregnated with a mixed precursor solution for forming a solid electrolyte having the same or different composition and containing at least a polymerizable monomer, a lithium salt, a photopolymerization initiator and a thermal polymerization initiator.
  • the other electrode material is impregnated with a mixed precursor solution for forming a solid electrolyte containing at least a polymerizable monomer, a lithium salt and a thermal polymerization initiator, and the one electrode material and the porous material are bonded together.
  • the first polymerization is performed by irradiating light in a temperature range of 30 to 100 ° C., and at that stage, a solid electrolyte is interposed between the positive electrode material and the negative electrode material, and the other is Lithium polymer secondary battery obtained by laminating the above electrode materials and then heating in a temperature range of 30 to 100 ° C to perform the second polymerization.
  • a method for manufacturing a lithium polymer secondary battery in which a solid electrolyte layer supported by a porous material is interposed between a positive electrode and a negative electrode, wherein at least one of the molded positive electrode material and the negative electrode material is formed.
  • a mixed precursor solution for forming a solid electrolyte containing at least a polymerizable monomer, a lithium salt, a photopolymerization initiator and a thermal polymerization initiator having the same or different composition is added to the electrode material and the porous material for the solid electrolyte layer. Impregnation, irradiate light at a temperature in the range of 30 to 100 ° C.
  • a method for producing a lithium polymer secondary battery in which a solid electrolyte layer supported by a porous material is interposed between a positive electrode and a negative electrode comprising: forming one of the molded positive electrode material and the negative electrode material A mixed precursor for forming a solid electrolyte comprising at least a polymerizable monomer, a lithium salt, a photopolymerization initiator and a thermal polymerization initiator of the same or different composition in the electrode material and the porous material for the solid electrolyte layer.
  • FIG. 1 is a schematic sectional view showing a basic structure of a lithium polymer secondary battery of the present invention.
  • FIG. 2 is a schematic diagram of a sheet-shaped lithium polymer secondary battery produced in Example 1 of the present invention.
  • FIG. 3 is a schematic sectional view showing a basic structure of another lithium polymer secondary battery of the present invention.
  • FIG. 4 is a graph showing the results of a charge / discharge test (relationship between current value and discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Example 11 and Comparative Examples 6 to 10.
  • FIG. 5 is a graph showing the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Examples 11 to 14 and Comparative Example 11.
  • FIG. 6 is a graph showing the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Examples 15 to 19.
  • FIG. 7 is a graph showing the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Examples 20 to 23.
  • FIG. 8 is a graph showing the results of a charge / discharge test (relationship between current value and discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Examples 11 and 24.
  • Fig. 9 is a graph showing the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of the sheet-shaped lithium polymer secondary batteries produced in Examples 11 and 25.
  • FIG. 10 is a graph showing the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of the sheet-shaped lithium polymer primary batteries produced in Examples 15 and 26.
  • the mixed precursor solution is impregnated with the porous material on the electrode surface in advance, and then mixed with the mixed precursor solution in the porous material and the mixed precursor solution on the electrode surface by light irradiation. Are simultaneously cured (polymerized) to form a solid electrolyte layer.
  • the light transmittance when the light (visible light, ultraviolet light) for curing the mixed precursor solution passes through the porous material is 50% or more, and it is desirable that the light transmittance is as large as possible.
  • the mixed precursor solution impregnated not only on the porous material side but also on the electrode side is sufficiently solidified, and the solidification of the organic electrolyte solution is sufficiently advanced.
  • the cycle characteristics of the battery are improved. Is improved.
  • the porous material has irregularities (surface roughness) of 1 to 5 m on its surface, the physical strength of the electrode surface and the solid electrolyte layer is improved.
  • FIG. 1 is a schematic sectional view showing a basic structure of a lithium polymer secondary battery of the present invention.
  • 1 is a porous material
  • 2 is a solid electrolyte
  • 3 is an electrode active material (electrode material)
  • 4 is a current collector.
  • the porous material in the solid electrolyte in the present invention is not particularly limited as long as it has a light transmittance of 50% or more. If the light transmittance is less than 50%, curing (solidification) on the electrode does not proceed sufficiently, the strength of the solid electrolyte becomes insufficient, and the performance of the battery deteriorates. Further realization The range of possible light transmittance is preferably 75% or more.
  • the porous material in the solid electrolyte according to the present invention has irregularities of 1 to 5 m on its surface. If the surface roughness of the porous material is less than 1 m, it is not preferable because the physical bonding strength between the solid electrolyte and the electrode becomes weak. Further, when the surface irregularity exceeds 5 m, the thickness of the solid electrolyte layer is likely to be uneven even if the physical bonding strength between the solid electrolyte and the electrode is sufficient, which is not preferable. When the thickness of the solid electrolyte layer is not uniform, current concentrates on a portion where the thickness of the solid electrolyte layer is thin, a load is applied to a specific portion in the electrode, and partial deterioration of the electrode occurs.
  • a porous material such as a polymer fiber and a microporous membrane separator formed from polyethylene and / or polypropylene can be used.
  • a step of forming irregularities suitable for the present invention on the surface is required, and the cost is increased. Therefore, a non-woven fabric is preferable as the porous material.
  • a material of the nonwoven fabric a material that does not dissolve or swell in an organic solvent contained in the mixed precursor solution for forming a solid electrolyte is preferable.
  • organic materials such as polyester-based polymers, polyolefin-based polymers and ether-based polymers, and inorganic materials such as glass.
  • a nonwoven fabric made of a polyester-based polymer is particularly preferable because the performance of the battery is hardly deteriorated.
  • the porous material has a thickness of 5 to: L O O m, preferably 150 °. If the thickness of the porous material is less than 5 m, a portion where the thickness of the solid electrolyte layer becomes 0 is generated, which may cause an internal short circuit of the battery, which is not preferable. On the other hand, if the thickness exceeds 100 m, the energy density of the battery may decrease, which is not preferable.
  • the porous material preferably has a porosity of 60% or more. If the porosity is small, the diffusion path of lithium ions is reduced, and the performance of the battery is lowered, which is not preferable.
  • Porous material those having a air permeability of 1 ⁇ 5 0 0 sec Z cm 3 is favorable Good. If the air permeability is less than 1 sec 3 cm 3 , it is not preferable because the ionic conductivity cannot be sufficiently obtained. On the other hand, if the air permeability exceeds 500 sec Z cm 3 , the mechanical strength is not sufficient and a short circuit of the battery is likely to occur, which is not preferable.
  • the solid electrolyte in the lithium polymer secondary battery of the present invention includes a polymerizable monomer for solidification, an organic solvent containing a lithium salt as a solute (organic electrolyte), and a polymerization initiator for promoting solidification if necessary.
  • a mixed precursor solution hereinafter, referred to as “precursor solution” or “precursor solution”
  • precursor solution which is solidified by a crosslinking reaction or a polymerization reaction.
  • Examples of the polymerizable monomer of the precursor solution include ethylene oxide, propylene oxide, and compounds having an acryloyl group, a methyl acryloyl group, an aryl group, or the like at a terminal group.
  • the polymer is polyfunctional with respect to the polymerization site so that the polymer forms a three-dimensional crosslinked gel structure.
  • These polymerizable monomers may be used alone or in combination of two or more. By mixing a polymerizable monomer having a monofunctional group and a polymerizable monomer having a polyfunctional group, a wide variety of crosslinked and non-crosslinked solid electrolytes can be formed.
  • the amount of the polymerizable monomer in the precursor solution is based on the total amount of the polymerizable monomer and the lithium salt in volume fraction:! ⁇ 50% is preferred, and 1 ⁇ : L 0% is particularly preferred.
  • organic solvent for the precursor solution examples include cyclic carbonates such as propylene carbonate, ethylene carbonate (EC), and butylene carbonate; chain carbonates such as getyl carbonate, dimethyl carbonate, and methyl ethyl carbonate; Lactones such as ton (GBL), ⁇ -valerolactone, 6-valerolactone; Cyclic ethers such as oral furan, 2-methyltetrahydrofuran, and dioxolane; ethers such as getyl ether, dimethoxetane, dietoxetane, and methoxhetoxetane; dimethyl sulfoxide; glymes such as methyl diglyme and edilglyme Alcohols such as ethylene glycol, methylcellosolve and glycerin; lumamide, N-ethylformamide, N, acetonitrile, propionitol, methoxyacetitol, 3-methoxypropionit
  • These solvents may be used alone or in combination of two or more, and examples thereof include a mixed solvent of EC and GBL.
