WO2013143085A1 - 一种固态电解质电池 - Google Patents

一种固态电解质电池 Download PDF

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Publication number
WO2013143085A1
WO2013143085A1 PCT/CN2012/073186 CN2012073186W WO2013143085A1 WO 2013143085 A1 WO2013143085 A1 WO 2013143085A1 CN 2012073186 W CN2012073186 W CN 2012073186W WO 2013143085 A1 WO2013143085 A1 WO 2013143085A1
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Prior art keywords
solid electrolyte
active material
positive electrode
electrode sheet
negative electrode
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PCT/CN2012/073186
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English (en)
French (fr)
Inventor
周明杰
钟玲珑
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201280068232.XA priority Critical patent/CN104094464A/zh
Priority to EP12873283.1A priority patent/EP2833462A4/en
Priority to US14/377,933 priority patent/US20150037655A1/en
Priority to PCT/CN2012/073186 priority patent/WO2013143085A1/zh
Priority to JP2015502039A priority patent/JP2015515094A/ja
Publication of WO2013143085A1 publication Critical patent/WO2013143085A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H01M10/0418—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes with bipolar electrodes
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H01M10/044—Small-sized flat cells or batteries for portable equipment with bipolar electrodes
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of batteries, and more particularly to a solid electrolyte battery.
  • a solid electrolyte is used for a battery, which is not a liquid electrolyte liquid, and its contact with the electrode is not completely immersed in contact with the liquid electrolyte, and therefore, the incomplete contact state between the solid electrolyte and the electrode greatly affects the battery. performance. For example, the contact resistance between the solid electrolyte and the electrode is increased, and the internal resistance of the battery is increased; in addition, lithium ions cannot migrate between the solid electrolyte and the electrode in an ideal state, which lowers the battery capacity.
  • the problem to be solved by the present invention is to provide a solid electrolyte battery having a small internal resistance of a battery and a large battery capacity.
  • a solid electrolyte battery comprises a positive electrode sheet, a negative electrode sheet, a plurality of composite electrode sheets and a plurality of solid electrolytes, and the number of solid electrolytes is one more than the number of composite electrode sheets; the positive electrode sheets and the negative electrode sheets are relatively spaced apart, and the composite electrode sheets are arranged Between the positive electrode sheet and the negative electrode sheet, and the two sides of the composite electrode sheet are respectively stacked with the positive electrode sheet and the negative electrode sheet through a solid electrolyte to form a solid electrolyte battery structure;
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material coated on a surface of the positive electrode current collector;
  • the negative electrode sheet includes a negative electrode current collector and an anode active material coated on a surface of the negative electrode current collector;
  • the composite electrode sheet includes a composite electrode current collector and a positive electrode active material and a negative electrode active material coated on both sides of the composite electrode current collector;
  • the positive electrode active material on the positive electrode sheet and the negative electrode active material on the composite electrode sheet are disposed correspondingly by a solid electrolyte; and at the same time, the negative electrode active material on the negative electrode sheet and the positive electrode active material on the composite electrode sheet The layers are disposed correspondingly by another solid electrolyte.
  • the positive electrode active material is a lithium salt of a graphite oxide derivative, and a polyethylene oxide is grafted on the surface of the graphite oxide of the lithium salt of the graphite oxide derivative, and the polyoxyethylene chain end is a hydroxyl lithium;
  • the negative electrode active material For graphene polyethylene oxide is grafted on the surface of graphene.
  • the positive electrode active material and the negative electrode active material both contain a conductive agent, and the conductive agent is added to provide conductive properties; the conductive agent is acetylene black.
  • the solid electrolyte includes a lithium salt, a polyethylene oxide, and a plasticizer, and the ratio of the amount of the polyoxyethylene to the lithium salt is calculated according to the molar amount of the oxygen element and the lithium element, and the oxygen element and the lithium element The molar ratio is 5 ⁇ 20:1; the plasticizer accounts for 5 ⁇ 50% of the total mass; the lithium salt includes LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 and LiAsF at least one of 6; the plasticizer is selected from carbonate-based or polar solvents; preferably the carbonates, ethylene carbonate, propylene carbonate or diethyl carbonate; the polar solvent is ethylene glycol Dimethyl ether or dimethyl sulfoxide.
  • the cathode current collector is preferably an aluminum foil and an anode current collector, preferably a copper foil; and the composite electrode current collector is preferably a titanium foil.
  • the surface of the positive electrode sheet, the composite electrode sheet, and the negative electrode sheet are coated with a positive electrode active material and a negative electrode active material which can form a positive and negative capacitor structure; the positive electrode active material and the negative electrode active material can be combined with a solid electrolyte Forming a good layered stacking arrangement, thereby greatly reducing the internal resistance of the battery, facilitating migration between ions, thereby increasing battery capacity.
  • the outer layers of the positive electrode active material and the negative electrode active material are coated with polyethylene oxide. Since the polyethylene oxide has good compatibility with the solid electrolyte, the lithium ions in the solid electrolyte can diffuse well to the positive electrode activity. Material and anode active material greatly reduce battery contact internal resistance The active migration of lithium ions between the solid electrolyte and the active materials of the positive and negative electrodes increases the battery capacity.
