CN113471526B - Multilayer structure composite electrolyte and solid-state lithium battery - Google Patents

Multilayer structure composite electrolyte and solid-state lithium battery Download PDF

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CN113471526B
CN113471526B CN202010239416.4A CN202010239416A CN113471526B CN 113471526 B CN113471526 B CN 113471526B CN 202010239416 A CN202010239416 A CN 202010239416A CN 113471526 B CN113471526 B CN 113471526B
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monomer
multilayer structure
structure composite
solid electrolyte
polymerization
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CN113471526A (en
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姬迎亮
周时国
廖华平
李帅鹏
张二勇
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Zhengzhou Yutong Group Co ltd
Yutong Bus Co Ltd
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Zhengzhou Yutong Group Co ltd
Yutong Bus 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
    • H01M10/0564—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/24—Esters of carbonic or haloformic acids, e.g. allyl carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Abstract

The invention relates to a multilayer structure composite electrolyte and a solid-state lithium battery, belonging to the technical field of lithium batteries. The multilayer structure composite electrolyte comprises a solid electrolyte base layer and a solid electrolyte cathode facing layer arranged on one surface of the solid electrolyte layer; the solid electrolyte negative electrode facing layer is formed by in-situ polymerization on one surface of the solid electrolyte base layer by taking a second polymerization monomer, an acrylate prepolymer and a lithium salt as main raw materials; the molecular weight of the acrylate prepolymer is 100-50000; the second polymerization monomer comprises a polymerization monomer B and an unsaturated carbonate monomer; the polymerized monomer B is selected from one or two of a compound shown in a formula I and a compound shown in a formula II. The multilayer structure composite electrolyte has excellent adhesive property and flexibility, is favorable for solving the problem of a negative electrode interface, particularly forms effective protection for a metal lithium negative electrode, and can effectively inhibit lithium dendrite and expansion of the lithium negative electrode.

Description

Multilayer structure composite electrolyte and solid lithium battery
Technical Field
The invention relates to a multilayer structure composite electrolyte and a solid-state lithium battery, belonging to the technical field of lithium batteries.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high output voltage, no memory effect, cyclic utilization, environmental friendliness and the like, and is widely applied. In recent years, development in the field of new energy vehicles and the like has put higher demands on lithium ion batteries, and particularly, development of batteries with high power, high energy density and high safety performance is urgently needed. At present, the commercialized lithium ion battery generally adopts highly flammable, explosive and volatile organic electrolyte components, and has extremely high potential safety hazard. Solid-state batteries that use solid-state electrolytes instead of highly flammable electrolytes are an important approach to solving battery safety problems.
All-solid-state lithium batteries have become secondary batteries that are most safe and most suitable for large-scale battery systems because they use solid materials such as high polymers and oxide-based ceramics as electrolytes instead of liquid electrolytes that are commonly used in lithium ion batteries. The graphite capacity of the cathode material commonly used in the lithium battery is too low, the pulverization of the alloy cathode material is ineffective due to the volume effect of the alloy cathode material after lithium is inserted, and the irreversible loss of lithium is large when the oxide-based cathode material is charged for the first time, so that the oxide-based cathode material is not suitable for all-solid batteries. The metal lithium is a metal negative electrode material with the largest specific capacity, but the metal lithium is easy to generate lithium dendrite in the use process, and the polymer solid electrolyte which is most researched and most applied has poor mechanical property, and is easy to be pierced by the lithium dendrite, so that the safety of the all-solid-state lithium ion battery is poor.
Disclosure of Invention
The invention aims to provide a multilayer-structure composite electrolyte which can solve the problem of poor safety of all-solid-state batteries in the prior art.
The invention also provides a solid lithium battery, and the contact resistance between the solid electrolyte and the negative plate is lower.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a multilayer structure composite electrolyte comprises a solid electrolyte base layer and a solid electrolyte negative electrode facing layer arranged on one side of the solid electrolyte layer;
the solid electrolyte base layer is formed by in-situ polymerization of a first polymerization monomer and lithium salt serving as main raw materials on a porous support material; the first polymerization monomer comprises a polymerization monomer A and an unsaturated carbonate monomer;
the solid electrolyte negative electrode facing layer is formed by in-situ polymerization of a second polymerization monomer, an acrylate prepolymer and a lithium salt which are used as main raw materials on one surface of the solid electrolyte base layer;
the molecular weight of the acrylate prepolymer is 100-50000;
the second polymerized monomer comprises a polymerized monomer B and an unsaturated carbonate monomer;
the polymerized monomer A and the polymerized monomer B are independently selected from compounds shown in formula I and/or compounds shown in formula II;
Figure BDA0002432060710000021
in the formula I, R 1 H, benzene ring or C1-C4 alkyl, and m is an integer more than or equal to 1;
in the formula II, R 2 Is H or-CH 3 ，R 3 Is H, benzene ring or C1-C4 alkyl, and n is an integer more than or equal to 1.
In the use process of the multilayer structure composite electrolyte, the solid electrolyte negative electrode facing layer arranged on one surface of the solid electrolyte base layer is in contact with the negative electrode, so that the multilayer structure composite electrolyte has excellent bonding performance and flexibility, is favorable for solving the problem of a negative electrode interface, particularly has an effective protection function on a metal lithium negative electrode, and can effectively inhibit lithium dendrites and expansion of the lithium negative electrode. In addition, the solid electrolyte base layer of the multilayer structure composite electrolyte has high ionic conductivity and wide electrochemical window at room temperature, and is favorable for improving the energy density of the battery.
