WO2015151145A1 - Accumulateur au lithium entierement solide - Google Patents

Accumulateur au lithium entierement solide Download PDF

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Publication number
WO2015151145A1
WO2015151145A1 PCT/JP2014/059405 JP2014059405W WO2015151145A1 WO 2015151145 A1 WO2015151145 A1 WO 2015151145A1 JP 2014059405 W JP2014059405 W JP 2014059405W WO 2015151145 A1 WO2015151145 A1 WO 2015151145A1
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negative electrode
solid
secondary battery
lithium secondary
electrolyte
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PCT/JP2014/059405
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English (en)
Japanese (ja)
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恵理奈 横山
純 川治
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株式会社日立製作所
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Priority to PCT/JP2014/059405 priority Critical patent/WO2015151145A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

  • the present invention relates to an all solid lithium secondary battery.
  • An all solid lithium secondary battery using a nonflammable or flame retardant gel electrolyte containing a lithium conductive polymer and an organic electrolyte (hereinafter also referred to as “solid electrolyte”) is a lithium using a liquid electrolyte. Compared with a secondary battery, higher heat resistance is possible. For this reason, the all-solid lithium secondary battery can improve safety and increase the energy density.
  • Patent Document 1 describes a secondary battery composed of a positive electrode, a solid electrolyte, and a negative electrode, wherein at least one of the positive electrode and the negative electrode is a polymer whose active material is a polymer.
  • a secondary battery characterized by being dispersed in a gel is described.
  • Patent Document 2 discloses that in a solid polymer electrolyte in which a positive electrode and a negative electrode including a polymer electrolyte are sandwiched between solid polymer electrolyte layers, a portion of the polymer electrolyte near the current collector of the positive electrode and / or the negative electrode is a gel.
  • An electrode for a solid polymer battery characterized in that the polymer electrolyte in a portion near the solid polymer electrolyte layer of the positive electrode and / or the negative electrode is completely solidified.
  • an all-solid lithium secondary battery when the concentration of the lithium conductive polymer in the gel electrolyte is high, the viscosity of the gel electrolyte generally increases, and as a result, the gel electrolyte becomes hard.
  • a material that can expand and contract during charging such as graphite
  • peeling may occur at the interface between the active material and the gel electrolyte when the charge / discharge cycle is repeated. In the above case, the lithium conduction path between the active material and the gel electrolyte is lost. Therefore, in an all-solid lithium secondary battery having a gel electrolyte containing a high concentration of lithium conductive polymer, the resistance may increase with time, and the capacity may decrease. It was difficult.
  • an object of the present invention is to provide a high-power all-solid lithium secondary battery.
  • the all-solid-state lithium secondary battery of the present invention comprises a gel electrolyte containing a lithium conductive polymer and an organic electrolyte in a range of 0.01 to 15% by mass relative to the total mass, a negative electrode active material, and A negative electrode having an electrode, a positive electrode, and a solid electrolyte disposed between the negative electrode and the positive electrode.
  • the method for producing an all solid lithium secondary battery of the present invention also includes forming a gel electrolyte by swelling a lithium conductive polymer with an organic electrolyte to form a gel electrolyte containing the lithium conductive polymer and the organic electrolyte. Process.
  • All-solid lithium secondary battery> The present invention relates to an all-solid lithium secondary battery.
  • the all-solid-state lithium secondary battery of the present invention needs to include a negative electrode, a positive electrode, and a solid electrolyte disposed between the negative electrode and the positive electrode.
  • the negative electrode needs to have a gel electrolyte, a negative electrode active material, and a negative electrode current collector.
  • the gel electrolyte and the negative electrode active material contained in the negative electrode constitute a negative electrode mixture layer.
  • “gel electrolyte” means an electrolyte in a gel form.
  • the gel electrolyte needs to contain a lithium conductive polymer and an organic electrolyte.
  • the gel electrolyte is preferably in a form in which a lithium conductive polymer is swollen with an organic electrolyte, that is, in a gel form.
  • the present inventors have obtained an all-solid lithium secondary as a result. It has been found that the output of the battery is improved.
  • the reason why the all solid lithium secondary battery of the present invention has the above-described characteristics can be explained as follows. Note that the present invention is not limited to the following actions and principles.
  • the active material and the gel electrolyte may be separated, and a gap may be generated between the active material and the gel electrolyte.
  • This phenomenon can occur remarkably when a material that can expand and contract during charging is used as the active material or conductive agent. If such voids occur, the lithium conduction path between the active material or conductive agent and the gel electrolyte may be lost, increasing the resistance and consequently reducing the capacity.
  • the all solid lithium secondary battery of the present invention uses a gel electrolyte containing a lithium conductive polymer at a lower concentration than the conventional product. The viscosity of the lithium conducting polymer usually increases depending on its concentration.