  • the organic solvent of the precursor solution If water is contained in the organic solvent of the precursor solution, a side reaction between the water and the solvent occurs during charge / discharge of the battery, leading to a decrease in the efficiency of the battery itself, a decrease in cycle life, and generation of gas. Problems occur. For this reason, it is necessary to minimize the amount of water contained in the organic solvent, and the content is preferably 100 ppm or less, more preferably 100 ppm or less. Therefore, in some cases, the organic solvent is treated by a known dehydration method using a hydride of an alkali metal such as molecular sieve, an alkali metal, an alkaline earth metal, or calcium hydride, or aluminum. Is preferred.
  • the solute in the precursor solution lithium perchlorate (L i C 1 0 4) , e Ufu' lithium (L i BF 4), the lithium Kisafuruorori phosphate (L i PF 6), 6 fluoride arsenic lithium, tri Furuorome evening Nsuruhon Sanli lithium (L 'i CF 3 S_ ⁇ 3), lithium halide, aluminate chloride Sanli lithium, lithium such as lithium bis full O Lome evening Nsuruhoniruimi de Salts, and at least one of them can be used.
  • solid electrolytes may be used for the positive electrode side, the negative electrode side, and the solid electrolyte disposed therebetween, and the solid electrolytes may be used in different mixing ratios.
  • concentration of the solute in the precursor solution is between 1.0 and 3.5 mol Zl, with 1.0 to 2.75 mol 1/1 being particularly preferred.
  • Polymerization initiators that may be added to the precursor solution to accelerate the crosslinking reaction or the polymerization reaction include phosphine oxides, acetophenones, benzophenones, monohydroxyketones, Michler ketones, benzyls, and benzoins.
  • Photopolymerization initiators such as benzoin ether-based, benzyldimethyl ketal-based compounds and the like. These initiators may be used alone or in combination of two or more.
  • phosphine oxide-based photopolymerization initiators are particularly preferred because of their high reactivity and excellent compatibility with the polymerizable monomers and organic solvents described below.
  • the addition amount of the photopolymerization initiator is preferably as small as possible in order to reduce reactions such as decomposition of the initiator during charge and discharge. However, when the amount is too small, the polymerization reaction does not sufficiently occur, and unreacted polymerizable monomers may remain, which is not preferable.
  • the amount of the photopolymerization initiator to be added is preferably from 100 to 100 p, based on the total amount including the polymerizable monomer and the lithium salt, and in some cases, the organic solvent.
  • the range of pm is preferable, the range of 100 to 500 ppm is more preferable, and the range of 100 to 300 ppm is more preferable.
  • a powder of a transition metal oxide or a lithium transition metal oxide as a positive electrode active material, a conductive agent, a binder, and, in some cases, a precursor It is formed by mixing solutions.
  • lithium transition metal oxide Lithium cobalt (L i x C o O 2 : 0 ⁇ x ⁇ 2), lithium acid nickel relay (L i x N i O 2 : 0 ⁇ x ⁇ 2), lithium acid nickel-cobalt composite oxide (L i x (n i have y C o y) 0 2: 0 ⁇ 2, 0 ⁇ y ⁇ 1), lithium ⁇ beam manganese (L i x M n 2 O 4: 0 ⁇ X ⁇ 2, L i x M n O 2: 0 ⁇ x ⁇ 2), lithium vanadium (Li V 2 0 5, L i VO 2), lithium acid tungsten (L i W_ ⁇ 3), molybdenum lithium acid (L i M o O 3) and the like.
  • Lithium cobalt Li i x C o O 2 : 0 ⁇ x ⁇ 2
  • lithium acid nickel relay Li i x N i O 2 :
  • Examples of the conductive agent include acetylene black, carbon materials such as graphite powder, metal powder, and conductive ceramics.
  • the conductive agent improves the electron conductivity of the positive electrode.
  • binder examples include fluoropolymers such as polytetrafluoroethylene and polyvinylidene fluoride, and polyolefin polymers such as polyethylene and polypropylene.
  • the mixing ratio thereof is such that 1 to 50 parts by weight of the conductive agent and 1 to 50 parts by weight of the binder (preferably 1 to 50 parts by weight) are added to 100 parts by weight of the transition metal oxide or the lithium transition metal oxide. 30 parts by weight).
  • the amount of the conductive agent is less than 1 part by weight, the resistance or polarization of the electrode increases, and the capacity as the electrode decreases, so that a practical lithium secondary battery cannot be constructed.
  • the amount of the conductive agent is more than 50 parts by weight, the amount of the transition metal oxide or the lithium transition metal oxide in the electrode is reduced, so that the capacity is undesirably reduced.
  • the amount of the binder is less than 1 part by weight, the binding ability is lost, and the electrode cannot be formed.
  • the negative electrode used in the lithium polymer secondary battery of the present invention is formed by mixing a negative electrode active material, a binder, and, in some cases, a precursor solution.
  • the negative electrode active material examples include lithium alloys such as lithium metal and lithium aluminum, and materials capable of inserting and removing lithium ions, such as conductive polymers such as polyacetylene, polythiophene, and polyparaphenylene, pyrolytic carbon, and catalysts.
  • conductive polymers such as polyacetylene, polythiophene, and polyparaphenylene
  • pyrolytic carbon and catalysts.
  • Pyrolysis carbon pyrolyzed in the presence of carbon, carbon fired from pitch, coke, tar, etc., carbon obtained by firing polymers such as cellulose, phenolic resin, natural graphite, artificial graphite, expanded graphite, etc. which graphite material, it is possible to use a substance alone or a composite material such as W monument 2, M o 0 2 which can be inserted 'elimination reactions of lithium ions.
  • pyrocarbon pyrocarbon decomposed in the presence of a catalyst in the gas phase
  • carbon fired from pitch coke, tar, etc.
  • carbon obtained by firing polymers such as cellulose and phenolic resin
  • natural Graphite materials such as graphite, artificial graphite and expanded graphite are preferred.
  • the negative electrode active material a highly crystalline graphite as a core material and a low crystalline carbon material or a graphite material having amorphous carbon adhered to the surface can be used.
  • the negative electrode preferably contains a carbon material in which amorphous carbon is attached to the surface of graphite particles as a negative electrode active material.
  • Such a graphite material has the effect of reducing the specific surface area of the core material, and significantly suppresses the decomposition reaction of the polymer (ion conductive polymer), organic electrolyte, and lithium salt that occurs at the negative electrode when the battery is charged. Therefore, it is preferable because it has an effect of improving the charge / discharge cycle life and suppressing gas generation due to the decomposition reaction.
  • the above-mentioned carbon material has specific properties related to the specific surface area measured by the BET method.
  • the pores are closed to some extent by the attachment of amorphous carbon, and the specific surface area is preferably 5 m 2 Zg or less. If the specific surface area exceeds 5 m 2 / g, the contact area with the ion-conductive polymer and the organic electrolyte increases, which is not preferable because the decomposition reaction easily occurs.
  • Such graphite materials are produced by attaching low-crystalline carbon to the surface of highly crystalline graphite by a gas-phase method, a liquid-phase method, a solid-phase method, or the like. It can be obtained by immersing it in coal-based heavy oil or heavy oil such as heavy oil, pulling it up, heating it at or above the carbonization temperature to decompose the heavy oil, and pulverizing it if necessary.
  • the carbon material preferably has a particle size distribution of about 0.1 to 150 / Xm, more preferably about 0.5 to 50. If the particle size is smaller than 0.1 ⁇ m, there is a high risk of causing an internal short circuit through the pores of the battery separator, which is not preferable. If the particle size is larger than 150 m, the uniformity of the electrode, the packing density of the active material, and the handling property in the process of manufacturing the electrode are reduced, and the particle size is larger than the net thickness of the electrode. It is not preferable because it becomes sharp.