Preferably, the acrylate prepolymer is selected from one or any combination of polyether acrylate prepolymer, polyester acrylate prepolymer, polyurethane acrylate prepolymer and epoxy acrylate prepolymer. Further preferably, the acrylate prepolymer is selected from one or any combination of polyether acrylate prepolymer, polyester acrylate prepolymer and polyurethane acrylate prepolymer. The polyether acrylate prepolymer is a reaction product of a polyether polyol and acrylic acid; the polyester acrylate prepolymer is a reaction product of a polyester polyol and acrylic acid, and can be prepared according to a known method.
Preferably, the mass ratio of the acrylate prepolymer to the second polymerization monomer is 1.
Preferably, the thickness of the solid electrolyte base layer is 5 to 500 μm, and more preferably 10 to 100 μm. The thickness of the solid electrolyte negative electrode facing layer is 0.05 to 100 μm, and more preferably 0.5 to 50 μm.
Preferably, the second polymeric monomer further comprises a vinyl monomer; the vinyl monomer in the second polymerized monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid. The vinyl monomer in the second polymerization monomer accounts for 10% or less, more preferably 5% or less of the total mass of the polymerization monomer B and the unsaturated carbonate monomer. The dissociation of lithium salt in the polymer solid electrolyte can be further promoted by adopting a proper vinyl monomer, and/or a structure with higher voltage resistance is introduced into the electrolyte structure, so that the ionic conductivity and electrochemical window of the solid electrolyte are further improved, and the solid electrolyte is endowed with better electrochemical performance. The vinyl monomer in the second polymerization monomer is further preferably acrylonitrile and/or styrene.
Preferably, in the second polymerization monomer, the mass ratio of the polymerization monomer B to the unsaturated carbonate monomer is 1.
Preferably, the raw material for forming the solid electrolyte negative electrode facing layer further includes an antioxidant, and the antioxidant in the raw material for forming the solid electrolyte negative electrode facing layer accounts for 5% or less, and more preferably 1% or less, of the total mass of the second polymeric monomer and the acrylate prepolymer.
Preferably, in the raw material for forming the negative electrode facing layer of the solid electrolyte, the lithium salt accounts for 10% to 50%, preferably 20% to 40%, of the total mass of the second polymeric monomer, the acrylate-based prepolymer and the lithium salt.
Preferably, in the first polymerization monomer, the mass ratio of the polymerization monomer a to the unsaturated carbonate monomer is 1.
Preferably, the first polymerized monomer further comprises a vinyl monomer; the vinyl monomer in the first polymerization monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid. The vinyl monomer in the first polymerization monomer accounts for 10% or less, more preferably 5% or less of the total mass of the polymerization monomer a and the unsaturated carbonate monomer. The vinyl monomer in the first polymerization monomer is further preferably acrylonitrile and/or styrene.
Preferably, the raw material for forming the solid electrolyte base layer further comprises an antioxidant, and the antioxidant in the raw material for forming the solid electrolyte base layer accounts for less than 5% of the mass of the first polymerized monomer.
Preferably, in the raw material for forming the solid electrolyte base layer, the mass of the lithium salt accounts for 10% to 50%, preferably 20% to 40%, of the total mass of the first polymeric monomer and the lithium salt.
Preferably, the molecular weight of the acrylate prepolymer is 500 to 20000.
In the raw material for forming the solid electrolyte negative electrode facing layer, the acrylic prepolymer accounts for 20% or less, preferably 10% or less, of the total mass of the second polymeric monomer and the acrylic prepolymer.
Preferably, in the formula I, m is more than or equal to 5 and less than or equal to 30. The polymerization monomer with the structure shown in the formula I is preferably one or any combination of polyethylene glycol monoallyl ether, polyethylene glycol allyl methyl ether, polyethylene glycol allyl ethyl ether, polyethylene glycol allyl phenyl ether and polyethylene glycol allyl isopropyl ether.
Preferably, in the formula II, n is more than or equal to 5 and less than or equal to 30. The polymerization monomer with the structure shown in the formula II is preferably one or any combination of polyethylene glycol acrylate, polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, polyethylene glycol phenyl ether acrylate, polyethylene glycol methyl ether methacrylate and polyethylene glycol phenyl ether methacrylate.
The porous support material can be a porous support material commonly used in the preparation of solid electrolytes in the prior art. Preferably, the porous support material is selected from one of non-woven fabric, cellulose membrane, fiber membrane, diaphragm, nylon cloth and paper. The non-woven fabric is selected from one of polyethylene terephthalate (PET) non-woven fabric and Polyimide (PI) non-woven fabric. The fiber film is selected from one of a glass fiber film and an aramid fiber film. The cellulose membrane is preferably a plant cellulose membrane. The diaphragm is selected from one of a PET diaphragm, a PI diaphragm, a Polyethylene (PE) diaphragm, a polypropylene (PP) diaphragm and a PE/PP composite diaphragm.
Preferably, the thickness of the porous support material is 5 to 100 μm, more preferably 10 to 30 μm, and still more preferably 12 to 20 μm. The pore diameter of the porous support material is 0.1 to 50 μm, more preferably 0.5 to 10 μm, and still more preferably 3 to 5 μm.
