CN106654362B - Composite solid electrolyte film, preparation method and lithium ion battery - Google Patents

Composite solid electrolyte film, preparation method and lithium ion battery Download PDF

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CN106654362B
CN106654362B CN201611112927.XA CN201611112927A CN106654362B CN 106654362 B CN106654362 B CN 106654362B CN 201611112927 A CN201611112927 A CN 201611112927A CN 106654362 B CN106654362 B CN 106654362B
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lithium
electrolyte
inorganic
composite
glue
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CN106654362A (en
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赵伟
李俊义
徐延铭
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Chongqing Guanyu Battery Co ltd
Zhuhai Coslight Battery Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/052—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
    • 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

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Abstract

Composite solid electrolyte film, preparation method and lithium ion battery, which includes porous support materials；Coated on the first composite layer in the porous support materials both side surface；Coated on the second composite layer on first composite layer；The inorganic accounting of second composite layer is lower than the inorganic accounting of the first composite layer.Addition porous support materials in the electrolyte membrane of the invention, to ensure that film flexibility and enhance the mechanical strength of film, and interface compatibility has can be improved in the dielectric film of sandwich structure, improves the cycle performance of battery.

Description

Composite solid electrolyte film, preparation method and lithium ion battery
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of composite solid electrolyte film and its preparation sides Method, and the solid lithium ion battery using the solid electrolyte film preparation.
Background technique
Lithium ion battery because energy density is high, have extended cycle life and it is environmental-friendly the features such as be widely used in it is mobile logical Believe in the electronic products such as equipment, laptop, digital camera, and gradually plays and make in electric vehicle and energy storage field With.The most commercial Li-ion battery of application is using materials such as positive and negative plate, liquid electrolyte and polyalkene diaphragms at present Material assembles.Since liquid electrolyte is inflammable and explosive, and the heated easily contraction of polyalkene diaphragm or thawing, easily lead to battery short circuit Explosion, affects the safety of lithium ion battery.
Solid electrolyte has both the ionic conductivity of liquid electrolyte and the electronic isolation of polyalkene diaphragm, can be simultaneously Liquid electrolyte and polyalkene diaphragm are substituted, to greatly improve the security performance of battery.In addition, using solid electrolyte film Short-circuit risks caused by Li dendrite can be reduced, make it possible lithium metal as lithium ion battery negative material, thus significantly Improve the energy density of lithium ion battery.
At present for solid state electrolysis Quality Research, main there are three classifications: first is that organic polyelectrolyte, second is that inorganic Solid electrolyte, third is that the composite electrolyte that organic polymer and inorganic solid electrolyte are combined.
The battery easy processing of organic polyelectrolyte, can continue to use existing lithium-ion electric pool process substantially, but room temperature Conductivity is low.The room-temperature conductivity of inorganic solid electrolyte is higher, but material cost is higher, and battery process is complicated, needs The many completely new battery production equipments of exploitation, cause cost further to increase.Composite electrolyte membrane has organic polymer electrolytic The workability of matter, and room-temperature conductivity can be improved to a certain extent, but there are bad mechanical strengths, and film to be caused to be easily broken It causes battery short circuit and positive and negative anodes interface compatibility poor the shortcomings that leading to the higher internal resistance of cell, poor circulation, and room temperature electricity Conductance also needs to be further increased.
Summary of the invention
The purpose of the present invention is to provide a kind of composite solid electrolyte film and its manufacturing methods, and apply the electrolyte The lithium ion battery of film, with solve low room-temperature conductivity existing for current composite electrolyte membrane, bad mechanical strength and film with just The poor problem of cathode interface compatibility.
To achieve the goals above, the present invention takes following technical solution:
Composite solid electrolyte film, comprising: porous support materials；Coated in the porous support materials both side surface First composite layer；Coated on the second composite layer on first composite layer；The inorganic of second composite layer accounts for Than the inorganic accounting for being lower than the first composite layer.