  • the gel electrolyte used for the all-solid-state lithium secondary battery of the present invention has a low viscosity as compared with the conventional product. Since the low-viscosity gel electrolyte has high fluidity, it can flow corresponding to the expansion and contraction of the active material or the conductive agent, and can substantially suppress the formation of voids. In the present specification, the above effect may be referred to as “a void filling effect”. As described above, the all-solid-state lithium secondary battery of the present invention exhibits high output without reducing the capacity even when the charge / discharge cycle is repeated over a long period of time due to the void filling effect by the lithium conductive polymer. can do.
  • the lithium conductive polymer can be used without particular limitation as long as it is a material usually used in the technical field.
  • Polymer compounds used in solid electrolytes such as polyiminophosphoranes and ionic liquid polymers (for example, polymers of imidazolium ionic liquid, pyridinium ionic liquid or aliphatic ionic liquid); polyvinyl alcohol, polyethylene glycol, polypropylene glycol , Polyvinylpyrrolidone, styrene-maleic anhydride copolymer, water-soluble polymer compounds such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose; crosslinkable polymer compounds such as styrene-butadiene rubber It can be given as well as high molecular amine compounds; olefin polymer compounds such as polyethylene and polypropylene; fluorine-based resin such as polyvinylidene fluoride and polytetrafluoroethylene.
  • polyiminophosphoranes and ionic liquid polymers for example, polymers of imidazolium ionic liquid, pyridinium ionic
  • the lithium conductive polymer may be in the form of a hydrolyzate, a cross-linked reaction product or an acid-modified product such as the above-mentioned polymer, or a modified product, or a neutralized salt with an acid or a base.
  • it may be in the form of a salt such as a metal salt.
  • the form of the copolymer of the monomer which comprises the polymer mentioned above may be sufficient. In either case, it can be used as a lithium conductive polymer in the present invention.
  • the lithium conductive polymer includes polyethylene oxide (PEO), polyacrylonitrile (PAN), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyphosphazene, polyiminophosphorane, and ionic liquid polymer.
  • PEO polyethylene oxide
  • PAN polyacrylonitrile
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • polyphosphazene polyiminophosphorane
  • ionic liquid polymer ionic liquid polymer
  • Particularly preferred lithium conducting polymers are those of the following formula: (In the formula, n, m, x and y are each independently an integer in the range of 1 to 10,000.) At least one polymer selected from the group consisting of compounds represented by:
  • the polymer described above is chemically and / or electrochemically stable with respect to other materials such as an organic electrolyte solution or a solid electrolyte contained in the all solid lithium secondary battery of the present invention.
  • the polymer is stable with respect to materials and / or conditions used in the method for producing an all solid lithium secondary battery of the present invention described below.
  • the polymer does not substantially dissolve and / or peel off due to the binder or the organic solvent used in the method for producing the all solid lithium secondary battery of the present invention. Therefore, by using the polymer as a lithium conductive polymer, the all solid lithium secondary battery of the present invention can be stably manufactured and used stably.
  • the average molecular weight of the lithium conductive polymer is preferably in the range of 1000 to 400000, more preferably in the range of 5000 to 400000, and particularly preferably in the range of 10000 to 300000.
  • lithium conductive polymers may aggregate in the method for producing an all solid lithium secondary battery of the present invention described below. . In this case, a good electron conduction path is not formed, and the output of the resulting all-solid lithium secondary battery may be reduced.
  • the average molecular weight of the lithium conductive polymer exceeds the upper limit of the above range, the viscosity becomes high, which may make it difficult to fill the voids of the active material or the conductive agent with the lithium conductive polymer. . In this case, the void filling effect by the lithium conductive polymer is reduced, and it may be difficult to increase the output of the resulting all-solid lithium secondary battery. Therefore, when the average molecular weight of the lithium conductive polymer is in the above range, the output of the resulting all solid lithium secondary battery can be improved.
  • the content of the lithium conductive polymer is defined by the following formula.
  • the content of the lithium conductive polymer needs to be in the range of 0.01 to 15% by mass with respect to the total mass of the gel electrolyte.
  • the content of the lithium conductive polymer is preferably in the range of 3 to 12% by mass and more preferably in the range of 5 to 10% by mass with respect to the total mass of the gel electrolyte.
  • the viscosity becomes low. For this reason, when the all-solid-state lithium secondary battery of this invention receives an impact, the liquid retention property of the gel electrolyte inside a battery becomes low, and this gel electrolyte may detach
  • the battery performance of the resulting all solid lithium secondary battery may be reduced.
  • the content of the lithium conductive polymer exceeds the upper limit of the above range, the viscosity increases. For this reason, fluidity
  • the lithium conduction path between the active material or conductive agent in the negative electrode and the gel electrolyte is lost, the resistance increases, and the capacity of the resulting all-solid lithium secondary battery may decrease. There is. Therefore, when the content of the lithium conductive polymer is in the above range, the output of the resulting all solid lithium secondary battery can be improved.
  • the characteristics of the output and resistance of the all-solid lithium secondary battery of the present invention can be evaluated based on, for example, the capacity maintenance ratio and the DC resistance value determined by the following evaluation test.