  • n The number of sheets after laminating the solid electrolyte and the composite electrode sheet, taking a positive integer
  • FIG. 2 is a schematic structural view of a solid electrolyte battery in a preferred embodiment; wherein the composite electrode sheet and the solid electrolyte are stacked in one piece;
  • FIG. 3 is a schematic structural view of a solid electrolyte battery in a preferred embodiment; wherein the composite electrode sheet and the solid electrolyte are laminated in three pieces;
  • Fig. 4 is a comparison of battery capacities of the solid electrolyte batteries prepared in Example 1 and Comparative Example 1.
  • a solid electrolyte battery provided by the present invention as shown in FIG. 1, comprises a positive electrode sheet 1, a negative electrode sheet 2, a plurality of composite electrode sheets 3, and a plurality of solid electrolytes 4, and the number of solid electrolytes 4 is larger than that of the composite electrode sheets 3.
  • the number of the positive electrode sheets 1 and the negative electrode sheets 2 are relatively spaced apart, the composite electrode sheets 3 are interposed between the positive electrode sheets 1 and the negative electrode sheets 2, and the composite electrode sheets 2 are respectively passed through the solid electrolyte 4 and the positive electrode sheets 1 and
  • the negative electrode sheets 2 are stacked to form a solid electrolyte battery structure, that is, a positive electrode sheet / (solid electrolyte 4 / composite electrode sheet 3) n / solid electrolyte 4 / negative electrode sheet 2; n is a laminated sheet of solid electrolyte 4 and composite electrode sheet 3 Number, take a positive integer;
  • the positive electrode sheet 1 includes a cathode current collector 11 and a cathode active material 12 coated on a surface of the cathode current collector 11; 2 includes a negative electrode current collector 21 and an anode active material 22 coated on the surface of the anode current collector 21; the composite electrode sheet 3 includes a composite electrode current collector 30 and a composite electrode current collector 30 Positive active material 31 and negative active material 32 on both sides;
  • the positive electrode active material 12 on the positive electrode sheet 1 and the negative electrode active material 32 on the composite electrode sheet 3 A capacitor structure is formed by laminating a solid electrolyte 4 in a corresponding manner; at the same time, the anode active material 22 on the anode sheet 2 and the cathode active material 31 on the composite electrode sheet 3 are formed. Another capacitor structure is formed by laminating between the other solid electrolytes 4; thus, the entire solid electrolyte battery is internally formed with two capacitor-type solid electrolyte batteries connected in series.
  • the positive electrode active material is a lithium salt of a graphite oxide derivative, and a polyethylene oxide is grafted on the surface of the graphite oxide of the lithium salt of the graphite oxide derivative, and the polyoxyethylene chain end is a hydroxyl lithium;
  • the negative electrode active material For graphene polyethylene oxide is grafted on the surface of the graphene.
  • the positive electrode active material and the negative electrode active material both contain a conductive agent, and the conductive agent is added to provide conductive properties; the conductive agent is acetylene black.
  • the solid electrolyte includes a lithium salt, a polyethylene oxide, and a plasticizer, and the ratio of the amount of the polyoxyethylene to the lithium salt is calculated according to the molar amount of the oxygen element and the lithium element, and the oxygen element and the lithium element The molar ratio is 5 ⁇ 20:1; the plasticizer accounts for 5 ⁇ 50% of the total mass; the lithium salt includes LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 and LiAsF at least one of 6; the plasticizer is selected from carbonate-based solvent or polar; the selection carbonates ethylene carbonate, propylene carbonate, dimethyl carbonate or diethyl carbonate, preferably ethylene carbonate , propylene carbonate or diethyl carbonate; the polar solvent is preferably ethylene glycol dimethyl ether, dimethyl sulfoxide, polyethylene glycol dimethyl ether or dibutyl phthalate, preferably ethylene glycol Meth
  • the current collector is made of a metal material, wherein the positive current collector may be an aluminum mesh or an aluminum foil, preferably an aluminum foil; the negative current collector is selected from a copper mesh or a copper foil, preferably a copper foil; From titanium mesh or titanium foil, titanium foil is preferred.
  • the number of laminated composite electrode sheets and solid electrolyte in the above specific embodiment may be one piece, or may be more than ten pieces or even hundreds of pieces. If the number of laminated composite electrode sheets and solid electrolyte is two or more, a plurality of capacitors are connected in series to form a battery structure, and the number of series determines the battery output voltage.
  • the number of the composite electrode sheets and the solid electrolyte laminated is one piece, and the structure of the solid electrolyte battery is: positive electrode sheet 1/ Solid electrolyte 4/ Composite electrode sheet 3/ Solid electrolyte 4/ Negative electrode sheet 2 .
  • the number of laminated composite electrode sheets and solid electrolyte is three.
  • the structure of the solid electrolyte battery is: positive electrode sheet 1 / solid electrolyte 4 / composite electrode sheet 3 / solid electrolyte 4 / composite electrode sheet 3 / Solid electrolyte 4 / composite electrode sheet 3 / solid electrolyte 4 / negative electrode sheet 2; that is, positive electrode sheet 1 / (solid electrolyte 4 / composite electrode sheet 3) 3 / solid electrolyte 4 / negative electrode sheet 2 .