Further, first composite layer by the electrolyte glue comprising inorganic electrolyte powder or includes inorganic electrolyte The electrolyte glue of matter powder, organic polymer and lithium salts is formed, and the content of inorganic electrolyte powder is that solid is molten in electrolyte glue The 5~100% of matter gross mass.
Further, the second composite layer by the electrolyte glue comprising organic polymer and lithium salts or includes inorganic electrolyte The electrolyte glue of powder, organic polymer and lithium salts is formed, and the content of inorganic electrolyte powder is that solid is molten in electrolyte glue The 0~95% of matter gross mass.
The preparation method of composite solid electrolyte film, comprising the following steps:
Solid solute is dissolved in solvent, the first compound adhesive is made, the solid solute of the first compound adhesive is inorganic electrolyte powder Body or including inorganic electrolyte powder and organic polymer and lithium salts；
Solid solute is dissolved in solvent, the secondth compound adhesive is made, the inorganic accounting of the second compound adhesive is compound lower than first The inorganic accounting of glue, the solid solute of the second compound adhesive include organic polymer and lithium salts or including inorganic electrolyte powder and have Machine polymer and lithium salts；
It by the first compound adhesive double spread or pours on porous support materials, after solvent evaporated, in porous support materials The first composite layer is formed in both side surface；
Second compound adhesive is coated with or is poured on the outer surface of the first composite layer, after solvent evaporated, is answered Close solid electrolyte membrane.
Further, the content of inorganic electrolyte powder is the 5~100% of solid solute gross mass in the first compound adhesive.
Further, the content of inorganic electrolyte powder is the 0~95% of solid solute gross mass in the second compound adhesive.
Further, when preparing the first compound adhesive, organic polymer, lithium salts are dissolved in solvent, is formed solid content for 1~ 10% organic polyelectrolyte glue, then mixing dispersion in glue is added in inorganic electrolyte powder and forms the first compound adhesive, or Inorganic electrolyte powder is added mixing dispersion in solvent and forms the first compound adhesive by person；The organic polymer is polyethylene glycol oxide Based polyalcohol or polycarbonate based polyalcohol, lithium salts are double trifluoromethanesulfonamide imine lithiums or lithium perchlorate or dioxalic acid boric acid Lithium or trifluoromethyl sulfonic acid lithium or lithium hexafluoro phosphate or LiBF4, inorganic electrolyte powder are oxide electrolyte or vulcanization Object electrolyte.
Further, when preparing the second composite layer, organic polymer, lithium salts are dissolved in solvent, forming solid content is 1 ~10% organic polyelectrolyte glue, then mixing dispersion in glue is added in inorganic electrolyte powder and forms the second compound adhesive, Or organic polymer, lithium salts are dissolved in solvent, form the second compound adhesive that solid content is 1~10%；The organic polymer Object is polyethylene glycol oxide based polyalcohol or polycarbonate based polyalcohol, and lithium salts is double trifluoromethanesulfonamide imine lithiums or perchloric acid Lithium or dioxalic acid lithium borate or trifluoromethyl sulfonic acid lithium or lithium hexafluoro phosphate or LiBF4, inorganic electrolyte powder are oxidation Object electrolyte or sulfide electrolyte.
Further, the lithia of organic polymer and lithium salts ratio is 1:40~1:5 in electrolyte glue.
Further, the polyethylene glycol oxide based polyalcohol is that polyoxyethylene or polyoxyethylene and other polymers are total Mixed, copolymerization or crosslinking product, the polycarbonate based polyalcohol are ethylene carbonate, polytrimethylene carbonate or poly- carbonic acid Acrylic ester.
Further, the oxide electrolyte is Li-La-Ti oxygen or lithium lanthanum zirconium oxygen or lithium aluminium titanium phosphorus or lithium aluminium germanium phosphorus, sulphur Compound electrolyte is Li2S-SiS2Or Li2S-P2S5Or Li2S-P2S5-GeS2。
Further, the inorganic accounting of second composite layer is lower by 5% or more than the inorganic accounting of the first composite layer.