  • the all-solid-state lithium secondary battery of this invention charges / discharges with a specific charging / discharging rate, and discharge in each cycle when performing initial charge capacity and N cycle (for example, 50 or 100 cycles) charge / discharge repeatedly Measure capacity.
  • N cycle for example, 50 or 100 cycles
  • charge / discharge charge / discharge repeatedly Measure capacity.
  • the voltage difference and electric current value when it discharges for 10 second are measured.
  • the capacity retention ratio and the direct current resistance of the all solid lithium secondary battery of the present invention are determined.
  • the organic electrolyte can be used without particular limitation as long as it is a material that is usually used in the technical field.
  • examples of the organic electrolyte include, but are not limited to, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, gamma butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, trimethoxymethane, 1,2-dimethoxyethane.
  • 1,2-diethoxyethane 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, dioxolane (eg 1,3-dioxolane), formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphate triester, diethyl ether, Sulfolane, 3-methyl-2-oxazolidinone, chloroethylene carbonate, chloropropylene carbonate, imidazolium ionic liquid, pyridinium ionic liquid And aliphatic ionic liquids, and mixtures thereof.
  • dioxolane eg 1,3-dioxolane
  • formamide dimethylformamide
  • methyl propionate ethyl propionate
  • phosphate triester diethyl ether
  • Sulfolane 3-methyl-2-oxazolidinone
  • chloroethylene carbonate chloropropylene carbonate
  • the organic electrolyte is at least one compound selected from the group consisting of propylene carbonate, ethylene carbonate, gamma-butyrolactone, imidazolium ionic liquid, pyridinium ionic liquid and aliphatic ionic liquid, and mixtures thereof. Of these, propylene carbonate is more preferable.
  • the all-solid-state lithium secondary battery of the present invention has a gel electrolyte that is a gel-like electrolyte. When the gel electrolyte does not contain an organic electrolyte, the lithium conductive polymer does not swell sufficiently, and it may be difficult to make the electrolyte in a gel form.
  • the lithium conductive polymer can be swollen so that the electrolyte can be in a gel form.
  • the organic electrolyte described above is chemically and / or electrochemically stable with respect to other materials such as a lithium conductive polymer or a solid electrolyte contained in the all solid lithium secondary battery of the present invention. . Further, the organic electrolyte is stable with respect to materials and / or conditions used in the method for producing the all solid lithium secondary battery of the present invention described below. Therefore, by using the organic electrolyte, the all solid lithium secondary battery of the present invention can be stably produced and used stably.
  • the gel electrolyte usually contains a lithium salt in addition to the lithium conductive polymer and the organic electrolyte.
  • the lithium salt include, but are not limited to, for example, LiPF 6, LiBF 4, LiClO 4, LiCF 3 SO 3, LiCF 3 CO 2, LiBOB, LiAsF 6, LiSbF 6, and lithium bis (fluorosulfonyl) imide ( LiFSI) or an imide salt of lithium such as lithium trifluoromethanesulfonylimide.
  • the lithium salt used in the all solid lithium secondary battery of the present invention is preferably at least one lithium salt selected from the group consisting of the above lithium salt compounds and mixtures thereof.
  • the negative electrode active material is a material in which lithium ions are inserted and desorbed by a lithium ion insertion and desorption reaction or a conversion reaction in the charge and discharge process.
  • the negative electrode active material can be used without particular limitation as long as it is a material that is normally used in this technical field and capable of reversibly inserting and extracting lithium ions.
  • Examples of the negative electrode active material include, but are not limited to, for example, carbon materials, silicon-based materials (for example, Si or SiO), tin-based materials, lithium titanate and lithium vanadium composite oxides with or without a substitution element. And alloys of lithium with one or more other metals (eg, tin, aluminum or antimony).
  • the carbon material is natural graphite, a composite carbonaceous material in which a film is formed on the surface of natural graphite by a dry CVD method or a wet spray method, a resin material such as epoxy or phenol, or a pitch-based material obtained from petroleum or coal.
  • the raw material include artificial graphite produced by firing, non-graphitizable carbon material, and the like.
  • the negative electrode active material is preferably a carbon material or lithium titanate.
  • the negative electrode active material may be used in the form of a mixture containing one or more of the materials as desired.
  • the negative electrode active material is usually used in the form of powder.
  • the particle size of the negative electrode active material powder is usually equal to or less than the thickness of the negative electrode mixture layer containing the gel electrolyte and the negative electrode active material.
  • the coarse particles are removed beforehand by means such as sieving classification or wind classification, and particles having a thickness equal to or less than the thickness of the negative electrode mixture layer Is preferably used.
  • the negative electrode mixture layer usually contains a negative electrode conductive agent and a negative electrode binder in addition to the gel electrolyte and the negative electrode active material.
  • the negative electrode conductive agent is a material used to supplement the electrical conductivity of the negative electrode active material.
  • the negative electrode conductive agent may be referred to as a conductive additive.
  • the negative electrode conductive agent include, but are not limited to, carbon materials such as acetylene black, carbon black, graphite, and amorphous carbon.