Preferably, the multilayer-structure composite electrolyte according to any of the above further comprises a solid electrolyte positive electrode-facing layer disposed on the other face of the solid electrolyte base layer; the solid electrolyte positive electrode facing layer is formed by in-situ polymerization of a third polymerization monomer, a polycarbonate polymer, a fast ion conductor and a lithium salt serving as main raw materials on the other surface of the solid electrolyte base layer; the third polymerized monomer comprises a polymerized monomer C and an unsaturated carbonate monomer; the polymerized monomer C is independently selected from one or two of a compound shown in a formula I and a compound shown in a formula II. The solid electrolyte anode facing layer arranged on the other surface of the solid electrolyte base layer introduces components such as high-voltage-resistant structural polymer, fast ion conductor and the like, can effectively relieve the damage of anode high-voltage materials to the solid electrolyte layer, has the advantages of high room-temperature ionic conductivity, wide electrochemical window and good oxidation resistance, and is suitable for a high-nickel ternary anode material system.
The polymerizable monomer C is selected without being affected by the polymerizable monomer A and the polymerizable monomer B.
Preferably, the mass ratio of the third polymerization monomer to the polycarbonate-based polymer to the fast ion conductor is 3 to 8.
Preferably, the thickness of the solid electrolyte cathode-facing layer is 0.05 to 100 μm, and more preferably 0.5 to 50 μm.
Preferably, the third polymeric monomer further comprises a vinyl monomer; the vinyl monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid. The vinyl monomer in the third polymerization monomer accounts for 10% or less, and more preferably 5% or less of the total mass of the polymerization monomer C and the unsaturated carbonate monomer. The vinyl monomer in the third polymerization monomer is further preferably acrylonitrile and/or styrene.
Preferably, in the third polymerization monomer, the mass ratio of the polymerization monomer C to the unsaturated carbonate monomer is 1.
Preferably, the raw material for forming the solid electrolyte anode facing layer further comprises an antioxidant, and the antioxidant in the raw material for forming the solid electrolyte anode facing layer accounts for less than 5% of the total mass of the third polymerized monomer, the polycarbonate polymer and the fast ion conductor.
Preferably, the polycarbonate polymer is selected from one or any combination of polyethylene carbonate, polypropylene carbonate, polyfluorinated ethylene carbonate, polyethylene carbonate and polyethylene ethylene carbonate.
Preferably, the polycarbonate-based polymer has a molecular weight of 200 to 500000. More preferably, the molecular weight of the polycarbonate-series polymer is 200 to 50000.
Preferably, the polycarbonate polymer accounts for 40% or less, preferably 30% or less, of the total mass of the third polymerization monomer, the carbonate polymer and the fast ion conductor.
Preferably, the fast ion conductor accounts for the third polymeric monomer, the carbonate polymer and the fast ion conductor50% or less, preferably 30% or less, of the total mass. The fast ion conductor is selected from Li 7 La 3 Zr 2 O 12 、Li x La 2/3-x TiO 3 (0<x<2/3)、Li 1+x AlxTi 2-x (PO4) 3 (0<x<2)、Li 1+x Al x Ge 2-x (PO 4 ) 3 (0<x<2)、LiAlO 2 、Li 7-x La 3 Zr 2-x Ta x O 12 (0<x<2)、Li 7-x La 3 Zr 2-x NbxO 12 (0<x<2)、Li 7+x Ge x P 3-x S 11 (0<x<3)、xLi 2 S·(100-x)P 2 S 5 (0<x<100 ) or any combination thereof.
Preferably, in the raw material for forming the solid electrolyte cathode facing layer, the lithium salt accounts for 10 to 50 percent, preferably 20 to 40 percent, of the total mass of the third polymerization monomer, the polycarbonate-based polymer and the lithium salt.
Preferably, the multilayer structure composite electrolyte of the present invention is prepared by a method comprising the steps of:
1) Coating slurry containing a first polymerization monomer, lithium salt and an initiator on a porous support material for in-situ polymerization and curing to prepare a solid electrolyte base layer;
2) And coating the slurry containing the second polymerization monomer, the acrylate prepolymer, the lithium salt and the initiator on one surface of the solid electrolyte base layer for in-situ polymerization and curing.
Preferably, the slurry in the step 1) also contains an antioxidant. The slurry in the step 2) also contains an antioxidant.
For a multilayer-structured composite electrolyte in which a solid electrolyte positive electrode-facing layer is provided on one side of a solid electrolyte base layer, the method for producing the multilayer composite electrolyte further comprises the steps of: and coating the slurry containing the third polymerization monomer, the polycarbonate polymer, the fast ion conductor, the lithium salt and the initiator on the other surface of the solid electrolyte base layer for in-situ polymerization and curing. Preferably, the slurry for preparing the solid electrolyte positive electrode facing layer further contains an antioxidant.
Preferably, the initiators used in step 1), step 2) and in the preparation of the solid electrolyte cathode facing layer are all photoinitiators.
The solid lithium battery adopts the technical scheme that:
a solid-state lithium battery comprises a basic battery unit, wherein the basic battery unit comprises a positive plate, a negative plate and the multilayer-structure composite electrolyte arranged between the positive plate and the negative plate, and the negative electrode of the solid-state electrolyte of the multilayer-structure composite electrolyte faces to the negative plate.
The solid lithium battery does not use any liquid electrolyte and does not contain any volatile and flammable organic liquid, so unsafe factors such as leakage, combustion, explosion and the like of the lithium ion battery are avoided, the solution of the safety problem of the lithium ion battery is facilitated, and the contact impedance of the solid electrolyte and a negative plate is reduced by adopting the multilayer structure composite electrolyte.