  • Examples of the conductive agent include carbon materials such as acetylene black and graphite powder, metal powders, and conductive ceramics.
  • the conductive agent improves the electron conductivity of the negative electrode.
  • binder examples include fluoropolymers such as polytetrafluoroethylene and polyvinylidene fluoride, and polyolefin polymers such as polyethylene and polypropylene.
  • the mixing ratio is preferably such that the binder is 1 to 50 parts by weight (preferably 1 to 30 parts by weight) with respect to 100 parts by weight of the negative electrode active material.
  • the amount of the binder is less than 1 part by weight, the binding ability is lost, and the electrode cannot be formed.
  • the amount of the binder is more than 50 parts by weight, the resistance or polarization of the electrode increases, and the amount of the negative electrode active material in the electrode decreases.
  • each electrode is obtained by dissolving the mixture in a solvent such as N-methyl-2-pyrrolidone to form a slurry, applying the slurry to a current collector, and drying. Thereafter, the electrode can be compressed to a desired thickness.
  • a solvent such as N-methyl-2-pyrrolidone
  • a conductive material such as a metal foil, a metal mesh, or a metal nonwoven fabric can be used as the current collector.
  • a porous material is placed on the surface of the electrode thus prepared, and the precursor solution is impregnated.
  • a method of disposing the porous material on the surface of the electrode there are a method of placing the porous material on the electrode surface, and a method of inserting the electrode into the bag-shaped porous material.
  • the method of impregnating the precursor solution include a method of immersion in the precursor solution and a method of immersion in the precursor solution under reduced pressure, vacuum, or pressure.
  • the precursor solution impregnated in the electrode and the porous material is simultaneously cured (polymerization reaction) by light irradiation to form a solid electrolyte layer.
  • Irradiation light includes electromagnetic waves such as radiation, visible light, and ultraviolet light. Visible light and ultraviolet light are preferable in view of the cost of the device, and ultraviolet light is particularly preferable.
  • the irradiation time depends on the type of light, but is preferably 2 minutes or less in order to polymerize in a temperature range of 30 to 100 ° C. Further, from the viewpoint of productivity, it is particularly preferable that the time is within 10 seconds.
  • the lithium polymer secondary battery according to Invention 1 is configured such that the positive electrode layer and the current collector, and the negative electrode layer and the current collector are respectively bonded to external electrodes, and the above-described solid electrolyte layer is interposed therebetween. You. In addition, by stacking a combination of a positive electrode and a negative electrode, a lithium polymer secondary battery having a large capacity can be formed.
  • the shape of the lithium polymer secondary battery of Invention 1 is not particularly limited, and examples thereof include a cylindrical shape, a button shape, a square shape, and a sheet shape, but are not limited thereto.
  • examples of the exterior material include a metal and an aluminum laminated resin film. These batteries are manufactured in an inert atmosphere, such as argon, or in dry air to prevent ingress of moisture. It is preferred to do so.
  • the lithium polymer secondary battery of Invention 1 is obtained by curing a polymerizable monomer only by photopolymerization, and further comprises adding a thermal polymerization initiator to the precursor solution to convert the polymerizable monomer into thermal polymerization and photopolymerization. By curing at a stage, a lithium polymer secondary battery having better cycle characteristics and battery performance can be obtained.
  • a lithium polymer secondary battery in which a solid electrolyte layer supported by a porous material having a light transmittance of 50% or more is interposed between a positive electrode and a negative electrode. At least one of the negative electrode materials and the porous material for the solid electrolyte layer contain at least a polymerizable monomer, a lithium salt, a photopolymerization initiator, and a thermal polymerization initiator having the same or different compositions.
  • the precursor solution for forming the solid electrolyte is impregnated, the porous material is integrated with the positive electrode material or the negative electrode material, and the first polymerization is performed by irradiating light at a temperature in the range of 30 to 100 ° C.
  • the positive electrode material and the negative electrode material are bonded together so that the solid electrolyte is interposed between the positive electrode material and the negative electrode material, and then heated in a temperature range of 30 to 100 ° C.
  • a lithium polymer secondary battery in which a solid electrolyte layer supported by a porous material having a light transmittance of 50% or more is interposed between a positive electrode and a negative electrode.
  • Solid electrolyte formation containing at least one polymerizable monomer, lithium salt, photopolymerization initiator, and thermal polymerization initiator of the same or different composition in either one of the negative electrode material and the porous material of the solid electrolyte
  • the other electrode material is impregnated with a precursor solution for forming a solid electrolyte containing at least a polymerizable monomer, a lithium salt and a thermal polymerization initiator, and the other electrode material is impregnated with the other electrode material.
  • the first polymerization is carried out by irradiating the porous material with a porous material and then irradiating light in a temperature range of 30 to 100, and at that stage, a solid electrolyte is interposed between the positive electrode material and the negative electrode material.
  • the lithium-ion secondary battery is obtained by laminating the other electrode material and then heating it in the temperature range of 30 to 100 ° C to perform the second polymerization.
  • the lithium polymer secondary battery of Invention 2 is the same as Invention 1 except for thermal polymerization.
  • organic peroxides such as disilver oxide and peroxyester are particularly preferable.
  • organic peroxides such as disilver oxide and peroxyester are particularly preferable.
  • (1) t-butyl benzoyl neodecanoate, (2) m-toluoyl benzoyl peroxyside, (3) 3,5,5-trimethylhexanoyl peroxy acid (4) t-hexyl peroxy vivate, etc. in terms of the charge-discharge characteristics of the resulting lithium polymer secondary battery, and in that there is little effect such as deterioration in rate characteristics and deterioration in cycle characteristics.
  • the above (1), (2) and (3) are particularly preferred.
  • the decomposition temperature for obtaining a half-life of 10 hours is preferably 40 or more, and the reaction is more preferably performed at a higher temperature.
  • the decomposition temperature for obtaining a half-life of 10 hours is 90 and the following is preferable.
  • the addition amount of the polymerization initiator is preferably as small as possible in order to reduce reactions such as decomposition of the initiator during charge and discharge. However, when the amount is too small, the polymerization reaction does not sufficiently occur, and unreacted polymerizable monomers may remain, which is not preferable.
  • the amount of thermal polymerization initiator to be added is 1 to 500 ppm based on the total amount including the polymerizable monomer and lithium salt, and in some cases, the organic solvent.
  • the range is preferably, and more preferably 50 to 100 ppm.
  • the negative electrode of the lithium polymer secondary battery according to the second aspect of the present invention preferably contains a carbon material obtained by attaching amorphous carbon to the surface of graphite particles as a negative electrode active material.
  • the method for producing a lithium polymer primary battery according to Invention 3 is a method for producing a polymerizable monomer, a lithium salt, or a polymer, wherein at least one of the positive electrode material and the negative electrode material is impregnated in the electrode material and the porous material for the solid electrolyte layer.
  • the precursor solution for forming a solid electrolyte containing at least an initiator is simultaneously prepared after lamination by two methods using light and heat in a temperature range of 30 to 100 and at least one method described above. It is characterized by conducting a polymerization reaction.
  • a solid electrolyte portion obtained by performing a polymerization reaction of a precursor solution impregnated in a positive electrode material and a negative electrode material is also referred to as a solid electrolyte matrix.
  • the solid electrolyte layer and the surface layer of the positive electrode and the negative electrode containing the solid electrolyte matrix can be combined with each other.
  • Each of these deep portions can be three-dimensionally polymerized (also referred to as “cross-linking” or “curing”) in a preferred manner to reduce unreacted polymerizable monomers and unreacted polymerization initiators.
  • the polymerization is carried out in a temperature range of 30 to 100 ° C, decomposition of the lithium salt can be prevented (preferably at 150 or less, more preferably at 100 ° C or less).
  • volatilization of the low boiling point solvent is suppressed (preferably 100 or less), and decomposition-activation of the thermal polymerization initiator (preferably at 30 ° C or more, more preferably at 40 or more) is suppressed. Can be promoted.
  • the polymerization reaction is performed simultaneously after the lamination, the resistance at each interface of the positive electrode solid electrolyte layer and the negative electrode is reduced, and the adhesion is improved.