  • the negative electrode conductive agent is usually used in the form of a powder.
  • the negative electrode active material is a metal oxide
  • the negative electrode active material itself has high electrical resistance. Therefore, the electrical conductivity of the negative electrode mixture layer can be ensured by including the negative electrode conductive agent having electric conductivity in the negative electrode mixture layer together with the negative electrode active material.
  • the negative electrode binder is a material used for bonding the negative electrode active material and the negative electrode conductive agent contained in the negative electrode mixture layer and bonding the negative electrode mixture layer to the negative electrode current collector.
  • the negative electrode binder include, but are not limited to, styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVDF), and a mixture thereof.
  • the negative electrode active material and the negative electrode conductive agent are usually used in the form of powder. Therefore, by including the negative electrode binder in the negative electrode mixture layer together with the negative electrode active material and the negative electrode conductive agent, the adhesion of the negative electrode mixture layer material is improved and the negative electrode mixture layer is adhered to the negative electrode current collector. be able to.
  • the negative electrode current collector can be used without particular limitation as long as it is a material usually used in the technical field.
  • Examples of the negative electrode current collector include, but are not limited to, materials such as aluminum, stainless steel, and titanium.
  • the material of the negative electrode current collector is preferably aluminum.
  • the positive electrode usually has a gel electrolyte containing a lithium conductive polymer and an organic electrolyte, a positive electrode active material, a positive electrode conductive agent, a positive electrode binder, and a positive electrode current collector.
  • the positive electrode conductive agent, the positive electrode binder, and the positive electrode active material included in the positive electrode constitute a positive electrode mixture layer.
  • the lithium conductive polymer and the organic electrolyte contained in the positive electrode mixture layer may be the same material as the lithium conductive polymer and the organic electrolyte contained in the negative electrode mixture layer, and are different from each other. It may be a material.
  • the lithium conductive polymer and the organic electrolyte contained in the positive electrode mixture layer can be appropriately selected from the materials contained in the positive electrode mixture layer described above.
  • the positive electrode current collector can be used without particular limitation as long as it is a material usually used in the technical field.
  • the positive electrode current collector include, but are not limited to, materials such as aluminum, stainless steel, and titanium.
  • the material of the positive electrode current collector is preferably aluminum.
  • the positive electrode active material is a material into which lithium ions are desorbed in the charging process and lithium ions desorbed from the negative electrode active material in the negative electrode mixture layer are inserted in the discharging process.
  • the positive electrode active material can be used without particular limitation as long as it is a material that can be reversibly inserted and desorbed reversibly, which is usually used in the art.
  • the positive electrode active material examples include, but are not limited to, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 3 , LiMn 2 O 3 , LiMnO 2 , Li 4 Mn 5 O 12 and LiMn 2-x M x O 2 (wherein M is at least one metal selected from the group consisting of Co, Ni, Fe, Cr, Zn and Ti, and x is 0.01 to 0.2), Li 2 Mn 3 MO 8 (Wherein M is at least one metal selected from the group consisting of Fe, Co, Ni, Cu and Zn), Li 1-x A x Mn 2 O 4 (wherein A is Mg) , B, Al, Fe, Co, Ni, Cr, Zn and Ca, and at least one metal selected from the group consisting of 0.01 to 0.1), LiNi 1-x M x O 2 ( In the formula, M is at least one metal selected from the group consisting of Co, Fe and Ga, and x is 0.01 to 0.2), LiFeO 2
  • the positive electrode active material is usually used in the form of a powder.
  • the particle size of the positive electrode active material powder is usually equal to or less than the thickness of the positive electrode mixture layer.
  • the coarse particles are removed in advance by means such as sieving classification or wind classification, and particles having a thickness equal to or less than the thickness of the positive electrode mixture layer Is preferably used.
  • the positive electrode conductive agent is a material used to supplement the electrical conductivity of the positive electrode active material.
  • the positive electrode conductive agent may be described as a conductive additive.
  • the positive electrode conductive agent include, but are not limited to, carbon materials such as acetylene black, carbon black, graphite, and amorphous carbon.
  • the positive electrode conductive agent is usually used in the form of a powder.
  • the positive electrode active material is usually a metal oxide. For this reason, the positive electrode active material itself has a high electrical resistance. Therefore, by including the positive electrode conductive agent having electric conductivity in the positive electrode mixture layer together with the positive electrode active material, the electric conductivity of the positive electrode mixture layer can be ensured.
  • the positive electrode binder is a material used for bonding the positive electrode active material and the positive electrode conductive agent contained in the positive electrode mixture layer and bonding the positive electrode mixture layer to the positive electrode current collector.
  • the positive electrode binder include, but are not limited to, styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVDF), and a mixture thereof.
  • the positive electrode active material and the positive electrode conductive agent are usually used in the form of powder. Therefore, by including the positive electrode binder in the positive electrode mixture layer together with the positive electrode active material and the positive electrode conductive agent, the adhesion of the positive electrode mixture layer material is improved and the positive electrode mixture layer is brought into close contact with the positive electrode current collector. be able to.