Further, the porous support materials are high porosity diaphragm or electrostatic spinning diaphragm or nonwoven cloth diaphragm or glass Glass web.
Lithium ion battery is formed by anode pole piece, cathode pole piece and membrane winding, and the diaphragm uses aforementioned composite solid The preparation method of dielectric film is made.
From the above technical scheme, in composite solid electrolyte film of the invention, due to joined porous support materials, Guaranteeing that film is flexible while enhancing the mechanical strength of film, is reducing risk short-circuit in battery preparation；Sandwich structure Dielectric film in, the inorganic solid electrolyte middle layer of the first composite layer --- i.e. high-content improves the ionic conductance of film Rate, the second composite layer --- i.e. the organic polyelectrolyte boundary layer of high-content is electrolysed the inorganic solid-state of high conductivity There is a buffer layer between matter middle layer and positive and negative plate, to improve interface compatibility, improves the cyclicity of battery Energy.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section of lithium ion battery of the present invention.
Specific embodiment
In order to above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention is cited below particularly, It is described below in detail.
As shown in Figure 1, solid lithium ion battery is generally formed by anode pole piece, cathode pole piece and membrane winding or lamination, Anode pole piece is usually that the positive electrodes such as LiFePO4, cobalt acid lithium, ternary material 2 are applied in aluminum foil current collector 1 to be made, cathode Pole piece is usually the negative electrode materials such as graphite or lithium metal 4 to be applied in copper foil current collector 5 to be made, or lithium titanate is applied to aluminium foil collection It is made on fluid.Diaphragm of the invention is the composite solid electrolyte film 3 with sandwich structure comprising porous support materials 6 and successively be coated on 6 both side surface of porous support materials on the first composite layer A and the second composite layer B, second is compound Glue-line B is coated on the outer surface of the first composite layer A.First composite layer A is not placed only in 6 surface of porous support materials On, and 6 internal voids of porous support materials are filled completely.
First composite layer A is formed by the electrolyte glue for containing inorganic electrolyte powder, organic polymer and lithium salts, electricity The content of inorganic electrolyte powder is the 5~100% of solid solute gross mass (disregarding solvent quality) in solution matter glue, i.e., inorganic Accounting is 5~100%, and the lithia ratio of organic polymer and lithium salts is 1:40~1:5.
Second composite layer B is formed by the electrolyte glue for containing inorganic electrolyte powder, organic polymer and lithium salts, electricity The content for solving inorganic electrolyte powder in matter glue is the 0~95% of solid solute gross mass, the lithium of organic polymer and lithium salts Oxygen ratio is 1:40~1:5.The inorganic accounting of second composite layer B is lower than the inorganic accounting of the first composite layer A, it is preferred that the The inorganic accounting of two composite layer B is more than 5% (containing 5%) lower than the inorganic accounting of the first composite layer A.
Organic polymer of the invention is polyethylene glycol oxide based polyalcohol or polycarbonate based polyalcohol, wherein polyoxygenated Polyvinyl can be the product that polyoxyethylene (PEO) or polyoxyethylene are blended with other polymers, are copolymerized or are crosslinked, and gather Carbohydrate-based polymers can be ethylene carbonate (PEC), polytrimethylene carbonate (PTMC) or polypropylene carbonate (PPC).
Lithium salts can be double trifluoromethanesulfonamide imine lithiums (LiTFSI), lithium perchlorate (LiClO4), dioxalic acid lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiTF), lithium hexafluoro phosphate (LiPF6) or LiBF4 (LiBF4) etc..
Solvent can be acetonitrile or water or N-Methyl pyrrolidone (NMP) etc..
Inorganic electrolyte powder is oxide electrolyte or sulfide electrolyte, and oxide electrolyte can be Li-La-Ti oxygen (LLTO), lithium lanthanum zirconium oxygen (LLZO), lithium aluminium titanium phosphorus (LATP), lithium aluminium germanium phosphorus (LAGP) etc., sulfide electrolyte can be Li2S- SiS2、Li2S-P2S5、Li2S-P2S5-GeS2Deng.