The solid-state lithium battery of the invention can contain one or two or more basic battery units, and when a plurality of basic battery units are contained, the basic battery units are constructed in a series connection, parallel connection or series-parallel connection combination mode.
Preferably, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer; the positive active material layer is obtained by coating and drying positive slurry containing a positive active material, a binder, a conductive agent, a polymer electrolyte and a solvent; the polymer electrolyte is obtained by polymerizing a fourth polymerization monomer and lithium salt under the action of an initiator by ultraviolet irradiation; the fourth polymerized monomer comprises a polymerized monomer D and an unsaturated carbonate monomer; the polymerized monomer D is independently selected from one or two of a compound shown in a formula I and a compound shown in a formula II. The polymerized monomer D is selected independently of other polymerized monomers.
Preferably, the fourth polymerized monomer further comprises a vinyl monomer; the vinyl monomer in the fourth polymerized monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid. The vinyl monomer in the fourth polymerization monomer accounts for 10% or less, and more preferably 5% or less of the total mass of the polymerization monomer D and the unsaturated carbonate monomer. The vinyl monomer in the fourth polymerizable monomer is more preferably acrylonitrile and/or styrene.
Preferably, in the fourth polymerizable monomer, the mass ratio of the polymerizable monomer D to the unsaturated carbonate monomer is 1.
Preferably, the positive electrode slurry further contains an antioxidant, and the antioxidant accounts for less than 5% of the mass of the polymer electrolyte.
Preferably, the polymer electrolyte in the positive electrode slurry accounts for 10-30% of the total mass of the positive electrode active material, the binder, the conductive agent and the polymer electrolyte.
Preferably, the positive active material is selected from one or any combination of layered lithium cobalt oxide, layered lithium nickel oxide, spinel type oxide, olivine type oxide. Further preferably, the positive electrode active material is selected from LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、Li 2 Mn 4 O 9 、Li 4 Mn 5 O 12 、LiFePO 4 、LiFexMn 1-x PO 4 (0≤x≤1)、LiCoPO 4 、Li 2 FeSiO 4 、LiNi 1-x Co x O 2 (0≤x≤1)、LiNi x Co y Mn z O 2 (x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, z is not less than 0 and not more than 1, and x + y + z = 1), liNi x Co y Al z O 2 (0. Ltoreq. X.ltoreq.1, 0. Ltoreq. Y.ltoreq.1, 0. Ltoreq. Z.ltoreq.1, and x + y + z = 1).
Preferably, during the preparation of the polymer electrolyte, the lithium salt is used in an amount of 30-60% of the total mass of the fourth polymerization monomer and the lithium salt.
The positive electrode current collector is not particularly limited, and may be a metal foil, a metal sheet, a metal mesh or a metal plate of at least one metal selected from iron, copper, aluminum, nickel, stainless steel, titanium, gold and platinum, preferably an aluminum foil.
The positive plate is prepared by adopting the method comprising the following steps: and uniformly coating the positive electrode slurry containing the positive electrode active substance, the conductive agent, the binder, the polymer electrolyte and the solvent on a positive electrode current collector, and drying to obtain the lithium ion battery. The positive electrode sheet may be rolled after drying in the preparation process, or may not be rolled.
Preferably, the binder used in the positive electrode sheet is selected from one or any combination of polyvinylidene fluoride (PVDF), vinylidene fluoride copolymer, polytetrafluoroethylene (PTFE) and polyacrylate.
The negative electrode material of the negative electrode sheet may be a metallic lithium or non-metallic lithium negative electrode active material. When the negative electrode material is metallic lithium, the negative electrode sheet can be a foil, a strip, a sheet or a plate containing the metallic lithium, and can be a lithium-copper composite strip (formed by compounding a lithium strip and a copper strip). When the negative electrode material is a non-metal lithium negative electrode active material, the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer. The negative electrode active material layer is a coating layer including a negative electrode active material, a conductive agent, and a negative electrode binder. The negative active material is selected from one or any combination of graphite, hard carbon, soft carbon, nano silicon, silicon oxide and a silicon-carbon composite material.
The negative electrode binder is selected from one or any combination of modified or unmodified styrene-butadiene rubber emulsion (SBR), polyacrylate emulsion, modified or unmodified polyacrylic acid, modified or unmodified polyacrylate, sodium alginate, sodium carboxymethylcellulose, modified or unmodified polyvinyl alcohol and polyamide.
The negative current collector is selected from metal foil, metal sheet, metal mesh or metal plate of at least one metal of iron, copper, aluminum, nickel, stainless steel, titanium, gold and platinum, and is preferably copper foil.
When the negative electrode material is a non-metal lithium negative electrode active substance, the negative electrode sheet is prepared by adopting the method comprising the following steps: and uniformly coating the negative electrode slurry containing the negative electrode active material, the conductive agent, the negative electrode binder and the solvent on a negative electrode current collector, and drying to obtain the lithium ion battery. The negative electrode sheet may be rolled after being dried during the preparation, or may not be rolled.
The conductive agent in the positive electrode active material layer and the negative electrode active material layer is independently selected from one or any combination of carbon black, graphite, carbon nanotubes, carbon fibers, graphene and activated carbon. The carbon black is preferably ketjen black and/or acetylene black.
The solvent used in the above method for preparing the positive and negative electrode sheets is a conventional solvent in the art, such as N-methylpyrrolidone.