  • the solid electrolyte can be used without particular limitation as long as it is a material usually used in the technical field. From the viewpoint of safety, a nonflammable inorganic solid electrolyte is preferable.
  • the solid electrolyte include, but are not limited to, Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 , LiAlGe (PO 4 ) 3 , Li 3.4 V 0.6 Si 0.4 O 4 and Li 2 P 2 O 6 .
  • Oxide glass perovskite oxides such as Li 0.34 La 0.51 TiO 2.94 , garnet oxides such as LiLaZrO 2 , sulfonylimide-based solids such as lithium bis (fluorosulfonyl) imide (LiFSI) or lithium trifluoromethanesulfonylimide Examples thereof include electrolytes, sulfide-based inorganic solid electrolytes, and polymer electrolytes.
  • the oxide may optionally contain a lithium halide such as LiCl or LiI. If desired, the solid electrolyte may be used in the form of a mixture containing one or more of the above materials.
  • FIG. 1 is a cross-sectional view of an all-solid lithium secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a main part of an all solid lithium secondary battery according to an embodiment of the present invention.
  • an all solid lithium secondary battery 100 of the present invention includes a negative electrode 80, a positive electrode 70, and a solid electrolyte 50 disposed between the negative electrode 80 and the positive electrode 70.
  • the negative electrode 80 includes a negative electrode current collector 20 and a negative electrode mixture layer 60.
  • the negative electrode mixture layer 60 includes a gel electrolyte containing a lithium conductive polymer and an organic electrolyte, and a negative electrode active material.
  • the positive electrode 70 includes the positive electrode current collector 10 and the positive electrode mixture layer 40.
  • the all solid lithium secondary battery 100 of the present invention is usually housed in a battery case 30.
  • the negative electrode mixture layer 60 and the positive electrode mixture layer 40 may have a laminated structure composed of a plurality of layers.
  • the positive electrode current collector 10 is electrically connected to the positive electrode mixture layer 40.
  • the positive electrode current collector 10 is usually an aluminum foil having a thickness of 10 to 100 mm, an aluminum perforated foil having a thickness of 10 to 100 mm and a hole diameter of 0.1 to 10 mm, an expanded metal, or a foam metal plate, etc. Is used.
  • the positive electrode current collector can be used without particular limitation as long as it has a shape usually used in the technical field.
  • the negative electrode current collector 20 is electrically connected to the negative electrode mixture layer 60.
  • a copper foil having a thickness of 10 to 100 mm, a copper perforated foil having a thickness of 10 to 100 mm and a hole diameter of 0.1 to 10 mm, an expanded metal, or a foam metal plate is usually used. Is done.
  • the negative electrode current collector can be used without particular limitation as long as it has a shape usually used in the technical field.
  • Battery case 30 accommodates positive electrode current collector 10, negative electrode current collector 20, positive electrode mixture layer 40, solid electrolyte layer 50, and negative electrode mixture layer 60.
  • the shape of the battery case 30 is a cylindrical shape, a flat oval shape, a flat oval shape, a square shape, or the like according to the shape of the electrode group composed of the positive electrode mixture layer 40, the solid electrolyte layer 50, and the negative electrode mixture layer 60. May be selected.
  • the material of the battery case 30 is selected from materials that are corrosion resistant to the non-aqueous electrolyte, such as aluminum, stainless steel, or nickel-plated steel.
  • the negative electrode mixture layer 60 includes a negative electrode active material 62, a lithium conductive polymer 63, a negative electrode conductive agent 64, a lithium salt 65, and an organic electrolyte. And a gel electrolyte containing 66.
  • the negative electrode mixture layer 60 is disposed so as to be sandwiched between the negative electrode current collector 20 and the solid electrolyte layer 50.
  • the negative electrode mixture layer 60 used in the all solid lithium secondary battery of the present invention has a low viscosity as compared with a conventional product, and thus has high fluidity.
  • the negative electrode active material 62 and / or the negative electrode conductive agent 64 expands and contracts by repeating the charge / discharge cycle, the negative electrode active material 62 and / or the negative electrode conductive agent 64 and the lithium conductive polymer 63, the negative electrode conductive agent 64, the formation of voids between the gel electrolyte containing the lithium salt 65 and the organic electrolyte 66 can be substantially suppressed.
  • the all-solid lithium secondary battery of the present invention can exhibit high output without decreasing its capacity even when the charge / discharge cycle is repeated over a long period of time. Therefore, it is possible to apply the all solid lithium secondary battery of the present invention to the use of a stationary lithium secondary battery such as a power storage battery.
  • the present invention also relates to a method for producing an all-solid lithium secondary battery.
  • the method for producing an all solid lithium secondary battery of the present invention includes a gel electrolyte forming step in which a lithium conductive polymer is swollen with an organic electrolyte to form a gel electrolyte containing the lithium conductive polymer and the organic electrolyte. It is necessary to include.