Porous support materials can be high porosity diaphragm, electrostatic spinning diaphragm, nonwoven cloth diaphragm, glass fiber mesh etc..
When preparing the first composite layer A, organic polymer, lithium salts are dissolved in solvent, forming solid content is 1~10% Organic polyelectrolyte glue, then mixing dispersion in glue is added in inorganic electrolyte powder and forms the first compound adhesive, first is answered It closes glue double spread or pours on porous support materials, after 20 DEG C~150 DEG C solvent evaporateds, i.e., in porous support materials two sides The first composite layer A is formed on surface.
When preparing the second composite layer B, organic polymer, lithium salts are dissolved in solvent, forming solid content is 1~10% Organic polyelectrolyte glue, then mixing dispersion in glue is added in inorganic electrolyte powder and forms the second compound adhesive；Second is answered It closes glue coating or pours on the outer surface of the first composite layer A, after 20 DEG C~150 DEG C solvent evaporateds, can be obtained three The composite solid electrolyte film of Mingzhi's structure.
Since the conductivity of inorganic solid electrolyte is usually above the conductivity of organic polyelectrolyte, but inorganic solid-state The poor compatibility of electrolyte and positive and negative plate, some inorganic solid electrolytes are directly contacted with lithium or even can be decomposed, because This, the present invention uses the composite layer of high inorganic accounting as the first composite layer, to improve conductivity, in the first composite layer Outside forms the second composite layer of low inorganic accounting, to improve interface compatibility, reduces interface impedance, improves circulating battery Energy.The compound adhesive comprehensive performance of compound adhesive or simple low inorganic accounting using multilayered structure than simple high inorganic accounting More preferably.
Below by specific embodiment and comparative example, the present invention is further illustrated.It is arrived used in following the description Reagent, material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available It obtains, related reagent can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
PEO and LiTFSI is dissolved in acetonitrile according to the ratio of lithia ratio 1:13, forms the organic polymer that solid content is 5% Object electrolyte glue adds LLTO mixing and is dispersed into the first compound adhesive that inorganic accounting is 60%；By PEO and LiTFSI according to lithium The ratio of oxygen ratio 1:18 is dissolved in acetonitrile, forms the organic polyelectrolyte glue that solid content is 6%, it is mixed to add lithium lanthanum zirconium oxygen It closes and is dispersed into the second compound adhesive that inorganic accounting is 10%；
First compound adhesive double spread is online in glass fibre, after 80 DEG C of solvent evaporateds, then by the second compound adhesive be coated with In on the first composite layer, after 90 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
It is made admittedly with composite solid electrolyte film collocation iron phosphate lithium positive pole piece and lithium cathode sheet using existing lamination process State lithium ion battery.
Comparative example 1
PEO and LiTFSI is dissolved in acetonitrile according to the ratio of lithia ratio 1:13, forms the organic polymer that solid content is 5% Object electrolyte glue, is added LLTO in organic polyelectrolyte glue, and mixing is dispersed into the compound adhesive of inorganic accounting 60%；
By compound adhesive by scraping embrane method knifing, after 90 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing lamination process with solid electrolyte membrane collocation iron phosphate lithium positive pole piece and lithium cathode sheet Ion battery.
Embodiment 2
By the copolymer and LiClO of PEO and PPO4Ratio according to lithia ratio 1:40 is soluble in water, and forming solid content is 1% organic polyelectrolyte glue adds LLZO mixing and is dispersed into the first compound adhesive that inorganic accounting is 10%；By PEO Copolymer and LiClO4Ratio according to lithia ratio 1:40 is soluble in water, forms the organic polyelectrolyte that solid content is 1% Glue adds the mixing of lithium lanthanum zirconium oxygen and is dispersed into the second compound adhesive that inorganic accounting is 5%；
By the first compound adhesive double spread on electrostatic spinning diaphragm, after 150 DEG C of solvent evaporateds, then the second compound adhesive applied It is distributed on the first composite layer, after 150 DEG C of solvent evaporateds, obtains composite solid electrolyte film；
With composite solid electrolyte film collocation lithium cobaltate cathode piece and lithium cathode sheet using existing winding process at solid-state lithium Ion battery.