  • the surface of the positive electrode sheet, the composite electrode sheet, and the negative electrode sheet are coated with a positive electrode active material and a negative electrode active material which can form a positive and negative capacitor structure; the positive electrode active material and the negative electrode active material can be combined with a solid electrolyte Forming a good layered stacking arrangement, thereby greatly reducing the internal resistance of the battery, facilitating migration between ions, thereby increasing battery capacity.
  • the outer layers of the positive electrode active material and the negative electrode active material are coated with polyethylene oxide. Since the polyethylene oxide has good compatibility with the solid electrolyte, the lithium ions in the solid electrolyte can diffuse well to the positive electrode activity. Material and anode active material greatly reduce battery contact internal resistance The active migration of lithium ions between the solid electrolyte and the active materials of the positive and negative electrodes increases the battery capacity.
  • the manufacturing method of the above solid electrolyte battery comprises the following process steps:
  • positive electrode active material lithium oxide oxide derivative, conductive agent and binder PVDF Dissolved in an organic solvent to form a colloidal positive active material
  • Preparation of positive electrode sheet coating the positive electrode active material on the surface of the positive current collector, and placing it for 1 ⁇ 24h , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of a desired specification;
  • Preparation of negative electrode sheet coating the surface of the negative electrode current collector with colloidal negative active material, and placing it for 1 ⁇ 24h Passing the negative active material into the negative current collector, drying and cutting into a negative electrode sheet of a desired specification;
  • a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 1 ⁇ 24h , the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, and dried to be cut into a composite electrode sheet of a desired specification;
  • step S4 the laminated structure of step S3, the residual organic solvent is removed by hot press molding to obtain a solid battery, as shown in FIG.
  • the conductive agent is acetylene black.
  • the solid electrolyte comprises a lithium salt, a polyethylene oxide and a plasticizer, and the ratio of the amount of the polyoxyethylene to the lithium salt is calculated according to the molar amount of the oxygen element and the lithium element, and the molar ratio of the oxygen element to the lithium element The ratio is 5 ⁇ 20:1; the plasticizer accounts for 5 ⁇ 50% of the total mass; the lithium salt includes LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 3 and LiAsF 6 At least one of; the plasticizer is selected from a carbonate or a polar solvent; the carbonate is preferably ethylene carbonate, propylene carbonate, dimethyl carbonate or diethyl carbonate; the polar solvent is preferably Ethylene glycol dimethyl ether, dimethyl sulfoxide, polyethylene glycol dimethyl ether or dibutyl phthalate.
  • the cathode current collector is selected from the group consisting of aluminum foil and the anode current collector is selected from the group consisting of copper foil; and the composite electrode current collector is selected from the group consisting of titanium foil.
  • the organic solvent is a tetrahydrofuran (THF) solution or a methylpyrrolidone (NMP) solution; preferably methylpyrrolidone ( NMP) solution.
  • Preparation of positive electrode active material mass ratio of 90 g of graphite oxide derivative lithium salt, 5 g of acetylene black and 5 g of binder PVDF The ratio of 90:5:5 is mixed and dissolved in a tetrahydrofuran solution to form a colloidal positive active material;
  • Preparation of positive electrode sheet coated with positive electrode active material on the surface of positive electrode current collector, placed for 1h , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of negative electrode sheet coating the surface of the negative electrode current collector with colloidal negative active material, and placing it for 1 hour , the negative active material is infiltrated into the negative current collector, dried and cut into a negative electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of composite electrode sheets a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 1 hour.
  • the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, dried, and then cut into composite electrode sheets of a desired specification.
  • the laminated structure of the step 3 is subjected to hot press molding to remove the residual tetrahydrofuran solution to obtain a solid battery.
  • Preparation of solid electrolyte 10g of LiBF 4 and 37.4g of PEO are dissolved in NMP solution, wherein the molar ratio of oxygen element to LiBF 4 in PEO is 8:1, and then 8.4g of plasticizer propylene carbonate is added to make up 15% of total mass. Forming a gel electrolyte, drying and solidifying to form a solid electrolyte;
  • Preparation of positive electrode sheet coating the positive electrode active material on the surface of the positive current collector, and placing it for 24 hours. , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of negative electrode sheet coating the surface of the negative current collector with a gel-like negative active material for 24h , the negative active material is infiltrated into the negative current collector, dried and cut into a negative electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of composite electrode sheets a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 24 hours.
  • the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, dried, and then cut into composite electrode sheets of a desired specification.
  • step 3 the residual NMP solution is removed by hot press molding to obtain a solid battery.
  • positive electrode active material 95 g of graphite oxide derivative lithium salt, 5.3 g of acetylene black and 5.3 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in NMP solution to form a colloidal positive active material;
  • negative active material 95 g of graphene derivative lithium salt, 5.3 g of acetylene black, and 5.3 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in NMP solution to form a colloidal negative active material;
  • Preparation of positive electrode sheet coating the positive electrode active material on the surface of the positive current collector, and placing it for 5 hours. , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of negative electrode sheet coating the surface of the negative electrode current collector with colloidal negative active material, and placing it for 5 hours , the negative active material is infiltrated into the negative current collector, dried and cut into a negative electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of composite electrode sheets a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 5 hours.
  • the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, dried, and then cut into composite electrode sheets of a desired specification.
  • step 3 the residual NMP solution is removed by hot press molding to obtain a solid battery.