  • This step includes, for example, (i) a step of mixing a lithium conductive polymer with an organic solvent to form a lithium conductive polymer slurry, and removing the organic solvent from the slurry to form a gel electrolyte precursor And a step of impregnating the precursor of the gel electrolyte with an organic electrolyte to form a gel electrolyte.
  • the lithium conductive polymer slurry may contain a lithium salt, a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder, if desired. In this case, the slurry of the lithium conductive polymer becomes a slurry of the negative electrode mixture layer material.
  • This step can also be carried out as a step including (ii) forming a gel electrolyte by impregnating the precursor of the gel electrolyte with an organic electrolyte and a lithium salt in the step (i).
  • the lithium conductive polymer slurry may contain a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder, if desired, but does not contain a lithium salt.
  • an organic electrolyte, a lithium salt, a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder are mixed with an organic solvent to conduct lithium. It can also be carried out as a process including a step of forming a slurry of a conductive polymer.
  • the lithium conductive polymer slurry is a slurry containing all the materials of the negative electrode mixture layer. Therefore, in the step (iii), it is not necessary to perform the step of forming the gel electrolyte by impregnating the precursor of the gel electrolyte with the organic electrolyte.
  • This step can also be carried out as a step of (iv) forming the gel electrolyte in step (i) by impregnating the gel electrolyte precursor with an organic electrolyte under reduced pressure, preferably in a vacuum state. .
  • the gel electrolyte can be filled in the voids in the negative electrode mixture layer and / or the voids in the negative electrode active material in a short time. Therefore, by carrying out this step according to step (iv), the battery characteristics of the resulting all-solid lithium secondary battery of the present invention can be improved.
  • the organic solvent used in the steps (i) to (iv) is not particularly limited.
  • the organic solvent normally used in the said technical field can be used.
  • the steps (i) to (iv) can be carried out under heating conditions as desired. Thereby, the gelation reaction of the gel electrolyte containing a lithium conductive polymer and an organic electrolyte can be promoted.
  • This step can also be carried out as a step including any combination of the steps (i) to (iv).
  • This step can also be carried out as a step of repeating a desired step a plurality of times in the steps (i) to (iv).
  • the negative electrode which has a some electrode compound-material layer can be formed.
  • the lithium conductive polymer, organic electrolyte, lithium salt, negative electrode active material, negative electrode conductive agent and negative electrode binder used in this step are appropriately selected from the materials for the all-solid lithium secondary battery of the present invention described above. can do.
  • the method for producing an all solid lithium secondary battery of the present invention preferably further includes a material laminating step of laminating the lithium conductive polymer and the negative electrode active material on the negative electrode current collector before the gel electrolyte forming step. .
  • the step of forming the precursor of the gel electrolyte is performed by applying a lithium conductive polymer slurry containing a lithium conductive polymer and an organic solvent to the surface of the negative electrode current collector.
  • the step of laminating and removing the organic solvent from the slurry to form a gel electrolyte precursor on the surface of the negative electrode current collector can be carried out.
  • the means for laminating the lithium conductive polymer slurry on the surface of the negative electrode current collector is not limited, and examples thereof include a doctor blade method, a dipping method, a spray method or a screen printing method. Can do.
  • the step of forming the gel electrolyte precursor on the surface of the negative electrode current collector is not limited.
  • the gel electrolyte precursor is applied to the surface of the negative electrode current collector by means of a roll press or the like. It can be carried out by pressing. By carrying out this step, the resulting negative electrode composite material layer in the all solid lithium secondary battery of the present invention can be formed into a desired shape.
  • the negative electrode current collector used in this step can be appropriately selected from the materials of the all solid lithium secondary battery of the present invention described above.
  • the positive electrode can be formed by a method usually used in the art.
  • the material for the positive electrode can be appropriately selected from the materials for the all solid lithium secondary battery of the present invention described above.
  • the positive electrode is preferably formed by applying the same procedure as the gel electrolyte forming step and the material laminating step described above. By applying the same procedure as that for the negative electrode to the formation of the positive electrode, the all solid lithium secondary battery of the present invention can be efficiently produced.
  • LTO LiTi 4 O 12
  • AB acetylene black
  • PVDF polyvinylidene fluoride
  • the polymer 1 was prepared as a lithium conductive polymer so as to have the above-described solid component mass ratio.
  • LTO was prepared as a powder having an average particle diameter of 20 ⁇ m, AB as a powder, PVDF as an NMP solution, and Polymer 1 as an NMP solution prepared by the above procedure.
  • the above materials were mixed in an agate mortar to prepare a slurry of the negative electrode mixture layer material. Thereafter, the slurry was applied to the surface of an aluminum foil having a thickness of 20 ⁇ m. The coated aluminum foil was left in a drier set at a temperature of 80 ° C., and NMP contained in the slurry was distilled off. The obtained aluminum foil was punched into a circle having a diameter of 15 mm together with the negative electrode mixture layer formed on the surface. The punched circular material was uniaxially pressed from above and below to obtain a negative electrode in which a negative electrode mixture layer having a density of about 1.6 cm / cm 3 was formed on the surface of the negative electrode current collector.