The initiator used in the preparation of the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer and the polymer electrolyte in the positive active material layer of the positive plate of the solid lithium battery of the multilayer structure composite electrolyte is a photoinitiator, and polymerization is carried out under the irradiation of ultraviolet rays. The curing process can also be carried out under the irradiation of ultraviolet rays. The light source of the ultraviolet light is not limited, and may be any one selected from a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, a xenon lamp, and a UV-LED lamp.
Preferably, the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer, and the polymer electrolyte in the positive electrode active material layer are prepared using an initiator independently selected from the group consisting of 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 2-isopropylthioxanthone, 4-dimethylamino-ethyl benzoate, 1-hydroxy-cyclohexylmonophenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, 4-chlorobenzophenone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-hydroxy-4 ' - (2-hydroxyethoxy) -2-methylpropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-phenylbenzophenone, 2-ethylhexyl 4- (dimethylamino) benzoate, 4' -bis (diethylamino) benzophenone, or any combination thereof, and further preferably 2-hydroxy-2-methyl-1-phenyl-1-propanone.
When the polymer electrolyte in the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer and the active material layer of the positive plate of the solid lithium battery of the multilayer-structure composite electrolyte is prepared, the photoinitiator adopted by the solid electrolyte base layer accounts for 0.01-10%, preferably 0.5-5% of the total mass of the first polymerization monomer and the acrylate prepolymer. The photoinitiator used in the solid electrolyte negative electrode facing layer accounts for 0.01-10% of the mass of the second polymeric monomer, and preferably 0.5-5%. The photoinitiator adopted by the solid electrolyte anode facing layer accounts for 0.01-10% of the mass of the third polymerized monomer, and preferably 0.5-5%. The photoinitiator used in the polymer electrolyte in the positive electrode active material layer accounts for 0.01 to 10% by mass, preferably 0.5 to 5% by mass, of the fourth polymerizable monomer.
The raw material of the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer, and the lithium salt used for the polymer electrolyte in the positive electrode active material layer of the solid lithium battery positive electrode sheet of the multilayer structure composite electrolyte are independently selected from one or any combination of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium aluminate, lithium nitrate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalato borate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluoroalkoxysulfonylimide, lithium difluoroalkylsulfonamide, lithium thiocyanate, lithium bistrifluoromethylsulfonylalkyl, lithium triflate, lithium methylchite, lithium bistrifluoromethyltetrafluoroborate, lithium dicyanoimidoate, and lithium diglycolate borate, and further preferably lithium bistrifluoromethylsulfonylimide.
Unsaturated carbonate monomers in the first polymerization monomer, unsaturated carbonate monomers in the second polymerization monomer, unsaturated carbonate monomers in the third polymerization monomer and unsaturated carbonate monomers in the fourth polymerization monomer of the multilayer structure composite electrolyte are independently selected from one or two of chain unsaturated carbonate monomers and cyclic unsaturated carbonate monomers.
Preferably, the chain unsaturated carbonate monomer has a structure shown in formula III:
Figure BDA0002432060710000081
in the formula III, R 4 Is H or-CH 3 ，R 5 H, benzene ring or C1-C4 alkyl.
Preferably, the unsaturated carbonate monomer in the first polymerization monomer, the unsaturated carbonate monomer in the second polymerization monomer, the unsaturated carbonate monomer in the third polymerization monomer, and the unsaturated carbonate monomer in the fourth polymerization monomer are independently selected from one or any combination of allyl methyl carbonate, propylene ethyl carbonate, propylene propyl carbonate, propylene butyl carbonate, methyl allyl methyl carbonate, methyl allyl ethyl carbonate, methyl allyl propyl carbonate, methyl allyl phenyl carbonate, vinylene carbonate, propylene carbonate, and vinyl ethylene carbonate. More preferably, the unsaturated carbonate monomer in the first polymerization monomer, the unsaturated carbonate monomer in the second polymerization monomer, the unsaturated carbonate monomer in the third polymerization monomer, and the unsaturated carbonate monomer in the fourth polymerization monomer are independently selected from one or any combination of allyl methyl carbonate, allyl phenyl carbonate, vinylene carbonate, and vinyl ethylene carbonate.
During preparation of the solid electrolyte base layer, the solid electrolyte cathode facing layer, the solid electrolyte anode facing layer and the anode active material layer of the anode plate of the solid lithium battery of the multilayer structure composite electrolyte, the adopted antioxidants are independently selected from one or any combination of aromatic amine antioxidants, hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants and composite antioxidants. For example, the antioxidant used in the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer, and the positive active material layer of the positive electrode sheet of the solid lithium battery in the multilayer composite electrolyte is independently selected from one or any combination of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, antioxidant 626, antioxidant 618, antioxidant 330, and antioxidant 300.
In the preparation process of the solid electrolyte base layer, the solid electrolyte negative electrode facing layer, the solid electrolyte positive electrode facing layer and the positive active material layer in the positive plate adopted by the solid lithium battery, the slurry can be coated by one of blade coating, dip coating and roll coating.
Drawings
Fig. 1 is a schematic structural view of a solid lithium battery of example 13 of the invention;
FIG. 2 is a graph showing the charge and discharge curves at room temperature for a solid lithium battery according to example 13 of the present invention;
fig. 3 is a graph showing the charge and discharge curves at room temperature of the solid lithium battery of example 14 of the present invention;
fig. 4 is a graph showing charging and discharging curves at room temperature of the solid lithium battery of example 15 of the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments.
In the following examples, examples 1 to 12 are examples of a multi-layer structure composite electrolyte and a method for preparing the same, and examples 13 to 22 are examples of a solid state lithium battery.