  • positive electrode active material 80 g of graphite oxide derivative lithium salt, 4.4 g of acetylene black and 4.4 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in a tetrahydrofuran solution to form a colloidal positive active material;
  • negative active material 80 g of graphene derivative lithium salt, 4.4 g of acetylene black and 4.4 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in a tetrahydrofuran solution to form a colloidal negative active material;
  • Preparation of positive electrode sheet coating the surface of the positive current collector with a gel-like positive active material, and placing it for 10 hours. , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of negative electrode sheet coating the surface of the negative electrode current collector with colloidal negative active material, and placing it for 10 hours , the negative active material is infiltrated into the negative current collector, dried and cut into a negative electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of composite electrode sheets a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 10 hours.
  • the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, dried, and then cut into composite electrode sheets of a desired specification.
  • the laminated structure of the step 3 is subjected to hot press molding to remove the residual tetrahydrofuran solution to obtain a solid battery.
  • positive electrode active material 85 g of graphite oxide derivative lithium salt, 4.7 g of acetylene black and 4.7 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in a tetrahydrofuran solution to form a colloidal positive active material;
  • negative active material 85 g of graphene derivative lithium salt, 4.7 g of acetylene black and 4.7 g of binder PVDF Mixing in a ratio of 90:5:5 by mass ratio, dissolving in a tetrahydrofuran solution to form a colloidal negative active material;
  • Preparation of positive electrode sheet coated with positive electrode active material on the surface of positive current collector, placed for 15h , the positive active material is infiltrated into the positive current collector, and dried to be cut into a positive electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of negative electrode sheet coating the surface of the negative current collector with a gel-like negative active material for 15h , the negative active material is infiltrated into the negative current collector, dried and cut into a negative electrode sheet of 60 mm ⁇ 40 mm;
  • Preparation of composite electrode sheets a gel-like positive active material and a negative active material are respectively coated on both surfaces of the composite electrode current collector, and placed for 15 hours.
  • the positive electrode active material and the negative electrode active material are respectively infiltrated into the negative electrode current collector, dried, and then cut into composite electrode sheets of a desired specification.