  • the surface layer of the solid electrolyte can be crosslinked.
  • Process request The required degree of shape stability can be obtained in a short time.
  • Examples of the light to be irradiated include those exemplified in the above invention 1, and ultraviolet light is particularly preferable.
  • the irradiation time is the same as that of the first invention.
  • the deep part of the solid electrolyte can be crosslinked, and the amount of unreacted polymerizable monomer and unreacted polymerization initiator in the solid electrolyte layer and the solid electrolyte matrix can be reduced.
  • the precursor solution used in the method for producing a lithium polymer secondary battery according to Invention 3 contains at least a polymerizable monomer, a lithium salt, a photopolymerization initiator and / or a thermal polymerization initiator.
  • Examples of the polymerizable monomer and lithium salt include those exemplified in Invention 1 above, and the blending amounts and addition amounts thereof are the same as in Invention 1 above.
  • Examples of the photopolymerization initiator include those exemplified in the above invention 1, and 2,4,6-trimethylbenzoyldiphenylphosphinoxide, bis (2,4,6-trimethylbenzoyl)- Phenylphosphinoxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are particularly preferred. Further, the amount of the photopolymerization initiator to be added is the same as in the above invention 1.
  • thermal polymerization initiator examples include those exemplified in Invention 2 above, and t-butyl peroxy neodecanoate, m-toluoyl benzoyl baroxide, or 3,5,5-trimethylhexanoyl paroxylate One oxide is particularly preferred.
  • the amount of the thermal polymerization initiator to be added is the same as that of the above-mentioned invention 2.
  • the precursor solution in invention 3 preferably contains an organic solvent.
  • the organic solvent is preferable because the ionic conductivity in the solid electrolyte is further improved, and the battery characteristics of the obtained lithium polymer secondary battery are improved.
  • the organic solvent examples include those exemplified in the above invention 1, and the amount of the organic solvent is the same as in the above invention 1.
  • Invention 3 is a method for manufacturing a lithium polymer secondary battery, comprising: Containing at least one electrode material and at least one electrode material and a porous material for the solid electrolyte layer, containing at least one polymerizable monomer, lithium salt, photopolymerization initiator, and thermal polymerization initiator of the same or different composition.
  • the precursor solution for forming the electrolyte is impregnated, and the first polymerization is performed by irradiating light in a temperature range of 30 to 100 ° C.
  • the solid electrolyte is interposed between the positive electrode material and the negative electrode material. It is characterized in that the second polymerization is carried out by heating in a temperature range of 30 to 100 ° C.
  • the positive electrode, the negative electrode, and the porous material impregnated with the precursor solution are separately irradiated with light in a temperature range of 30 to 100 ° C. to perform the first polymerization, and thereafter, At the stage where both electrodes and the porous material are bonded, or the above-mentioned bonded material is sandwiched between two exterior materials (for example, an aluminum laminated resin film) and thermally fused to form a sheet. At the stage of producing the battery or at the stage of producing the battery, heating is performed in a temperature range of 30 to 100 ° C. to perform the second polymerization, thereby producing a lithium polymer secondary battery.
  • the method for producing a lithium polymer secondary battery of the present invention is characterized in that a polymerizable monomer having the same or different composition is added to one of the molded positive electrode material and the negative electrode material and the porous material for the solid electrolyte layer.
  • the other electrode material is then bonded so that a solid electrolyte is interposed between the positive electrode material and the negative electrode material at that stage, and then applied in a temperature range of 30 to 100. Heat and polymerize for the second time And performing.
  • either the positive electrode or the negative electrode impregnated with the precursor solution is bonded to the porous material impregnated with the precursor solution, and the laminate is subjected to a temperature range of 30 to 100.
  • the first polymerization is performed by irradiating light, and thereafter, the laminated body is bonded to the other electrode, or the above-described bonding is performed. Is sandwiched between two exterior materials (for example, an aluminum laminated resin film), and then heat-sealed to produce a sheet-shaped battery or at a stage where the battery is produced, at a temperature of 30 to 100 ° C.
  • the second polymerization is carried out by heating in the temperature range described above to produce a lithium polymer secondary battery.
  • the precursor solution subjected to polymerization by light irradiation contains a photopolymerization initiator
  • the precursor solution subjected to polymerization by heating contains a thermal polymerization initiator
  • the precursor solution subjected to polymerization by the above two methods is used.
  • the body solution contains the two types of polymerization initiators.
  • the precursor solution impregnated into either the positive electrode or the negative electrode contains 2
  • the electrode containing the photopolymerization initiator is polymerized, and then the electrode that does not contain the photopolymerization initiator is bonded between the two exterior materials.
  • heating is performed in a temperature range of 30 to 100 to perform a second polymerization, thereby forming a lithium polymer secondary battery. The production is preferable because the interface resistance can be reduced.
  • the precursor solutions to be impregnated into the positive electrode and the negative electrode to be a solid electrolyte matrix have different compositions.
  • the precursor solutions to be impregnated into the positive electrode and the negative electrode to be a solid electrolyte matrix have different compositions.
  • the negative electrode contains a carbon material having amorphous carbon attached to the surface of graphite particles as a negative electrode active material.
  • a polymerizable monomer and a lithium salt, and in some cases, a mixture of a polymerization initiator and an organic solvent are impregnated with the polymerizable monomer.
  • a positive electrode can be formed by polymerizing one.
  • the above mixture, a polymerizable monomer and a lithium salt, in some cases, a polymerization initiator and an organic solvent may be mixed and polymerized.
  • a negative electrode can be formed by impregnating a mixture of a polymerizable monomer and a lithium salt, and in some cases, a polymerization initiator and an organic solvent, and polymerizing the polymerizable monomer.
  • a polymerizable monomer and a lithium salt in some cases, a polymerization initiator and an organic solvent may be mixed and polymerized.
  • porous material constituting the solid electrolyte layer examples include the porous materials exemplified in Invention 1.
  • the weight ratio of the solid electrolyte (ion conductive compound) to the porous material constituting the solid electrolyte layer is suitably in the range of 91: 9 to 50:50.
  • the weight ratio of the ion conductive compound is higher than 91, sufficient mechanical strength cannot be obtained, and when it is lower than 50, the ion conductivity cannot be sufficiently obtained, which is not preferable.
  • the solid electrolyte layer in the lithium polymer secondary battery of the present invention does not need to have a single layer structure, but may have a multilayer structure. Further, the surface of the solid electrolyte layer may be treated to prevent the diffusion of the solvent between the positive electrode Z solid electrolyte layer or the negative electrode and the solid electrolyte layer, and to improve the adhesion at the interface between the solid electrolyte layers. .
  • the shape of the lithium polymer secondary battery obtained by Invention 3 is the same as that of Invention 1 and Invention 2. According to the present invention, there is also provided a lithium polymer secondary battery (Invention 4) obtained by the production method of Invention 3 described above.
  • a lithium polymer secondary battery of the present invention was produced according to the following procedure.
  • the positive electrode active material was synthesized lithium cobalt acid L i C o 0 2 in a known manner.
  • the obtained sample was pulverized in a mortar and mixed with 10 wt% acetylene black as a conductive agent and 10 wt% Teflon (R) resin powder as a binder. This mixture was dissolved in a solvent of N-methyl-2-pyrrolidone to form a slurry, and the obtained slurry was applied on aluminum foil by a doctor blade method and pressed.
  • the surface of the positive electrode produced in this manner was covered with a nonwoven fabric made of a polyester-based polymer having a thickness of 25 m, an ultraviolet transmittance of 95%, and a surface roughness of ⁇ 5 zm.
  • a precursor solution was prepared by mixing the copolymer with 10% by weight of the organic electrolyte and a photopolymerization initiator. The obtained precursor solution was impregnated into a nonwoven fabric and polymerized by irradiation with ultraviolet rays.
  • Natural graphite powder was used as the negative electrode active material. About 1 Owt% of Teflon (R) resin powder was mixed with natural graphite powder as a binder. This mixture was dissolved in a solvent of N-methyl-2-pyrrolidone to form a slurry, and the obtained slurry was applied to a copper foil, dried, and then pressed.