Comparative example 2
By PEO copolymer and LiClO4Ratio according to lithia ratio 1:40 is soluble in water, formed solid content be 1% it is organic Polymer dielectric glue adds LLZO mixing and is dispersed into the compound adhesive that inorganic accounting is 10%；
By compound adhesive by scraping embrane method knifing, after 150 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
With solid electrolyte membrane collocation lithium cobaltate cathode piece and lithium cathode sheet using existing winding process at solid lithium ion Battery.
Embodiment 3
PEC and LiBOB is dissolved in NMP according to the ratio of lithia ratio 1:5, forms the organic polymer that solid content is 10% Electrolyte glue adds LATP mixing and is dispersed into the first compound adhesive that inorganic accounting is 30%；By PEC and LiBOB according to lithia It is more soluble in water than the ratio of 1:6, the organic polyelectrolyte glue that solid content is 9% is formed, the mixing point of lithium lanthanum zirconium oxygen is added Dissipate into the second compound adhesive that inorganic accounting is 15%；
By the first compound adhesive double spread on nonwoven cloth diaphragm, after 150 DEG C of solvent evaporateds, then the second compound adhesive is coated with In on the first composite layer, after 130 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
It is made admittedly with composite solid electrolyte film collocation ternary material positive plate and lithium cathode sheet using existing lamination process State lithium ion battery.
Comparative example 3
PEC and LiBOB is dissolved in NMP according to the ratio of lithia ratio 1:5, forms the organic polymer that solid content is 10% Electrolyte glue adds LATP mixing and is dispersed into the compound adhesive that inorganic accounting is 30%；
By compound adhesive by scraping embrane method knifing, after 150 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing lamination process with solid electrolyte membrane collocation ternary material positive plate and lithium cathode sheet Ion battery.
Embodiment 4
By PEO and LiTF being dissolved in acetonitrile according to lithia ratio 1:20, forms the organic polymer that solid content is 7% and be electrolysed Matter glue adds LAGP mixing and is dispersed into the first compound adhesive that inorganic accounting is 50%；By PEO and LiTF according to lithia ratio 1:15 Ratio be dissolved in acetonitrile, formed solid content be 6% organic polyelectrolyte glue, add LAGP mixing be dispersed into it is inorganic The second compound adhesive that accounting is 5%；
By the first compound adhesive double spread on high porosity diaphragm, after 20 DEG C of solvent evaporateds, then the second compound adhesive applied It is distributed on the first composite layer, after 20 DEG C of solvent evaporateds, obtains composite solid electrolyte film；
It is made admittedly with composite solid electrolyte film collocation lithium cobaltate cathode piece and graphite cathode piece using existing lamination process State lithium ion battery.
Comparative example 4
PEO and LiTF is dissolved in acetonitrile according to the ratio of lithia ratio 1:20, forms the organic polymer that solid content is 7% Electrolyte glue adds LAGP mixing and is dispersed into the compound adhesive that inorganic accounting is 50%；
By compound adhesive by scraping embrane method knifing, after 20 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing lamination process in solid electrolyte membrane collocation lithium cobaltate cathode piece and graphite cathode piece Ion battery.
Embodiment 5
By PTMC and LiPF6It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polymer that solid content is 4% Object electrolyte glue, adds Li2S-SiS2Mixing is dispersed into the first compound adhesive that inorganic accounting is 40%；By PTMC and LiPF6It presses It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polyelectrolyte glue that solid content is 4%, it is mixed to add LAGP It closes and is dispersed into the second compound adhesive that inorganic accounting is 10%；
First compound adhesive double spread is online in glass fibre, after 60 DEG C of solvent evaporateds, then by the second compound adhesive be coated with In on the first composite layer, after 50 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
Existing winding process system is used with composite solid electrolyte film collocation ternary material positive plate and lithium titanate anode piece At solid lithium ion battery.