  • the laminated structure of the step 3 is subjected to hot press molding to remove the residual tetrahydrofuran solution to obtain a solid battery.
  • Preparation of positive electrode active material mass ratio of 90 g of lithium oxide of graphite oxide, 5 g of acetylene black and 5 g of binder PVDF The ratio of 90:5:5 is mixed and dissolved in a tetrahydrofuran solution to form a colloidal positive active material;
  • Preparation of negative active material mass ratio of 90g graphene, 5g acetylene black and 5g binder PVDF The ratio of 90:5:5 is mixed and dissolved in a tetrahydrofuran solution to form a colloidal negative active material.
  • Example 4 is a comparison of battery capacities of the solid electrolyte batteries prepared in Example 1 and Comparative Example 1. As shown in FIG. 4, Example 1 The curve semicircle is smaller than the curve semicircle of Comparative Example 1, indicating that the internal resistance of the solid electrolyte battery produced in Example 1 is lowered, that is, the battery capacity is increased.

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Abstract

一种固态电解质电池，包括正极片（1）、负极片（2）、若干片复合电极片（3）和若干片固态电解质（4），其中固态电解质（4）的数量比复合电极片（3）的数量多一片。正极片（1）与负极片（2）相对间隔设置，复合电极片（3）介于正极片（1）和负极片（2）之间，且复合电极片（3）两侧分别通过固态电解质（4）与正极片（1）和负极片（2）层叠设置，形成固态电解质电池结构。根据本发明的固态电解质电池，由于正极片（1）、复合电极片（3）、负极片（2）的表面均涂敷有可以形成正负电容器结构的正极活性材料和/或负极活性材料，正极活性材料和负极活性材料能与固态电解质（4）形成良好的层状层叠结构，进而大大的降低电池的内阻，有利于离子的迁移，从而提高了电池容量。

Description

一种固态电解质电池
技术领域
本发明涉及电池领域，尤其涉及 一种固态电解质电池 。
背景技术
近来许多类型的便携电子设备，如，内装摄像机的录像机、便携式电话或便携式计算机已登场亮相，人们正致力于降低它们的尺寸和重量。同时，这些电子设备一般采用二次电池。这些二次电池中，薄型锂电池、折叠式电池的研究和实验正蓬勃地开展。对于这些电池的电解质，正着力进行固态电解质的研究。特别是具有溶于高分子材料的锂盐的高分子固态电解质或含有塑化剂的胶化的固态电解质正引起注意。
用固态电解质降低电池厚度比用液态电解质更有意义，同时没有电池漏液的危险。然而，固态电解质用于电池，它不是液态电解质的液体，其与电极的接触就不像液态电解质那样完全浸没接触，因此，固态电解质与电极之间的非完全接触状态也就极大地影响了电池性能。如，增大了固态电解质与电极之间的接触电阻，电池的内阻增大；此外，锂离子不能以理想状态在固态电解质与电极之间迁移，也就降低了电池容量。
发明内容
本发明所要解决的问题在于提供一种电池内阻小、电池容量大的固态电解质电池。
一种固态电解质电池，包括正极片、负极片、若干片复合电极片以及若干片固态电解质，且固态电解质的数量比复合电极片的数量多一片；正极片与负极片相对间隔设置，复合电极片介于正极片和负极片之间，且复合电极片两侧分别通过固态电解质与所述正极片和负极片层叠设置，形成固态电解质电池结构；其中，
所述正极片包括正极集流体以及涂覆在正极集流体表面的正极活性材料；
所述负极片包括负极集流体以及涂覆在负极集流体表面的负极活性材料；
所述复合电极片包括复合电极集流体以及涂覆在复合电极集流体两侧面的正极活性材料和负极活性材料；
所述固态电解质电池结构中，正极片上的正极活性材料与复合电极片上的负极活性材料之间通过一固态电解质相对应层叠设置；同时，负极片上的负极活性材料与复合电极片上的正极活性材料之间通过另一固态电解质相对应层叠设置。
所述固态电解质电池中，正极活性材料为氧化石墨衍生物锂盐，在所述氧化石墨衍生物锂盐的氧化石墨表面嫁接有聚氧化乙烯，且聚氧化乙烯链端为羟基锂；负极活性材料为石墨烯，在石墨烯表面的嫁接有聚氧化乙烯。
所述固态电解质电池中，优选，所述正极活性材料中和负极活性材料中均包含有导电剂，导电剂的加入，可以提供导电性能；所述导电剂为乙炔黑。
所述固态电解质电池中，所述固态电解质包括锂盐、聚氧化乙烯和塑化剂，且聚氧化乙烯与锂盐的用量比例按照氧元素与锂元素摩尔量进行计算的，氧元素与锂元素的摩尔比为 5~20:1 ；所述塑化剂占总质量的 5~50% ；所述锂盐包括 LiPF6 、 LiBF4 、 LiCF3SO3 、 LiN(SO2CF3)2 及 LiAsF6 中的至少一种；所述塑化剂选自碳酸酯类或者极性溶剂；所述碳酸酯类优选碳酸乙烯酯、碳酸丙烯酯或碳酸二乙酯；所述极性溶剂为乙二醇二甲醚或二甲基亚砜。
所述固态电解质电池中，所述正极集流体优选铝箔和负极集流体优选铜箔；所述复合电极集流体优选钛箔。
本发明提供的固态电解质电池，由于正极片、复合电极片、负极片的表面均涂覆有可以形成正负电容器结构的正极活性材料和负极活性材料；正极活性材料和负极活性材料能与固态电解质形成良好的层状层叠设置，进而大大的降低电池的内阻，有利于离子之间的迁移，也就提高了电池容量。