  • Teflon (R) resin powder was mixed with natural graphite powder as a binder. This mixture was dissolved in a solvent of N-methyl-2-pyrrolidone to form a slurry, and the obtained slurry was applied to a copper foil, dried, and then pressed.
  • Fig. 2 shows a schematic diagram of this battery.
  • reference numeral 5 denotes a positive electrode integrated with a porous material
  • 6 denotes a negative electrode
  • 7 denotes a current collecting tab
  • 8 denotes an exterior aluminum laminated resin film (exterior resin film).
  • the performance of the lithium polymer secondary battery was evaluated by the following method.
  • the battery was initially charged and discharged at a constant current of 10 mA. Note that the upper limit in charging was 4. IV and the lower limit was 3.0 V. This initial discharge capacity was defined as the capacity of this battery. Further, thereafter, charge and discharge were repeated at 100 mA, the discharge capacity after 500 cycles was measured, and the capacity retention was calculated from this capacity and the following equation.
  • Capacity retention (%) Discharge capacity after 500 cycles / battery capacity
  • a sheet-shaped lithium polymer secondary battery was prepared in the same manner as in Example 1 except that a nonwoven fabric having a light transmittance of 50% was used, and the performance of the battery was evaluated by the method described in Example 1. did.
  • a sheet-shaped lithium polymer secondary battery was produced in the same manner as in Example 1 except that a porous polyethylene having a thickness of 25 mm, an ultraviolet transmittance of 70%, and a surface roughness of ⁇ 5 m was used as the nonwoven fabric.
  • the battery was manufactured, and the performance of the battery was evaluated by the method described in Example 1.
  • a sheet-like lithium polymer secondary battery was prepared in the same manner as in Example 1 except that a nonwoven fabric having a light transmittance of 45% was used, and the performance of the battery was evaluated by the method described in Example 1. evaluated.
  • a sheet-shaped lithium polymer secondary battery was prepared in the same manner as in Comparative Example 1 except that a nonwoven fabric having a surface roughness of 1 m was used. The performance of the battery was evaluated by the method described.
  • Table 1 shows the battery capacity and cycle characteristics of the lithium polymer secondary batteries produced in Examples 1 to 3 and Comparative Examples 1 and 2.
  • the lithium polymer secondary battery of the present invention (Example) has a larger battery capacity after 500 cycles and superior cycle characteristics as compared with the conventional one (Comparative Example). Understand.
  • Example 1 was repeated except that a precursor solution in which a thermal polymerization initiator was further mixed in addition to the photopolymerization initiator was used, and that thermal polymerization was performed by heating at 60 ° C for 72 hours after sealing.
  • a sheet-shaped lithium polymer secondary battery was produced in the same manner as in Example 1 and the performance of the battery was evaluated by the method described in Example 1.
  • a sheet-shaped lithium polymer secondary battery was prepared in the same manner as in Example 4 except that a porous polypropylene having a thickness of 26 / im and an ultraviolet transmittance of 95% was used as the nonwoven fabric.
  • the performance of the battery was evaluated by the method described in (1).
  • a sheet-shaped lithium polymer secondary battery was prepared in the same manner as in Example 5, except that thermal polymerization was performed by heating at 80 for 6 hours. The performance of the battery was evaluated by the method described.
  • a sheet-shaped lithium polymer primary battery was prepared in the same manner as in Example 5 except that thermal polymerization was performed by heating at 100 ° C. for 1 hour, and the battery was manufactured by the method described in Example 1. The performance was evaluated.
  • a sheet-shaped lithium polymer secondary battery was prepared in the same manner as in Example 5 except that thermal polymerization was performed by heating at 110 ° C for 0.5 hour, and the method described in Example 1 was used. The performance of the battery was evaluated.
  • a positive electrode was produced in the same manner as in Example 1.
  • the prepared positive electrode was bonded to a porous material made of a nonwoven fabric made of a polyester polymer having a thickness of 25 Um, an ultraviolet transmittance of 95%, and a surface roughness of ⁇ 5 m.
  • organic electrolyte solution ethylene carbonate Natick preparative 5 0 wt% and ⁇ - to Puchiroraku tons 5 0 wt% of the mixed solvent obtained by dissolving a L i PF 6 in 1 mo 1 1, E Chirenokishido propylene O sulfoxide co
  • a precursor solution was prepared by mixing the polymer with 10% by weight based on the organic electrolyte, a photopolymerization initiator and a thermal polymerization initiator. The obtained precursor solution was impregnated into a porous material, and polymerized by ultraviolet irradiation to obtain a positive electrode + solid electrolyte layer.
  • a negative electrode was produced in the same manner as in Example 1.
  • the precursor solution obtained by removing the photopolymerization initiator from the above composition was impregnated into the produced negative electrode.
  • the positive electrode + solid electrolyte layer and the negative electrode were adhered to each other, sandwiched between two pieces of an aluminum muramine resin film, and sealed by heat fusion. After sealing, thermal polymerization was performed by heating at 100 ° C. for 1 hour to produce a sheet-shaped lithium polymer secondary battery.
  • a sheet-like lithium polymer secondary battery was produced in the same manner as in Example 4 except that the battery was evaluated, and the performance of the battery was evaluated by the method described in Example 1.
  • Table 2 shows the battery capacity and cycle characteristics of the lithium polymer secondary batteries produced in Examples 4 to 9 and Comparative Example 3. Table 2
  • Example 4 show that the two-stage polymerization of light (electromagnetic wave) and heat improves the retention of cycle characteristics.
  • the heating temperature in the thermal polymerization is preferably in a temperature range up to 100.
  • Example 8 when the precursor solution was used in combination with a mixture of a photopolymerization initiator and a thermal polymerization initiator and a mixture of only a thermal polymerization initiator, the battery capacity was increased. It can be seen that the cycle characteristics are improved. This is thought to be the result of improved adhesion at the interface between the electrode and the solid electrolyte.
  • Example 9 From the results of Example 9, it was found that amorphous carbon was It can be seen that the use of a carbon material (surface amorphous graphite) to which carbon is adhered improves the retention of cycle characteristics. This is considered to be the result of suppressing the decomposition reaction by the organic electrolyte and the like at the negative electrode.
  • a lithium polymer primary battery shown in FIG. 3 was produced.
  • ultraviolet rays having a maximum output wavelength of 365 nm were used for ultraviolet irradiation in photopolymerization.
  • FIG. 3 is a schematic sectional view showing a basic structure of another lithium polymer secondary battery of the present invention.
  • 11 is an electrode terminal
  • 12 is a solid electrolyte layer
  • 13 is a positive electrode material and solid electrolyte (positive electrode layer)
  • 14 is a positive electrode current collector
  • 15 is a negative electrode current collector
  • 16 is a positive electrode current collector.
  • Negative electrode material and solid electrolyte (negative electrode layer). 17 is an exterior material made of aluminum laminated resin film to block the battery from the outside air.
  • the obtained precursor solution was cast on a glass substrate having an area of 12.25 cm 2 , a spacer having a thickness of 50 m was bitten, and a glass substrate was mounted thereon and fixed. First, ultraviolet light was irradiated for 5 seconds at an intensity of 200 mWZ cm 2 . The thickness of the obtained solid electrolyte was 50.
  • the Jiakuri rate monomers containing a copolymer of polyethylene O dimethylsulfoxide and polypropylene O sulfoxide is a polymerizable monomer which is a precursor of a solid electrolyte
  • L i PF 6 is 4.5 wt%
  • photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide was 0.2% by weight
  • t-butyl peroxyneodecanoate was 0.02% by weight as a thermal polymerization initiator.
  • the positive electrode was left under reduced pressure for 5 minutes, the precursor solution was injected, and left for another 15 minutes. Thereafter, ultraviolet rays were irradiated at an intensity of 200 mW / cm 2 for 5 seconds.
  • the thickness of the obtained positive electrode layer was 80 m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are bonded together, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. did. After the production of the battery, thermal polymerization was performed by heating at 60 at 24 hours.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the Jiakuri rate monomers containing a copolymer of polyethylene O dimethylsulfoxide and polypropylene O sulfoxide is a polymerizable monomer which is a precursor of a solid electrolyte, L i PF 6 is 4.5 wt%, as a thermal polymerization initiator
  • the precursor solution was obtained by dissolving t-butylperoxyneodecanoet so as to be 0.02% by weight.