Comparative example 5
By PTMC and LiPF6It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polymer that solid content is 4% Object electrolyte glue, adds Li2S-SiS2Mixing is dispersed into the compound adhesive that inorganic accounting is 40%；
By compound adhesive by scraping embrane method knifing, after 60 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
It is made admittedly with solid electrolyte membrane collocation ternary material positive plate and lithium titanate anode piece using existing winding process State lithium ion battery.
Embodiment 6
By PPC and LiBF4It is dissolved in acetonitrile according to the ratio of lithia ratio 1:20, forms the organic polymer that solid content is 5% Object electrolyte glue, adds Li2S-P2S5Mixing is dispersed into the first compound adhesive that inorganic accounting is 99%；By PPC and LiBF4It presses It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polyelectrolyte glue that solid content is 4%, add Li2S- P2S5Mixing is dispersed into the second compound adhesive that inorganic accounting is 6%；
First compound adhesive double spread is online in glass fibre, after 50 DEG C of solvent evaporateds, then by the second compound adhesive be coated with In on the first composite layer, after 60 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
It is made admittedly with composite solid electrolyte film collocation ternary material positive plate and lithium cathode sheet using existing winding process State lithium ion battery.
Comparative example 6
By PPC and LiBF4It is dissolved in acetonitrile according to the ratio of lithia ratio 1:20, forms the organic polymer that solid content is 5% Object electrolyte glue, adds Li2S-P2S5Mixing is dispersed into the compound adhesive that inorganic accounting is 99%；
By compound adhesive by scraping embrane method knifing, after 50 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing winding process with solid electrolyte membrane collocation ternary material positive plate and lithium cathode sheet Ion battery.
Embodiment 7
By PEO and LiBF4It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polymer that solid content is 5% Object electrolyte glue adds LAGP mixing and is dispersed into the first compound adhesive that inorganic accounting is 5%；By PEO and LiBF4According to lithia Ratio than 1:15 is dissolved in acetonitrile, forms the organic polyelectrolyte glue that solid content is 5%, and the second of the present embodiment is compound Inorganic electrolyte powder is added without in glue, i.e. the inorganic accounting of the second compound adhesive is 0%；
First compound adhesive double spread is online in glass fibre, after 50 DEG C of solvent evaporateds, then by the second compound adhesive be coated with In on the first composite layer, after 60 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
It is made admittedly with composite solid electrolyte film collocation iron phosphate lithium positive pole piece and lithium cathode sheet using existing winding process State lithium ion battery.
Comparative example 7
By PEO and LiBF4It is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forms the organic polymer that solid content is 5% Object electrolyte glue adds LAGP mixing and is dispersed into the compound adhesive that inorganic accounting is 5%；
By compound adhesive by scraping embrane method knifing, after 50 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing winding process with solid electrolyte membrane collocation iron phosphate lithium positive pole piece and lithium cathode sheet Ion battery.
Embodiment 8
Use Li2S-P2S5-GeS2Mixing, which is scattered in, is made the dispersion liquid that inorganic accounting is 100% in acetonitrile, i.e., inorganic accounting For 100% the first compound adhesive；PEO and LiTFSI is dissolved in acetonitrile according to the ratio of lithia ratio 1:15, forming solid content is 5% organic polyelectrolyte glue, adds Li2S-P2S5-GeS2Mixing be dispersed into inorganic accounting be 95% it is second compound Glue；
First compound adhesive double spread is online in glass fibre, after 50 DEG C of solvent evaporateds, then by the second compound adhesive be coated with In on the first composite layer, after 60 DEG C of solvent evaporateds, composite solid electrolyte film is obtained；
It is made admittedly with composite solid electrolyte film collocation iron phosphate lithium positive pole piece and lithium cathode sheet using existing winding process State lithium ion battery.