另外，在正极活性材料和负极活性材料的外层均涂覆有聚氧化乙烯，由于聚氧化乙烯与固态电解质有很好的相容性，固态电解质中的锂离子能很好的扩散到正极活性材料和负极活性材料上，大大地降低了电池接触内阻 ; 锂离子在固态电解质与正、负极活性材料之间活跃的迁移，也就提高了电池容量。
附图说明
图 1 为较佳实施例中的固态电解质电池结构示意图；其中， n 为固态电解质和复合电极片层叠后的片数，取正整数；
图 2 为较佳实施例中的固态电解质电池结构示意图；其中，复合电极片和固态电解质层叠后的数量为一片；
图 3 为较佳实施例中的固态电解质电池结构示意图；其中，复合电极片和固态电解质层叠后的数量为三片；
图 4 为实施例 1 和对比例 1 制得的固态电解质电池的电池容量对比图。
具体实施方式
本发明提供的一种固态电解质电池，如图 1 所示，包括正极片 1 、负极片 2 、若干片复合电极片 3 以及若干片固态电解质 4 ，且固态电解质 4 的数量比复合电极片 3 的数量多一片；正极片 1 与负极片 2 相对间隔设置，复合电极片 3 介于正极片 1 和负极片 2 之间，且复合电极片 2 两侧分别通过固态电解质 4 与所述正极片 1 和负极片 2 层叠设置，形成固态电解质电池结构，即正极片 /( 固态电解质 4/ 复合电极片 3)n/ 固态电解质 4/ 负极片 2 ； n 为固态电解质 4 和复合电极片 3 层叠后的片数，取正整数；其中：
所述正极片 1 包括正极集流体 11 以及涂覆在正极集流体 11 表面的正极活性材料 12 ；所述负极片 2 包括负极集流体 21 以及涂覆在负极集流体 21 表面的负极活性材料 22 ；所述复合电极片 3 包括复合电极集流体 30 以及涂覆在复合电极集流体 30 两侧面的正极活性材料 31 和负极活性材料 32 ；
所述固态电解质电池结构中，正极片 1 上的正极活性材料 12 与复合电极片 3 上的负极活性材料 32 之间通过一固态电解质 4 相对应层叠设置，形成以电容器结构；同时，负极片 2 上的负极活性材料 22 与复合电极片 3 上的正极活性材料 31 之间通过另一固态电解质 4 相对应层叠设置，形成另一电容器结构；这样，这整个固态电解质电池内部则形成两个串联连接的电容器式固态电解质电池。
所述固态电解质电池中，正极活性材料为氧化石墨衍生物锂盐，在所述氧化石墨衍生物锂盐的氧化石墨表面嫁接有聚氧化乙烯，且聚氧化乙烯链端为羟基锂；负极活性材料为石墨烯，在所述石墨烯表面的嫁接有聚氧化乙烯。
所述固态电解质电池中，优选，所述正极活性材料中和负极活性材料中均包含有导电剂，导电剂的加入，可以提供导电性能；所述导电剂为乙炔黑。
所述固态电解质电池中，所述固态电解质包括锂盐、聚氧化乙烯和塑化剂，且聚氧化乙烯与锂盐的用量比例按照氧元素与锂元素摩尔量进行计算的，氧元素与锂元素的摩尔比为 5~20:1 ；所述塑化剂占总质量的 5~50% ；所述锂盐包括 LiPF6 、 LiBF4 、 LiCF3SO3 、 LiN(SO2CF3)2 及 LiAsF6 中的至少一种；所述塑化剂选自碳酸酯类或者极性溶剂；所述碳酸酯类选择碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯或碳酸二乙酯，优选碳酸乙烯酯、碳酸丙烯酯或碳酸二乙酯；所述极性溶剂优选乙二醇二甲醚、二甲基亚砜、聚乙二醇二甲醚或邻苯二甲酸二丁酯，优选乙二醇二甲醚或二甲基亚砜。
所述固态电解质电池中，集流体均为金属材质，其中所述正极集流体可以为铝网或铝箔，优选铝箔；负极集流体选自铜网或铜箔，优选铜箔；复合电极集流体选自钛网或钛箔，优选钛箔。
上述具体实施例中的复合电极片和固态电解质层叠后的数量可能是一片，也可能是十多片，甚至上百片。如果复合电极片和固态电解质层叠后的数量为两个以上，则相当于多个电容器串联形成电池结构，串联数量决定了电池输出电压。
如图 2 所示，复合电极片和固态电解质层叠后的数量为一片，该固态电解质电池的结构为：正极片 1/ 固态电解质 4/ 复合电极片 3/ 固态电解质 4/ 负极片 2 。
如图 3 所示，复合电极片和固态电解质层叠后的数量为三片，该固态电解质电池的结构为：正极片 1/ 固态电解质 4/ 复合电极片 3/ 固态电解质 4/ 复合电极片 3/ 固态电解质 4/ 复合电极片 3/ 固态电解质 4/ 负极片 2 ；即正极片 1/ （固态电解质 4/ 复合电极片 3 ） 3 / 固态电解质 4/ 负极片 2 。
本发明提供的固态电解质电池，由于正极片、复合电极片、负极片的表面均涂覆有可以形成正负电容器结构的正极活性材料和负极活性材料；正极活性材料和负极活性材料能与固态电解质形成良好的层状层叠设置，进而大大的降低电池的内阻，有利于离子之间的迁移，也就提高了电池容量。
另外，在正极活性材料和负极活性材料的外层均涂覆有聚氧化乙烯，由于聚氧化乙烯与固态电解质有很好的相容性，固态电解质中的锂离子能很好的扩散到正极活性材料和负极活性材料上，大大地降低了电池接触内阻 ; 锂离子在固态电解质与正、负极活性材料之间活跃的迁移，也就提高了电池容量。
上述固体电解质电池的制作方法，包括如下工艺步骤：
S1 、制备正极活性材料、负极活性材料以及固态电解质
正极活性材料的制备：将氧化石墨衍生物锂盐、导电剂和粘合剂 PVDF 溶于有机溶剂中，形成胶状正极活性材料；
负极活性材料的制备：将石墨烯衍生物锂盐、导电剂和粘合剂 PVDF 溶于有机溶剂中，形成胶状负极活性材料；
固态电解质的制备：将锂盐和聚氧化乙烯（ PEO ）溶于有机溶剂中，再加入塑化剂，形成胶状电解液，干燥、固化成型，制得固态电解质；
S2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 1~24h ，使正极活性材料向正极集流体内渗透，干燥后切割成所需规格的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 1~24h ，使负极活性材料向负极集流体内渗透，干燥后切割成所需规格的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 1~24h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片；
S3 、按照正极片 /( 固态电解质 / 复合电极片 )n/ 固态电解质 / 负极片的顺序，层叠放置在一起；其中， n 为固态电解质和复合电极片层叠后的片数，取正整数；
S4 、对步骤 S3 的层叠结构，经热压成型去除残余的有机溶剂，得到固态电池，如图 1 所示。
上述工艺步骤中，导电剂为乙炔黑。