  • the obtained precursor solution was cast on a glass substrate having an area of 12.2.5 cm 2 , a spacer having a thickness of 50 / im was bitten, and a glass substrate was mounted thereon and fixed. At 60, thermal polymerization was performed by heating for 24 hours.
  • the thickness of the obtained solid electrolyte was 50.
  • the Jiakuri rate monomers containing a copolymer of polyethylene O dimethylsulfoxide and polypropylene O sulfoxide is a polymerizable monomer which is a precursor of a solid electrolyte, L i PF 6 is 4.5 wt%, as a thermal polymerization initiator
  • the precursor solution was obtained by dissolving t-butylperoxyneodecanoet so as to be 0.02% by weight.
  • the positive electrode was left under reduced pressure for 5 minutes, the precursor solution was injected, and left for 15 minutes. Then, it was fixed by sandwiching it between glass plates, and was subjected to thermal polymerization by heating at 60 ° C for 24 hours.
  • the thickness of the obtained positive electrode layer was 80 m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer is 85 m and the thickness is 7 mm.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are bonded together, sandwiched between two sheets of aluminum and muramineto resin films, and thermally fused to form a sheet-shaped battery. Produced.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the Jiaku relay Bok monomer containing a copolymer of polyethylene O dimethylsulfoxide and polypropylene O sulfoxide is a polymerizable monomer which is a precursor of a solid electrolyte, L i PF 6 is 4.5 wt%, photoinitiator
  • a precursor solution was obtained by dissolving 2,4,6-trimethylbenzoyldiphenylphosphinoxydoca as an agent so as to be 0.2% by weight.
  • the obtained precursor solution was cast on a glass substrate having an area of 12.25 cm 2 , a spacer having a thickness of 50 m was bitten, and the glass substrate was mounted thereon and fixed. Ultraviolet rays were irradiated for 5 seconds at an intensity of SOO mWZ cm 2 .
  • the thickness of the obtained solid electrolyte is 50 m.
  • the Jiakuri rate monomers containing a copolymer of polyethylene O dimethylsulfoxide and polypropylene O sulfoxide is a polymerizable monomer which is a precursor of a solid electrolyte, L i PF 6 is 4.5 wt%, as a photopolymerization initiator
  • the precursor solution was obtained by dissolving 2,4,6-trimethylbenzoyldiphenylphosphonide so as to be 0.2% by weight.
  • the positive electrode was left under reduced pressure for 5 minutes, the precursor solution was injected, and left for another 15 minutes. Thereafter, ultraviolet rays were irradiated for 5 seconds at an intensity of 20 O mW / cm 2 .
  • the thickness of the obtained positive electrode layer was 80 wm.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer is 85 fim.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained were attached to each other, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-like battery. .
  • Example 10 Five batteries were prepared for each of Example 10 and Comparative Examples 4 and 5, and charged at a constant current of 2.3 mA until the battery voltage reached 4. IV. Charged at constant voltage for 12 hours. Each battery was discharged at a constant current of 23 mA until the battery voltage reached 2.75 V.
  • Table 3 shows the initial charge / discharge efficiency of each battery.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, ultraviolet rays were irradiated for 5 seconds at an intensity of 200 mWZ cm 2 .
  • the thickness of the obtained positive electrode layer was 80 im.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are laminated, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. did. After the battery was produced, thermal polymerization was performed by heating at 60 for 24 hours.
  • the ionic conductivity of the solid electrolyte layers of Examples 10 and 11 was measured as follows.
  • the impedance of the solid electrolyte layer at 20 ° C was measured with an impedance analyzer. The resistance value was measured from the obtained c01e-c01e plot, and the ionic conductivity was determined.
  • Example 11 The ionic conductivities of the solid electrolyte layers of Example 10 and Example 11 were 0.92 mS / cm and 5.1 mSZcm, respectively. From these results, it was found that a battery using a lithium ion conductive gel containing an organic solvent for the solid electrolyte layer and the solid electrolyte matrix inside the electrode (Example 11) uses a lithium ion conductive polymer. It was found that the battery had better battery characteristics than the battery (Example 10).
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • a precursor solution was obtained by further dissolving t-butyl peroxy neodecanoate as a thermal polymerization initiator to a concentration of 0.02% by weight.
  • a 25 m-thick nonwoven fabric was immersed in the obtained precursor solution and left under reduced pressure for 15 minutes. The nonwoven fabric was taken out and subjected to thermal polymerization by heating at 60 ° C. for 24 hours to produce a gel solid electrolyte.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, thermal polymerization was performed by heating at 60 ° C for 24 hours. The thickness of the obtained positive electrode layer was 80 m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 ⁇ m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are bonded together, sandwiched between two aluminum laminate resin films, and thermally fused to produce a sheet-shaped battery. did.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, ultraviolet rays were irradiated for 5 seconds at an intensity of 200 mWZ cm 2 .
  • the thickness of the obtained positive electrode layer was 80.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are laminated, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. did,
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the precursor solution was prepared by adjusting the ratio to 93: 7.
  • the obtained precursor solution was cast on a glass substrate having an area of 12.25 cm 2 , a spacer having a thickness of 50 m was bitten, and the glass substrate was placed and fixed thereon. After that, an electron beam with an acceleration voltage of 250 kV and an electron beam of 8 Mrad was irradiated in an inert gas atmosphere.
  • the thickness of the obtained solid electrolyte was 50 xm.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Then, in inert gas atmosphere, acceleration voltage 25 An electron beam of 0 kV and an electron beam of 8 Mrad was irradiated. The thickness of the obtained positive electrode layer was 80 m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 8.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are laminated, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. did.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the obtained precursor solution was cast on a glass substrate having an area of 12.2.55 cm 2 , a spacer having a thickness of 50 m was placed thereon, and the glass substrate was placed and fixed thereon. After that, an electron beam with an acceleration voltage of 250 kV and an electron beam of 8 Mrad was irradiated in an inert gas atmosphere. The thickness of the obtained solid electrolyte was 5 O zm.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. After that, an electron beam with an acceleration voltage of 250 kV and an electron beam of 8 Mrad was irradiated in an inert gas atmosphere. The thickness of the obtained positive electrode layer was 80 ⁇ m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer is 85 Xm.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are bonded together, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-like battery. did. After the production of the battery, thermal polymerization was performed by heating at 60 ° C. for 24 hours.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, ultraviolet light was irradiated for 180 seconds at an intensity of 7 mWZcm 2 .
  • the thickness of the obtained positive electrode layer was 80 m.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 Atm.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained were attached to each other, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-like battery. . After the production of the battery, thermal polymerization was performed by heating at 110 ° C. for 1 hour.
  • Example 11 Fifty batteries each of Example 11 and Comparative Examples 6 to 10 were manufactured, and a short-circuit check was performed.
  • the number of short circuits in the battery of Comparative Example 6 was 2 out of 50, but the number of short circuits in all other batteries was 0 out of 50. From this result, it was found that a battery using a solid electrolyte in a gel state, which was thermally polymerized using a thermal polymerization initiator, could cause a short circuit during assembly.
  • Example 11 and Comparative Examples 6 to 10 were charged at a constant current of 2.3 mA until the battery voltage reached 4.IV, and after reaching 4.1 V, the batteries were charged at a constant voltage for 12 hours. .
  • Each battery was discharged at a constant current of 2.3 mA, 5 mA, 10 mA, and 20 mA until the battery voltage reached 2.75 V.
  • Figure 4 shows the results of the charge / discharge test (relationship between current value and discharge capacity) for each battery.
  • Example 11 The same procedures as in Example 11 were performed except that the heat treatment conditions for thermal polymerization by heating after battery production were set to 80 at 6 hours, 90 at 2 hours, and 100 at 1 hour, respectively.
  • the sheet-shaped battery of No. 8 was produced.
  • the batteries of Examples 11 to 14 and Comparative Example 11 were charged at a constant current of 2.3 mA, until the battery voltage reached 4.IV. 4. After reaching IV, 12 hours at the constant voltage Charged. Each battery was discharged at a constant current of 2.3 mA until the battery voltage reached 2.75 V.