Comparative example 8
Use Li2S-P2S5-GeS2The dispersion liquid that it is 100% at inorganic accounting in acetonitrile that mixing, which is scattered in,；
By the dispersion liquid by scraping embrane method knifing, after 50 DEG C of solvent evaporateds, solid electrolyte membrane is obtained；
Solid-state lithium is made using existing winding process with solid electrolyte membrane collocation iron phosphate lithium positive pole piece and lithium cathode sheet Ion battery.
Solid lithium ion battery made from embodiment 1-8 and comparative example 1-8 is tested, 25 DEG C of specific capacities is tested and plays Account for the ratio of theoretical specific capacity, short circuit ratio, test method after 1C/1C cycle life, 25 DEG C of internal resistance sizes, battery assemblies at 60 DEG C Referring to company standard, test result is as shown in table 1.
Table 1
As known from Table 1, solid lithium ion battery made from the composite solid electrolyte film using the method for the present invention preparation, and Comparative example is compared, specific capacity play account for theoretical specific capacity ratio significantly improve, internal resistance decline, cycle life increase, battery it is short The decline of road rate.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article Widest range.

Claims (16)

1. composite solid electrolyte film characterized by comprising
Porous support materials；
Coated on the first composite layer in the porous support materials both side surface, first composite layer is by comprising inorganic The electrolyte glue of electrolyte powder, organic polymer and lithium salts is formed, and the content of inorganic electrolyte powder is solid in electrolyte glue The 10~99% of body solute gross mass, first composite layer are filled in the porous support materials internal voids simultaneously；
Coated on the second composite layer on first composite layer, second composite layer is by including inorganic electrolyte powder The electrolyte glue of body, organic polymer and lithium salts is formed, and the content of inorganic electrolyte powder is solid solute in electrolyte glue The 5~95% of gross mass；
The inorganic accounting of second composite layer is lower than the inorganic accounting of the first composite layer.
2. composite solid electrolyte film according to claim 1, it is characterised in that: organic polymer and lithium in electrolyte glue The lithia ratio of salt is 1:40~1:5.
3. composite solid electrolyte film according to claim 1, it is characterised in that: the inorganic of the second composite layer accounts for The inorganic accounting low 5% or more of the first composite layer frequently.
4. composite solid electrolyte film according to claim 1, it is characterised in that: the porous support materials are high hole Rate diaphragm or electrostatic spinning diaphragm or nonwoven cloth diaphragm or glass fiber mesh.
5. composite solid electrolyte film according to claim 1, it is characterised in that: the organic polymer is polyoxyethylene Alkenyl polymer or polycarbonate based polyalcohol, lithium salts are double trifluoromethanesulfonamide imine lithiums or lithium perchlorate or dioxalic acid boron Sour lithium or trifluoromethyl sulfonic acid lithium or lithium hexafluoro phosphate or LiBF4, inorganic electrolyte powder are oxide electrolyte or sulphur Compound electrolyte.
6. composite solid electrolyte film according to claim 5, it is characterised in that: the polyethylene glycol oxide based polyalcohol is The product that polyoxyethylene or polyoxyethylene are blended with other polymers, are copolymerized or are crosslinked, the polycarbonate based polyalcohol are Ethylene carbonate, polytrimethylene carbonate or polypropylene carbonate.