上述工艺步骤中，所述固态电解质包括锂盐、聚氧化乙烯和塑化剂，且聚氧化乙烯与锂盐的用量比例按照氧元素与锂元素摩尔量进行计算的，氧元素与锂元素的摩尔比为 5~20:1 ；所述塑化剂占总质量的 5~50% ；所述锂盐包括 LiPF6 、 LiBF4 、 LiCF3SO3 、 LiN(SO2CF3)3 及 LiAsF6 中的至少一种；所述塑化剂选自碳酸酯类或者极性溶剂；所述碳酸酯类优选碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯或碳酸二乙酯；所述极性溶剂优选乙二醇二甲醚、二甲基亚砜、聚乙二醇二甲醚或邻苯二甲酸二丁酯。
上述工艺步骤中，所述正极集流体选自铝箔和负极集流体选自铜箔；所述复合电极集流体选自钛箔。
上述工艺步骤中，有机溶剂为四氢呋喃（ THF ）溶液或甲基吡咯烷酮（ NMP ）溶液；优选甲基吡咯烷酮（ NMP ）溶液。
下面结合附图，对本发明的较佳实施例作进一步详细说明。
实施例 1
1 、制备正极活性材料、负极活性材料以及固态电解质
正极活性材料的制备：将 90g 氧化石墨衍生物锂盐、 5g 乙炔黑和 5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 90g 石墨烯衍生物锂盐、 5g 乙炔黑和 5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状负极活性材料；
固态电解质的制备：将 10g LiPF6 和 14.5g 聚氧化乙烯（ PEO ）溶于四氢呋喃溶液中，其中 PEO 中的氧元素与 LiPF6 的摩尔比 5:1 ，再加入 1.3g 塑化剂碳酸乙烯酯占总质量 5% ，形成胶状电解液，干燥、固化成型，制得固态电解质；
2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 1h ，使正极活性材料向正极集流体内渗透，干燥后切割成 60mm × 40mm 的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 1h ，使负极活性材料向负极集流体内渗透，干燥后切割成 60mm × 40mm 的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 1h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片。
3 、按照正极片 / 固态电解质 / 复合电极片 / 固态电解质 / 负极片的顺序，层叠放置在一起。
4 、对步骤 3 的层叠结构，经热压成型去除残余的四氢呋喃溶液，得到固态电池。
实施例 2
1 、制备正极活性材料、负极活性材料以及固态电解质 正极活性材料的制备：将 100g 氧化石墨衍生物锂盐、 5.5g 乙炔黑和 5.5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于 NMP 溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 100g 石墨烯衍生物锂盐、 5.5g 乙炔黑和 5.5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于 NMP 溶液中，形成胶状负极活性材料；
固态电解质的制备：将 10g LiBF4 和 37.4gPEO 溶于 NMP 溶液中，其中 PEO 中的氧元素与 LiBF4 的摩尔比 8:1 ，再加入 8.4g 塑化剂碳酸丙烯酯占总质量 15% ，形成胶状电解液，干燥、固化成型，制得固态电解质；
2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 24h ，使正极活性材料向正极集流体内渗透，干燥后切割成 60mm × 40mm 的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 24h ，使负极活性材料向负极集流体内渗透，干燥后切割成 60mm × 40mm 的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 24h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片。
3 、按照正极片 / （固态电解质 / 复合电极片） 5 / 固态电解质 / 负极片的顺序，层叠放置在一起。
4 、对步骤 3 的层叠结构，经热压成型去除残余的 NMP 溶液，得到固态电池。
实施例 3
1 、制备正极活性材料、负极活性材料以及固态电解质
正极活性材料的制备：将 95g 氧化石墨衍生物锂盐、 5.3g 乙炔黑和 5.3g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于 NMP 溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 95g 石墨烯衍生物锂盐、 5.3g 乙炔黑和 5.3g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于 NMP 溶液中，形成胶状负极活性材料；
固态电解质的制备：将 10g LiCF3SO3 和 28.4gPEO 溶于 NMP 溶液中，其中 PEO 中的氧元素与 LiCF3SO3 的摩尔比 10:1 ，再加入 12.8g 塑化剂碳酸二乙酯占总质量 25% ，形成胶状电解液，干燥、固化成型，制得固态电解质。
2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 5h ，使正极活性材料向正极集流体内渗透，干燥后切割成 60mm × 40mm 的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 5h ，使负极活性材料向负极集流体内渗透，干燥后切割成 60mm × 40mm 的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 5h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片。
3 、按照正极片 / （固态电解质 / 复合电极片） 20 / 固态电解质 / 负极片的顺序，层叠放置在一起。
4 、对步骤 3 的层叠结构，经热压成型去除残余的 NMP 溶液，得到固态电池。
实施例 4
1 、制备正极活性材料、负极活性材料以及固态电解质
正极活性材料的制备：将 80g 氧化石墨衍生物锂盐、 4.4g 乙炔黑和 4.4g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 80g 石墨烯衍生物锂盐、 4.4g 乙炔黑和 4.4g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状负极活性材料；