  • the produced negative electrode was put in a container in which about 1 ml of propylene carbonate (PC) (organic electrolyte solution) was previously injected, and the entire negative electrode was placed in contact with the PC.
  • PC propylene carbonate
  • the whole container was depressurized to be in a vacuum state for 1 minute. By the decompression operation, PC was impregnated into the negative electrode mixture layer. After 30 minutes, the negative electrode was removed from the container. The obtained negative electrode was left in a glove box to evaporate PC remaining on the surface of the negative electrode. By the said operation, the negative electrode in which the gel electrolyte was formed was obtained.
  • the amount of PC evaporation was adjusted so that the gel concentration defined by the following formula was 10% by mass.
  • LiCoO 2 as a positive electrode active material
  • 5 parts by mass of acetylene black (AB) as a conductive additive 5 parts by mass of polyvinylidene fluoride (PVDF) as a positive electrode binder
  • 10 parts by mass of polymer 1 as lithium As a conductive polymer, it prepared so that it might become said solid component mass ratio.
  • LiCoO 2 was prepared as a powder having an average particle size of 10 ⁇ m, AB as a powder, PVDF as an NMP solution, and Polymer 1 as an NMP solution prepared by the above procedure. The above materials were mixed in an agate mortar to prepare a slurry of the positive electrode mixture layer material.
  • the slurry was applied to the surface of an aluminum foil having a thickness of 20 ⁇ m.
  • the coated aluminum foil was left in a drier set at a temperature of 80 ° C., and NMP contained in the slurry was distilled off.
  • the obtained aluminum foil was punched into a circle having a diameter of 15 mm together with the positive electrode mixture layer formed on the surface.
  • the punched circular material was uniaxially pressed from above and below to obtain a positive electrode in which a positive electrode mixture layer having a density of about 1.6 cm / cm 3 was formed on the surface of the positive electrode current collector.
  • the produced positive electrode was put in a container in which about 1 ml of propylene carbonate (PC) (organic electrolyte solution) was injected in advance, and the entire positive electrode was placed in contact with the PC.
  • PC propylene carbonate
  • the whole container was depressurized to be in a vacuum state for 1 minute.
  • the positive electrode mixture layer was impregnated with PC.
  • the positive electrode was taken out of the container.
  • the obtained positive electrode was left in a glove box to evaporate PC remaining on the surface of the positive electrode.
  • a positive electrode on which a gel electrolyte was formed was obtained.
  • the amount of PC evaporation was adjusted so that the gel concentration defined by the above formula was 10% by mass.
  • Example 2 The production of the all-solid-state lithium secondary battery of Example 2 was the same as the procedure of Example 1, except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 5% by mass. was performed in the same procedure as described above.
  • Example 3 The production of the all-solid-state lithium secondary battery of Example 3 was the same as that of Example 1, except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 12% by mass. Was performed in the same procedure as described above.
  • Example 4 The production of the all-solid lithium secondary battery of Example 4 was performed except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 3% by mass in the procedure of Example 1. Was performed in the same procedure as described above.
  • Example 5 Production of the all-solid-state lithium secondary battery of Example 5 was the same as that of Example 1, except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 15% by mass. Was performed in the same procedure as described above.
  • Example 6 The production of the all-solid-state lithium secondary battery of Example 6 was the same as that of Example 1, except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 0.01% by mass. Was performed in the same procedure as described above.
  • Example 7 Preparation of the all-solid-state lithium secondary battery of Example 7 was carried out in the procedure of Example 1, with the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer represented by the following formula (II): (In the formula, n are each independently an integer in the range of 1 to 10,000.) The procedure was the same as described above except that the compound was changed to the compound represented by (average molecular weight: 300,000).
  • Example 8 In the production of the all solid lithium secondary battery of Example 8, in the procedure of Example 1, the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was expressed by the following formula (III): (Wherein x and y are each independently an integer ranging from 1 to 10000) The procedure was the same as described above except that the compound was changed to the compound represented by (average molecular weight: 300,000).
  • Example 9 The all-solid lithium secondary battery of Example 9 was prepared by replacing the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer with the following formula (IV) in the procedure of Example 1. (In the formula, n are each independently an integer in the range of 1 to 10,000.) The procedure was the same as described above except that the compound was changed to the compound represented by (average molecular weight: 300,000).
  • Example 10 The all-solid lithium secondary battery of Example 10 was prepared in the same manner as described above except that the charge / discharge rate in the evaluation test of electrochemical characteristics was changed to 0.1 C in the procedure of Example 1.
  • Example 11 The all-solid lithium secondary battery of Example 11 was prepared in the same manner as described above, except that the charge / discharge rate in the electrochemical property evaluation test was changed to 0.5 C in the procedure of Example 1.
  • Example 12 The all-solid lithium secondary battery of Example 12 was produced in the same manner as described above, except that the charge / discharge rate in the electrochemical property evaluation test was changed to 0.1 C in the procedure of Example 7.