7. composite solid electrolyte film according to claim 5, it is characterised in that: the oxide electrolyte is Li-La-Ti Oxygen or lithium lanthanum zirconium oxygen or lithium aluminium titanium phosphorus or lithium aluminium germanium phosphorus, sulfide electrolyte are Li2S-SiS2Or Li2S-P2S5Or Li2S-P2S5- GeS2。
8. the preparation method of composite solid electrolyte film, which comprises the following steps:
Solid solute is dissolved in solvent, the first compound adhesive is made, the solid solute of the first compound adhesive includes inorganic electrolyte powder And organic polymer and lithium salts, the content of inorganic electrolyte powder are the 10~99% of solid solute gross mass；
Solid solute is dissolved in solvent, the second compound adhesive is made, the inorganic accounting of the second compound adhesive is lower than the nothing of the first compound adhesive Machine accounting, the solid solute of the second compound adhesive include inorganic electrolyte powder and organic polymer and lithium salts, inorganic electrolyte powder The content of body is the 5~95% of solid solute gross mass；
It by the first compound adhesive double spread or pours on porous support materials, after solvent evaporated, in porous support materials two sides The first composite layer is formed on surface, first composite layer is filled in the porous support materials internal voids simultaneously；
Second compound adhesive is coated with or is poured on the outer surface of the first composite layer, after solvent evaporated, obtains composite solid State dielectric film.
9. the preparation method of composite solid electrolyte film according to claim 8, it is characterised in that: the first compound adhesive of preparation When, organic polymer, lithium salts are dissolved in solvent, form the organic polyelectrolyte glue that solid content is 1~10%, then by nothing Machine electrolyte powder is added mixing dispersion in glue and forms the first compound adhesive, or inorganic electrolyte powder is added in solvent and is mixed Dispersion forms the first compound adhesive；
The organic polymer is polyethylene glycol oxide based polyalcohol or polycarbonate based polyalcohol, and lithium salts is double fluoroform sulphonyl Amine imine lithium or lithium perchlorate or dioxalic acid lithium borate or trifluoromethyl sulfonic acid lithium or lithium hexafluoro phosphate or LiBF4, it is inorganic Electrolyte powder is oxide electrolyte or sulfide electrolyte.
10. the preparation method of composite solid electrolyte film according to claim 8, it is characterised in that: preparation second is compound When glue-line, organic polymer, lithium salts are dissolved in solvent, form the organic polyelectrolyte glue that solid content is 1~10%, then Mixing dispersion in glue is added in inorganic electrolyte powder and forms the second compound adhesive, or organic polymer, lithium salts are dissolved in solvent In, form the second compound adhesive that solid content is 1~10%；
The organic polymer is polyethylene glycol oxide based polyalcohol or polycarbonate based polyalcohol, and lithium salts is double fluoroform sulphonyl Amine imine lithium or lithium perchlorate or dioxalic acid lithium borate or trifluoromethyl sulfonic acid lithium or lithium hexafluoro phosphate or LiBF4, it is inorganic Electrolyte powder is oxide electrolyte or sulfide electrolyte.
11. the preparation method of composite solid electrolyte film according to claim 8, it is characterised in that: have in electrolyte glue The lithia of machine polymer and lithium salts ratio is 1:40~1:5.
12. the preparation method of composite solid electrolyte film according to claim 9 or 10, it is characterised in that: the polyoxy Changing polyvinyl is the product that polyoxyethylene or polyoxyethylene are blended with other polymers, are copolymerized or are crosslinked, described poly- Carbohydrate-based polymers are ethylene carbonate, polytrimethylene carbonate or polypropylene carbonate.
13. the preparation method of composite solid electrolyte film according to claim 9 or 10, it is characterised in that: the oxidation Object electrolyte is Li-La-Ti oxygen or lithium lanthanum zirconium oxygen or lithium aluminium titanium phosphorus or lithium aluminium germanium phosphorus, and sulfide electrolyte is Li2S-SiS2Or Li2S-P2S5Or Li2S-P2S5-GeS2。
14. the preparation method of composite solid electrolyte film according to claim 8, it is characterised in that: described second is compound The inorganic accounting of glue-line is lower by 5% or more than the inorganic accounting of the first composite layer.
15. the preparation method of composite solid electrolyte film according to claim 8, it is characterised in that: the open support Material is high porosity diaphragm or electrostatic spinning diaphragm or nonwoven cloth diaphragm or glass fiber mesh.
16. lithium ion battery is formed by anode pole piece, cathode pole piece and membrane winding, it is characterised in that: the diaphragm is using such as The preparation method of the described in any item composite solid electrolyte films of claim 8-15 is made.
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