The polyether acrylate prepolymer used in the examples was the reaction product of a polyether polyol and acrylic acid, and the polyester acrylate prepolymer was the reaction product of a polyester polyol and acrylic acid, all prepared according to methods known in the industry.
Example 1
The multilayer structure composite electrolyte comprises a solid electrolyte base layer, a solid electrolyte cathode facing layer arranged on one surface of the solid electrolyte base layer, and a solid electrolyte anode facing layer arranged on the other surface of the solid electrolyte base layer;
the solid electrolyte base layer is formed by in-situ polymerization of a first polymerization monomer, lithium salt and an initiator serving as main raw materials on a porous support material; the porous supporting material is PET non-woven fabric, the thickness is 20 μm, and the aperture is 3 μm; the thickness of the solid electrolyte base layer is 80 μm;
the solid electrolyte negative electrode facing layer is formed by in-situ polymerization of a second polymerization monomer, an acrylate prepolymer, a lithium salt and an initiator serving as main raw materials on one surface of a solid electrolyte base layer; the acrylate prepolymer is polyether acrylate prepolymer, and the weight average molecular weight (hereinafter abbreviated as Mw) is 1000; the thickness of the solid electrolyte negative electrode facing layer was 2 μm;
the solid electrolyte anode facing layer is formed by in-situ polymerizing a third polymerized monomer, a polycarbonate polymer, a fast ion conductor, a lithium salt and an initiator serving as main raw materials on the other surface of the solid electrolyte base layer; the polycarbonate polymer is polyethylene carbonate (Mw = 2000), and the fast ion conductor is Li 1+x Al x Ge 2-x (PO 4 ) 3 (0<x<2, abbreviated lag); the thickness of the solid electrolyte anode-facing layer was 5 μm;
the first, second and third polymeric monomers are all methoxypolyethylene glycol acrylate (i.e., a compound of formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13) and vinylene carbonate, and the mass ratio is 1.2;
lithium salts adopted by the solid electrolyte base layer, the solid electrolyte cathode facing layer and the solid electrolyte anode facing layer are all bis (trifluoromethyl) sulfonyl imide lithium, and initiators are all 2-hydroxy-2-methyl-1-phenyl-1-acetone;
in the raw materials of the solid electrolyte base layer, the mass ratio of a first polymerization monomer, a lithium salt and an initiator is 4;
in the raw materials of the facing layer of the solid electrolyte negative electrode, the mass ratio of a second polymeric monomer, an acrylate prepolymer, a lithium salt and an initiator is 4;
in the raw materials of the positive electrode facing layer of the solid electrolyte, the mass ratio of the third polymeric monomer, the polycarbonate polymer, the fast ion conductor, the lithium salt and the initiator is 4.
The preparation method of the multilayer structure composite electrolyte of the embodiment comprises the following steps:
1) Weighing and uniformly mixing the components according to the formula of each electrolyte solution shown in the table 1 to respectively obtain an electrolyte solution A, an electrolyte solution B and an electrolyte solution C;
2) Fixing PET non-woven fabric (with thickness of 20 μm and aperture of 3 μm) on a release film, coating electrolyte solution B on the upper surface of the PET non-woven fabric by a blade coater, polymerizing and curing under ultraviolet light, and peeling off the release film to obtain a solid electrolyte base layer (with thickness of 80 μm and containing PET non-woven fabric);
3) Coating an electrolyte solution A on the stripping surface of the solid electrolyte base layer, and curing in situ under ultraviolet light to obtain a solid electrolyte cathode facing layer (the thickness is 2 μm);
4) And then coating the electrolyte solution C on the other surface of the solid electrolyte base layer, and curing in situ under ultraviolet light to obtain a solid electrolyte anode facing layer (with the thickness of 5 microns).
TABLE 1 respective electrolyte solution formulations
Figure BDA0002432060710000101
Figure BDA0002432060710000111
Example 2
The multilayer structure composite electrolyte comprises a solid electrolyte base layer, a solid electrolyte cathode facing layer arranged on one side of the solid electrolyte base film, and a solid electrolyte anode facing layer arranged on the other side of the solid electrolyte base film;
the solid electrolyte base layer is formed by in-situ polymerization of a first polymerization monomer, lithium salt, an antioxidant and an initiator serving as main raw materials on a porous support material; the porous supporting material is PET non-woven fabric, the thickness is 20 μm, and the aperture is 3 μm; the thickness of the solid electrolyte base layer is 80 μm;
the solid electrolyte negative electrode facing layer is formed by in-situ polymerization of a second polymerization monomer, an acrylate prepolymer, a lithium salt, an antioxidant and an initiator serving as main raw materials on one surface of a solid electrolyte base layer; the acrylate prepolymer is polyether acrylate prepolymer, and Mw is 1000; the thickness of the solid electrolyte negative electrode facing layer was 2 μm;
the positive electrode facing layer of the solid electrolyte is mainly composed of a third polymerization monomer, a polycarbonate polymer, a fast ion conductor, a lithium salt, an antioxidant and an initiatorThe raw materials are prepared by in-situ polymerization on the other surface of the solid electrolyte base layer; the polycarbonate polymer is polyethylene carbonate (Mw = 2000), and the fast ion conductor is Li 1+x Al x Ge 2-x (PO 4 ) 3 (0<x<2, abbreviated as LAGP) solid electrolyte negative electrode facing layer thickness of 5 μm;
the first polymerized monomer, the second polymerized monomer and the third polymerized monomer are all polyethylene glycol methyl ether methacrylate (namely, the compound shown in the formula II, R) 2 、R 3 Both methyl, n is 13) and vinylene carbonate, the mass ratio of the compound shown in the formula II to the vinylene carbonate in the first polymerized monomer and the second polymerized monomer is 2, and the mass ratio of the compound shown in the formula II to the vinylene carbonate in the third polymerized monomer is 2.8;
lithium salts adopted by the solid electrolyte base layer, the solid electrolyte cathode facing layer and the solid electrolyte anode facing layer are all bis (trifluoromethyl) sulfonyl imide lithium, antioxidants are all antioxidant 1010, and initiators are all 2-hydroxy-2-methyl-1-phenyl-1-acetone;
in the raw materials of the solid electrolyte base layer, the mass ratio of a first polymerization monomer, lithium salt, an antioxidant and an initiator is 4;
in the raw materials of the facing layer of the solid electrolyte negative electrode, the mass ratio of a second polymerization monomer, an acrylate prepolymer, a lithium salt, an antioxidant and an initiator is (4);
in the raw materials of the facing layer of the solid electrolyte anode, the mass ratio of a third polymerization monomer, a polycarbonate polymer, a fast ion conductor, a lithium salt, an antioxidant and an initiator is (4.4).