固态电解质的制备：将 10g LiN(SO2CF3)2 和 23.0g 聚氧化乙烯 PEO 溶于四氢呋喃溶液中，其中 PEO 中的氧元素与 LiN(SO2CF3)3 的摩尔比 15:1 ，再加入 17.8g 塑化剂乙二醇二甲醚占总质量 35% ，形成胶状电解液，干燥、固化成型，制得固态电解质。
2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 10h ，使正极活性材料向正极集流体内渗透，干燥后切割成 60mm × 40mm 的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 10h ，使负极活性材料向负极集流体内渗透，干燥后切割成 60mm × 40mm 的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 10h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片。
3 、按照正极片 / （固态电解质 / 复合电极片） 50 / 固态电解质 / 负极片的顺序，层叠放置在一起。
4 、对步骤 3 的层叠结构，经热压成型去除残余的四氢呋喃溶液，得到固态电池。
实施例 5
1 、制备正极活性材料、负极活性材料以及固态电解质
正极活性材料的制备：将 85g 氧化石墨衍生物锂盐、 4.7g 乙炔黑和 4.7g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 85g 石墨烯衍生物锂盐、 4.7g 乙炔黑和 4.7g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状负极活性材料；
固态电解质的制备：将 10g LiAsF6 和 44.9gPEO 溶于四氢呋喃溶液中，其中 PEO 中的氧元素与 LiAsF6 的摩尔比 20:1 ，再加入 27.5g 塑化剂二甲基亚砜占总质量 50% ，形成胶状电解液，干燥、固化成型，制得固态电解质。
2 、制备正极片、负极片以及复合电极片
正极片的制备：在正极集流体表面涂覆胶状的正极活性材料，放置 15h ，使正极活性材料向正极集流体内渗透，干燥后切割成 60mm × 40mm 的正极片；
负极片的制备：在负极集流体表面涂覆胶状的负极活性材料，放置 15h ，使负极活性材料向负极集流体内渗透，干燥后切割成 60mm × 40mm 的负极片；
复合电极片的制备：在复合电极集流体的两个表面分别涂覆胶状的正极活性材料和负极活性材料，放置 15h ，使正极活性材料和负极活性材料分别向负极集流体内渗透，干燥后切割成所需规格的复合电极片。
3 、按照正极片 / （固态电解质 / 复合电极片） 100 / 固态电解质 / 负极片的顺序，层叠放置在一起。
4 、对步骤 3 的层叠结构，经热压成型去除残余的四氢呋喃溶液，得到固态电池。
对比例 1
对比例 1 与实施例 1 相比，不同之处在于步骤 1 ，即正负极活性材料的制备，其他步骤与实施例 1 的相应步骤相同。
正极活性材料的制备：将 90g 氧化石墨的锂盐、 5g 乙炔黑和 5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状正极活性材料；
负极活性材料的制备：将 90g 石墨烯、 5g 乙炔黑和 5g 粘合剂 PVDF 按质量比 90:5:5 的比例混合后溶于四氢呋喃溶液中，形成胶状负极活性材料。
图 4 为实施例 1 和对比例 1 制得的固态电解质电池的电池容量对比图；由图 4 可知，实施例 1 的曲线半圆小于对比例 1 的曲线半圆，表明实施例 1 制得的固态电解质电池的内阻降低了，也就是说电池容量提升了。
应当理解的是，上述针对本发明较佳实施例的表述较为详细，并不能因此而认为是对本发明专利保护范围的限制，本发明的专利保护范围应以所附权利要求为准。

Claims (10)

  1. 一种固态电解质电池，其特征在于，包括正极片、负极片、若干片复合电极片以及若干片固态电解质，且固态电解质的数量比复合电极片的数量多一片；正极片与负极片相对间隔设置，复合电极片介于正极片和负极片之间，且复合电极片两侧分别通过固态电解质与所述正极片和负极片层叠设置，形成固态电解质电池结构；其中，
    所述正极片包括正极集流体以及涂覆在正极集流体表面的正极活性材料；
    所述负极片包括负极集流体以及涂覆在负极集流体表面的负极活性材料；
    所述复合电极片包括复合电极集流体以及涂覆在复合电极集流体两侧面的正极活性材料和负极活性材料；
    所述固态电解质电池中，正极片上的正极活性材料与复合电极片上的负极活性材料之间通过一固态电解质相对应层叠设置，同时，负极片上的负极活性材料与复合电极片上的正极活性材料之间通过另一固态电解质相对应层叠设置。
  2. 根据权利要求 1 所述的固态电解质电池，其特征在于，正极活性材料为氧化石墨衍生物锂盐，在所述氧化石墨衍生物锂盐的氧化石墨表面嫁接有聚氧化乙烯，且聚氧化乙烯链端为羟基锂；负极活性材料为石墨烯，在所述石墨烯表面的嫁接有聚氧化乙烯。
  3. 根据权利要求 1 或 2 所述的固态电解质电池，其特征在于，所述正极活性材料和负极活性材料中均包含有导电剂。
  4. 根据权利要求 3 所述的固态电解质电池，其特征在于，所述导电剂为乙炔黑。
  5. 根据权利要求 1 所述的固态电解质电池，其特征在于，所述固态电解质包括锂盐、聚氧化乙烯和塑化剂，且聚氧化乙烯与锂盐的用量比例按照氧元素与锂元素摩尔量进行计算的，氧元素与锂元素的摩尔比为 5~20:1 ；所述塑化剂占总质量的 5~50% 。
  6. 根据权利要求 5 所述的固态电解质电池，其特征在于，所述锂盐包括 LiPF6 、 LiBF4 、 LiCF3SO3 、 LiN(SO2CF3)2 及 LiAsF6 中的至少一种。
  7. 根据权利要求 5 所述的固态电解质电池，其特征在于，所述塑化剂选自碳酸酯类或者极性溶剂。
  8. 根据权利要求 7 所述的固态电解质电池，其特征在于，所述碳酸酯类选自碳酸乙烯酯、碳酸丙烯酯或碳酸二乙酯。
  9. 根据权利要求 7 所述的固态电解质电池，其特征在于，所述极性溶剂选自乙二醇二甲醚或二甲基亚砜。
  10. 根据权利要求 1 所述的固态电解质电池，其特征在于，所述正极集流体为铝箔；负极集流体为铜箔；所述复合电极集流体为钛箔。
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CN101192684A (zh) * 2006-11-30 2008-06-04 日产自动车株式会社 双极性电池及其制造方法
CN101425600A (zh) * 2007-11-01 2009-05-06 日产自动车株式会社 双极型二次电池、电池组及安装了这些电池的车辆
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