  • Example 13 The all-solid lithium secondary battery of Example 13 was prepared in the same manner as described above, except that the charge / discharge rate in the evaluation test of electrochemical characteristics was changed to 0.1 C in the procedure of Example 8.
  • Example 14 The all-solid lithium secondary battery of Example 13 was prepared in the same manner as described above, except that the charge / discharge rate in the evaluation test of electrochemical characteristics was changed to 0.1 C in the procedure of Example 9.
  • Comparative Example 1 The production of the all-solid lithium secondary battery of Comparative Example 1 was performed except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 20% by mass in the procedure of Example 1. Was performed in the same procedure as described above.
  • Comparative Example 2 The production of the all-solid lithium secondary battery of Comparative Example 2 was performed except that the concentration of the lithium conductive polymer in the gel electrolyte of the negative electrode mixture layer and the positive electrode mixture layer was changed to 50% by mass in the procedure of Example 1. Was performed in the same procedure as described above.
  • Comparative Example 5 The production of the all-solid lithium secondary battery of Comparative Example 5 was carried out in the same manner as in Example 1, except that the composition of the negative electrode layer was 90.6 parts by mass of the negative electrode active material LiTi 4 O 12 , 4.7 parts by mass of the conductive auxiliary agent acetylene black (AB ), And 4.7 parts by mass of PVDF solid component mass ratio, the electrode composition of the positive electrode is 90 parts by mass of positive electrode active material LiCoO 2 , 5 parts by mass of conductive auxiliary agent acetylene black (AB), 5 parts by mass of The procedure was the same as above except that the solid component mass ratio of PVDF was changed.
  • Table 1 shows the evaluation test results of the electrochemical characteristics of the all-solid lithium secondary batteries of Examples and Comparative Examples.
  • this invention is not limited to an above-described Example, Various modifications are included.
  • the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described. Further, it is possible to add, delete, and / or replace another configuration with respect to a part of the configuration of each embodiment.

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Abstract

　La présente invention concerne un accumulateur au lithium entièrement solide à rendement élevé. Elle se rapporte à un accumulateur au lithium entièrement solide qui comprend : une électrode négative comportant un électrolyte sous forme de gel, qui contient un polymère électroconducteur au lithium et un électrolyte organique à raison de 0,01-15 % en masse de la masse totale, un matériau actif d'électrode négative et un collecteur de courant d'électrode négative ; une électrode positive ; et un électrolyte solide, qui est placé entre l'électrode négative et l'électrode positive.
PCT/JP2014/059405 2014-03-31 2014-03-31 Accumulateur au lithium entierement solide WO2015151145A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112072164A (zh) * 2020-08-28 2020-12-11 蜂巢能源科技有限公司 固态锂电池及其制备方法
CN113823768A (zh) * 2021-08-27 2021-12-21 天津空间电源科技有限公司 一种适用于固态电池的正极制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11297357A (ja) * 1998-04-07 1999-10-29 Hitachi Maxell Ltd ポリマーリチウムイオン二次電池の製造方法
JP2000003728A (ja) * 1998-06-15 2000-01-07 Mitsubishi Chemicals Corp リチウム二次電池及びその製造方法
JP2000123871A (ja) * 1998-10-13 2000-04-28 Yuasa Corp 固体電解質リチウム二次電池
JP2002025618A (ja) * 2000-07-05 2002-01-25 Matsushita Electric Ind Co Ltd リチウムポリマー二次電池の製造方法
JP2007213930A (ja) * 2006-02-08 2007-08-23 Nissan Motor Co Ltd バイポーラ電池、組電池およびこれらを搭載した車両
JP4228541B2 (ja) * 1998-09-01 2009-02-25 ソニー株式会社 非水系ゲル電解質電池の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11297357A (ja) * 1998-04-07 1999-10-29 Hitachi Maxell Ltd ポリマーリチウムイオン二次電池の製造方法
JP2000003728A (ja) * 1998-06-15 2000-01-07 Mitsubishi Chemicals Corp リチウム二次電池及びその製造方法
JP4228541B2 (ja) * 1998-09-01 2009-02-25 ソニー株式会社 非水系ゲル電解質電池の製造方法
JP2000123871A (ja) * 1998-10-13 2000-04-28 Yuasa Corp 固体電解質リチウム二次電池
JP2002025618A (ja) * 2000-07-05 2002-01-25 Matsushita Electric Ind Co Ltd リチウムポリマー二次電池の製造方法
JP2007213930A (ja) * 2006-02-08 2007-08-23 Nissan Motor Co Ltd バイポーラ電池、組電池およびこれらを搭載した車両

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112072164A (zh) * 2020-08-28 2020-12-11 蜂巢能源科技有限公司 固态锂电池及其制备方法
CN113823768A (zh) * 2021-08-27 2021-12-21 天津空间电源科技有限公司 一种适用于固态电池的正极制备方法
CN113823768B (zh) * 2021-08-27 2024-03-22 天津空间电源科技有限公司 一种固态电池的制备方法

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