The preparation method of the multilayer structure composite electrolyte of the embodiment comprises the following steps:
1) Weighing and uniformly mixing the components according to the formula of each electrolyte solution shown in the table 2 to respectively obtain an electrolyte solution A, an electrolyte solution B and an electrolyte solution C;
2) Fixing PET non-woven fabric (with thickness of 20 μm and aperture of 3 μm) on a release film, coating electrolyte solution B on the upper surface of the PET non-woven fabric by a blade coater, polymerizing and curing under ultraviolet light, and peeling off the release film to obtain a solid electrolyte base layer (with thickness of 80 μm and containing PET non-woven fabric);
3) Coating an electrolyte solution A on the stripping surface of the solid electrolyte base layer, and curing in situ under ultraviolet light to obtain a solid electrolyte cathode facing layer (the thickness is 2 μm);
4) And then coating the electrolyte solution C on the other surface of the solid electrolyte base layer, and curing in situ under ultraviolet light to obtain a solid electrolyte anode facing layer (with the thickness of 5 microns).
TABLE 2 electrolyte solution formulation
Figure BDA0002432060710000121
Example 3
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the thickness of the solid electrolyte base layer was 100 μm. The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 4
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the porous supporting material is PET non-woven fabric with the thickness of 12 mu m and the aperture of 5 mu m; the thickness of the solid electrolyte base layer was 25 μm. The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 5
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 in that: the first, second and third polymeric monomers are all methoxypolyethylene glycol acrylate (i.e., a compound of formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13), vinylene carbonate and acrylonitrile, and the mass ratio is 1.1.
The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 6
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 in that: the first, second and third polymeric monomers are all methoxypolyethylene glycol acrylate (i.e., a compound of formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13), vinylene carbonate and styrene, and the mass ratio is 1.1.
The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 7
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 in that: the adopted acrylate prepolymer is polyester acrylate prepolymer, and Mw is 5000.
The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 8
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the polycarbonate polymer is polypropylene carbonate, and Mw =50000.
The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 9
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the first, second and third polymeric monomers are polyethylene glycol monoallyl ether (i.e., a compound of formula I, R) 1 Is methyl, n is 10) and vinylene carbonate, and the mass ratio is 1.2.
The method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 10
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the first, second and third polymeric monomers are all methoxypolyethylene glycol acrylate (i.e., a compound of formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13) and allylphenyl carbonate (i.e. a compound of formula III, R 4 Is hydrogen, R 5 Benzene ring), the mass ratio is 1.2;
the method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 11
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 1 only in that: the first, second and third polymeric monomers are all polyethylene glycol phenyl ether acrylate (i.e., a compound of formula II, R 2 Is hydrogen, R 3 Is a benzene ring, n is 13) and vinylene carbonate, and the mass ratio is 1.2;
the method for producing the multilayer structure composite electrolyte of the present example was performed with reference to the method for producing the multilayer structure composite electrolyte of example 1.
Example 12
The multilayer structure composite electrolyte of the present example is different from the multilayer structure composite electrolyte of example 2 only in that: the solid electrolyte base layer and the solid electrolyte cathode facing layer do not contain an antioxidant.
The method for producing the multilayer-structured composite electrolyte of this example was performed in accordance with the method for producing the multilayer-structured composite electrolyte of example 2, except that the antioxidant in the electrolyte solution a and the electrolyte solution B was omitted.
Example 13
The solid-state lithium battery of the present embodiment is an all-solid-state lithium battery, and includes a basic battery unit 1, as shown in fig. 1, the basic battery unit 1 includes a positive electrode sheet 2, a negative electrode sheet 3, and a multilayer-structure composite electrolyte 4 sandwiched between the positive and negative electrode sheets; the negative plate 3 is a lithium-copper composite belt;
the adopted multilayer structure composite electrolyte is the multilayer structure composite electrolyte of the embodiment 1, and the negative electrode of the solid electrolyte of the multilayer structure composite electrolyte faces to the negative plate;
the positive plate 2 comprises a positive current collector and a positive active material layer arranged on the positive current collector, and is prepared by adopting a method comprising the following steps: adding an N-methyl pyrrolidone solvent into a positive active material NCM811, conductive carbon black SP, a binder PVDF and a polymer electrolyte according to the mass ratio of 7.6;
the polymer electrolyte is prepared by adopting a method comprising the following steps:
1) The methoxypolyethylene glycol acrylate (i.e., the compound of formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13), vinylene carbonate and lithium bistrifluoromethylsulfonyl imide, and are uniformly mixed; the mass ratio of the methoxy polyethylene glycol acrylate to the vinylene carbonate is 7, and the mass ratio of the total mass of the methoxy polyethylene glycol acrylate and the vinylene carbonate to the bis (trifluoromethyl) sulfonyl imide lithium is 5;
2) Adding a photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixed solution obtained in the step 1), and uniformly mixing; the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone accounts for 1 percent of the total mass of the methoxypolyethylene glycol acrylate and the vinylene carbonate;
3) And (3) dropwise adding the mixed solution obtained in the step 2) into a tetrafluoroethylene plate mold, and carrying out in-situ curing under an ultraviolet lamp to obtain the polymer electrolyte.