  • Figure 5 shows the cycle characteristics (relationship between cycle number and discharge capacity) of each battery.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • an organic electrolyte was prepared by dissolving in a mixed solvent of EC and GBL (EC content: 35% by volume) so that Li BF 4 became 1 M.
  • the organic electrolyte and the diacrylate monomer containing a copolymer of polyethylene oxide and polypropylene oxide, which are polymerizable monomers that are precursors of the solid electrolyte, are adjusted to have a weight ratio of 93: 7.
  • 0.1% by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide was further used as a photopolymerization initiator, and t-butyl peroxyneodecaine was used as a thermal polymerization initiator.
  • the precursor was dissolved to a concentration of 0.01% by weight to obtain a precursor solution.
  • a nonwoven cloth having a thickness of 25 m was immersed in the obtained precursor solution, and allowed to stand under reduced pressure for 15 minutes.
  • the nonwoven fabric was taken out and irradiated with ultraviolet light at an intensity of 200 mW / cm 2 for 5 seconds to produce a gel solid electrolyte.
  • the positive electrode was left under reduced pressure for 5 minutes, and the precursor solution prepared above was injected. It was left for another 15 minutes. Thereafter, ultraviolet rays were irradiated for 5 seconds at an intensity of 200 mWZ cm 2 .
  • the thickness of the obtained positive electrode layer was 80 / xm.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 ⁇ m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained were attached to each other, sandwiched between two aluminum laminated resin films, and heat-sealed to produce a sheet-shaped battery. After the production of the battery, thermal polymerization was performed by heating at 60 ° C. for 72 hours.
  • Examples 16 to 1 were carried out in the same manner as in Example 15 except that oxoxide, 1-hydroxy-cyclohexyl-phenylketone and 2,2-dimethoxy-2-phenylacetophenone were used. Nine sheet batteries were produced.
  • the batteries of Examples 15 to 19 were charged at a constant current of 2.3 mA until the battery voltage reached 4. IV. After reaching 4. IV, the batteries were charged at a constant voltage for 12 hours. Each battery was discharged at a constant current of 2.3 mA until the battery voltage reached 2.75 V.
  • Figure 6 shows the cycle characteristics (relationship between cycle number and discharge capacity) of each battery.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • L i PF 6 is dissolved to be 1 M, were prepared organic electrolyte solution.
  • a 93: 7 weight ratio of the organic electrolyte solution and a diacrylate monomer containing a copolymer of polyethylene oxide and polypropylene oxide, which are polymerizable monomers that are precursors of the solid electrolyte. was prepared.
  • bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide was further added at 0.1% by weight as a photopolymerization initiator, and t-butylperoxyneoxane was used as a thermal polymerization initiator.
  • the precursor solution was obtained by dissolving the decanoate so as to be 0.01% by weight.
  • a 25 m-thick nonwoven fabric was immersed in the obtained precursor solution and left under reduced pressure for 15 minutes.
  • the nonwoven fabric was taken out and irradiated with ultraviolet rays at an intensity of 200 mWZcm2 for 5 seconds to produce a gel-like solid electrolyte.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, ultraviolet rays were irradiated at an intensity of 200 mW / cm 2 for 5 seconds.
  • the thickness of the obtained positive electrode layer was 80.
  • a negative electrode layer was prepared in the same manner as the positive electrode layer.
  • the thickness of the obtained negative electrode layer was 85 m.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained were attached to each other, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-like battery. . After the production of the battery, thermal polymerization was performed by heating at 60 ° C. for 72 hours.
  • the batteries of Examples 20 to 23 were charged at a constant current of 2.3 mA until the battery voltage reached 4. IV. After reaching 4. IV, the batteries were charged at a constant voltage for 12 hours. Each battery was discharged at a constant current of 2.3 mA until the battery voltage reached 2.75 V.
  • Figure 7 shows the cycle characteristics (relationship between cycle number and discharge capacity) of each battery.
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • L i PF 6 is dissolved to be 1 M, were prepared organic electrolyte solution.
  • a nonwoven cloth having a thickness of 25 m was immersed in the obtained precursor solution, and allowed to stand under reduced pressure for 15 minutes.
  • the nonwoven fabric was taken out and irradiated with ultraviolet light at an intensity of 200 mWZ cm 2 for 5 seconds to produce a gel solid electrolyte.
  • the negative electrode was allowed to stand under reduced pressure for 5 minutes, a solution obtained by adding 3 wt% of vinylene carbonate to the precursor solution prepared above was injected, and the solution was further allowed to stand for 15 minutes. Thereafter, ultraviolet rays were irradiated for 5 seconds at an intensity of 200 mWZ cm 2 .
  • the thickness of the obtained negative electrode layer was 85.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained were attached to each other, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. . After the production of the battery, thermal polymerization was performed by heating at 60 at 24 hours.
  • the batteries of Examples 11 and 24 were charged at a constant current of 2.3 mA until the battery voltage reached 4. IV. After reaching 4. IV, the batteries were charged at a constant voltage for 12 hours. Each battery was discharged at a constant current of 2.3 mA, 5 mA, 10 mA> 2 O mA until the battery voltage reached 2.75 V.
  • Figure 8 shows the results of the charge / discharge test (relationship between current value and discharge capacity) for each battery.
  • Example 24 a lithium polymer secondary battery in which the solid electrolyte contained in the positive electrode layer and the solid electrolyte contained in the negative electrode layer had different compositions (Example 24) had the same composition. It was found that the battery had better battery characteristics than the battery (Example 11).
  • a positive electrode and a negative electrode were obtained in the same manner as in Example 10.
  • L i PF 6 is dissolved to be 1 M, were prepared organic electrolyte solution.
  • the organic electricity The dissolution liquid and the diacrylate monomer containing a copolymer of polyethylene oxide and polypropylene oxide, which are polymerizable monomers that are precursors of the solid electrolyte, are adjusted to have a weight ratio of 93: 7.
  • This mixed solution was further added with 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator in an amount of 0.2% by weight, and as a thermal polymerization initiator, t-butylvinyloxyneodecanoate.
  • t-butylvinyloxyneodecanoate was dissolved to be 0.02% by weight to obtain a precursor solution.
  • a 25 zm-thick nonwoven fabric was immersed in the obtained precursor solution, and left under reduced pressure for 15 minutes.
  • the positive electrode was left under reduced pressure for 5 minutes, the above-prepared precursor solution was injected, and left for further 15 minutes. Thereafter, the nonwoven fabric impregnated with the precursor solution prepared above was fixed on a positive electrode, and irradiated with ultraviolet light at an intensity of 200 mW / cm 2 for 5 seconds. The total thickness of the obtained positive electrode layer and solid electrolyte layer was 105 m.
  • a mixed solvent of EC and GBL (EC content 35 vol%), was dissolved so as to L i PF 6 force 1 M, to prepare an organic electrolytic solution.
  • a precursor solution was obtained by further dissolving t-butyl vinyl neodecanoate as a thermal polymerization initiator in an amount of 0.02% by weight.
  • the negative electrode was left under reduced pressure for 5 minutes, the precursor solution prepared above was injected, and the mixture was further left for 15 minutes.
  • the positive electrode layer, the solid electrolyte layer, and the negative electrode layer thus obtained are bonded together, sandwiched between two aluminum laminate resin films, and heat-sealed to produce a sheet-shaped battery. did.
  • thermal polymerization was performed by heating at 60 ° C. for 24 hours.
  • the batteries of Examples 11 and 25 were charged at a constant current of 2.3 mA until the battery voltage reached 4. IV.
  • the batteries were charged at a constant voltage for 12 hours. Each battery was discharged at a constant current of 2.3 mA until the battery voltage reached 2.75 V.
  • Figure 9 shows the cycle characteristics (the relationship between the number of cycles and the discharge capacity) of each battery.
  • the battery of Example 25 had better battery characteristics than the battery of Example 11. That is, one of a positive electrode and a negative electrode, into which a precursor solution to which a photopolymerization initiator and a thermal polymerization initiator are added, is injected, and the non-woven fabric that becomes a solid electrolyte layer and is impregnated with the precursor solution. In addition, the first polymerization reaction (photopolymerization) was performed, and this was combined with the other electrode into which the precursor solution to which only the thermal polymerization initiator was added (no photopolymerization initiator was added) was injected.
  • photopolymerization photopolymerization
  • the battery (Example 25) produced by performing the second polymerization reaction was a precursor obtained by adding both a photopolymerization initiator and a thermal polymerization initiator to both electrodes and the solid electrolyte layer.
  • the battery had better battery characteristics than the battery prepared by the first photopolymerization and the second thermopolymerization (Example 11). It was found that according to the polymerization method of Example 25, the load characteristics were improved because the adhesion at each interface of the positive electrode layer, the solid electrolyte layer, and the negative electrode layer was improved.
  • a gel solid electrolyte, a positive electrode layer and a negative electrode layer were prepared in the same manner as in Example 15, and a battery was prepared by combining these.
  • thermal polymerization was performed by heating at 60 ° C. for 72 hours.
  • the batteries of Examples 15 and 26 were charged at a constant current of 2.3 mA until the battery voltage reached 4. IV. After reaching 4.1 V, the batteries were charged at a constant voltage for 12 hours. Each battery was discharged at a constant current of 2.3 mA until the battery voltage reached 2.75 V.
  • Figure 10 shows the cycle characteristics (relationship between cycle number and discharge capacity) of each battery.
  • the present invention has been specifically described. However, the present invention is not limited to these, and it is possible to use optimal combinations for various purposes.
  • the present invention it is possible to reduce the amount of unreacted monomer and unreacted polymerization initiator that become a solid electrolyte inside the composite electrode, and at the same time, improve the adhesion at each interface of the positive electrode layer / solid electrolyte layer and the negative electrode layer Therefore, it is possible to provide a lithium polymer secondary battery having excellent battery characteristics and high load characteristics, particularly excellent cycle characteristics, and excellent stability in battery characteristics.

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Abstract

L'invention concerne une batterie lithium polymère comprenant un électrolyte solide entre une anode et une cathode, l'électrolyte solide étant constitué d'un matériau poreux formé intégralement avec l'anode ou avec la cathode et possédant un facteur de transmission d'au moins 50 %, un électrolyte organique et un polymère. L'invention concerne aussi un procédé de production consistant à imprégner soit un matériau d'anode, soit un matériau de cathode, ou un matériau poreux, d'un électrolyte solide, constituant une solution précurseur de mélange contenant un monomère polymérique, un sel de lithium, un initiateur de photopolymérisation et un initiateur de thermopolymérisation, ou à imprégner aussi l'autre matériau d'électrode d'un électrolyte solide constituant une solution précurseur de mélange contenant un monomère polymérique, un sel de lithium, un initiateur de photopolymérisation et un initiateur de thermopolymérisation, à empâter ensemble un matériau d'électrode et un matériau poreux, à irradier le matériau empâté d'un rayonnement lumineux à une température comprise entre 30 et 100 °C afin de réaliser une première polymérisation, à empâter l'autre matériau d'électrode et à chauffer le matériau empâté à une température comprise entre 30 et 100 °C afin de compléter une seconde polymérisation.
PCT/JP2002/002872 2001-03-27 2002-03-25 Batterie lithium polymere et procede de production correspondant WO2002078114A1 (fr)

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JP2011530782A (ja) * 2008-08-05 2011-12-22 エルジー・ケム・リミテッド ゲルポリマー電解質二次電池の製造方法、及びそれによって製造されたゲルポリマー電解質二次電池
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JP2014212103A (ja) * 2013-04-04 2014-11-13 本田技研工業株式会社 電解質−正極構造体及びそれを備えるリチウムイオン二次電池
CN108695558A (zh) * 2018-05-22 2018-10-23 浙江锋锂新能源科技有限公司 一种全固态电池芯及包含该电池芯的高性能固态电池
KR20190009757A (ko) * 2016-05-19 2019-01-29 시크파 홀딩 에스에이 다공성 물질의 함침을 위한 방법 및 조성물
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JP2020509565A (ja) * 2017-05-15 2020-03-26 エルジー・ケム・リミテッド 全固体電池用固体電解質膜の製造方法及び該方法によって製造された固体電解質膜
JP2020098696A (ja) * 2018-12-17 2020-06-25 パナソニックＩｐマネジメント株式会社 全固体電池
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JP2011530782A (ja) * 2008-08-05 2011-12-22 エルジー・ケム・リミテッド ゲルポリマー電解質二次電池の製造方法、及びそれによって製造されたゲルポリマー電解質二次電池
US8916297B2 (en) 2008-08-05 2014-12-23 Lg Chem, Ltd. Method of preparing gel polymer electrolyte secondary battery and gel polymer electrolyte secondary battery
JP2015111587A (ja) * 2008-08-05 2015-06-18 エルジー・ケム・リミテッド ゲルポリマー電解質二次電池の製造方法、及びそれによって製造されたゲルポリマー電解質二次電池
US9362592B2 (en) 2008-08-05 2016-06-07 Lg Chem, Ltd. Method of preparing gel polymer electrolyte secondary battery and gel polymer electrolyte secondary battery
US20140220436A1 (en) * 2013-02-05 2014-08-07 Seiko Epson Corporation Method for producing electrode assembly, electrode assembly, and lithium battery
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KR102340764B1 (ko) 2016-05-19 2021-12-21 시크파 홀딩 에스에이 다공성 물질의 함침을 위한 방법 및 조성물
KR20190009757A (ko) * 2016-05-19 2019-01-29 시크파 홀딩 에스에이 다공성 물질의 함침을 위한 방법 및 조성물
JP2019523309A (ja) * 2016-05-19 2019-08-22 シクパ ホルディング ソシエテ アノニムＳｉｃｐａ Ｈｏｌｄｉｎｇ Ｓａ 多孔性材料を含浸させるための方法及び配合物
JP7003364B2 (ja) 2016-05-19 2022-01-20 シクパ ホルディング ソシエテ アノニム 多孔性材料を含浸させるための方法及び配合物
US11342578B2 (en) 2017-05-15 2022-05-24 Lg Energy Solution, Ltd. Method for manufacturing solid electrolyte membrane for all solid type battery and solid electrolyte membrane manufactured by the method
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CN108695558B (zh) * 2018-05-22 2021-05-07 浙江锋锂新能源科技有限公司 一种全固态电池芯及包含该电池芯的高性能固态电池
CN108695558A (zh) * 2018-05-22 2018-10-23 浙江锋锂新能源科技有限公司 一种全固态电池芯及包含该电池芯的高性能固态电池
JP2020098696A (ja) * 2018-12-17 2020-06-25 パナソニックＩｐマネジメント株式会社 全固体電池
JP7182160B2 (ja) 2018-12-17 2022-12-02 パナソニックＩｐマネジメント株式会社 全固体電池
JPWO2020183806A1 (ja) * 2019-03-14 2021-11-11 セイコーエプソン株式会社 ガーネット型固体電解質の前駆体溶液、ガーネット型固体電解質の前駆体溶液の製造方法およびガーネット型固体電解質
JP7081719B2 (ja) 2019-03-14 2022-06-07 セイコーエプソン株式会社 ガーネット型固体電解質の前駆体溶液、ガーネット型固体電解質の前駆体溶液の製造方法およびガーネット型固体電解質
WO2020183806A1 (fr) * 2019-03-14 2020-09-17 セイコーエプソン株式会社 Solution de précurseur d'électrolyte solide au grenat, procédé de production d'une solution de précurseur d'électrolyte solide au grenat, et électrolyte solide au grenat
JP2022535256A (ja) * 2019-07-16 2022-08-05 ファクトリアル インク． リチウムイオン電池及びその他の用途のための電極
US11804603B2 (en) 2019-07-16 2023-10-31 Factorial Inc. Electrodes for lithium-ion batteries and other
JP7439138B2 (ja) 2019-07-16 2024-02-27 ファクトリアル インク． リチウムイオン電池及びその他の用途のための電極

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JP4365098B2 (ja) 2009-11-18

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