Example 14
The solid-state lithium battery of the present example is different from the solid-state lithium battery of example 13 only in that: the positive active material in the positive plate is replaced by lithium manganese iron phosphate.
Example 15
The solid-state lithium battery of the present example is different from the solid-state lithium battery of example 13 only in that: the positive electrode active material in the positive electrode sheet is lithium cobaltate.
Example 16
The solid-state lithium battery of the present example is different from the solid-state lithium battery of example 13 only in that: the multilayer-structure composite electrolyte used was the multilayer-structure composite electrolyte of example 2.
Example 17
The solid-state lithium battery of the present example differs from the solid-state lithium battery of example 13 only in that: the multilayer-structure composite electrolyte used was the multilayer-structure composite electrolyte of example 5.
Example 18
The solid-state ion battery of the present example differs from example 13 only in that: methoxy polyethylene glycol acrylate (i.e. compound shown as formula II, R) in polymer electrolyte 2 Is hydrogen, R 3 Is methyl, n is 13) and vinylene carbonate in a mass ratio of 8.
The method for preparing the polymer electrolyte in this example refers to the method for preparing the polymer electrolyte in example 13.
Example 19
The solid-state lithium battery of the present example differs from example 13 only in that: methoxy polyethylene glycol acrylate (i.e. compound shown as formula II, R) in polymer electrolyte 2 Is hydrogen, R 3 Is methyl, n is 13) and vinylene carbonate in a mass ratio of 5.
The method for preparing the polymer electrolyte in this example refers to the method for preparing the polymer electrolyte in example 13.
Example 20
The solid-state lithium battery of the present example differs from example 13 only in that: methoxy polyethylene glycol acrylate and vinylene carbonate in the polymer electrolyte are respectively replaced by polyethylene glycol phenyl ether acrylate (namely a compound shown as a formula II, R) 2 Is hydrogen, R 3 Is a benzene ring, n is 13) and allyl phenyl carbonate (namely, the compound shown in the formula III, R 4 Is hydrogen, R 5 Is a benzene ring).
The method for preparing the polymer electrolyte in this example refers to the method for preparing the polymer electrolyte in example 13.
Example 21
The solid-state lithium battery of the present example differs from example 13 only in that: methoxy polyethylene glycol acrylate and vinylene carbonate in the polymer electrolyte are respectively replaced by polyethylene glycol monoallyl ether (namely, a compound shown in formula I, R) 1 Is methyl, n is 10) and vinylene carbonate.
The method for preparing the polymer electrolyte in this example refers to the method for preparing the polymer electrolyte in example 13.
Example 22
The solid-state lithium battery of the present example differs from example 13 only in that: the polymer electrolyte also contains acrylonitrile and antioxidant 1010, wherein the acrylonitrile is methoxy polyethylene glycol acrylate (namely a compound shown as a formula II, R) 2 Is hydrogen, R 3 Is methyl, n is 13) and vinylene carbonate, and the antioxidant 1010 accounts for 0.5 percent of the total mass of the polymer electrolyte.
Experimental example 1
In this experimental example, the room temperature ionic conductivity of the multilayer structure composite electrolytes of examples 1 to 12 was measured, and the results are shown in table 1.
The room-temperature ionic conductivity of the multilayer structure composite electrolyte is tested by an EIS method: cutting the prepared multilayer structure composite electrolyte into a wafer with the diameter of 18mm, then clamping the wafer between two stainless steel electrodes (SS) to assemble an SS/SPE/SS blocking electrode, wherein the ionic conductivity of the electrolyte is indirectly obtained by testing the alternating current impedance spectrum of the blocking electrode by an electrochemical workstation, and the testing frequency range of the alternating current impedance spectrum is 10 6 HZ-0.1 HZ. The ionic conductivity (σ) is calculated by the following formula:
Figure BDA0002432060710000161
wherein R (Ω) is the resistance of the sample, L (cm) is the thickness of the sample, and S (cm) 2 ) Is the area of the sample. The thickness of the sample was measured by a thickness gauge.
Table 1 room temperature ionic conductivity of the multi-layer structure composite electrolytes of examples 1 to 12
Figure BDA0002432060710000162
Figure BDA0002432060710000171
Experimental example 2
The solid lithium batteries of examples 13 to 15 were respectively subjected to a charge-discharge performance test at room temperature under the conditions of a charge-discharge magnification of 0.1C/0.1C, a cut-off magnification of 0.05C, and a charge cut-off voltage of 4.3V; the discharge cut-off voltage of example 13 and example 15 was 3.0V, the discharge cut-off voltage of example 14 was 2.5V, and the test results are shown in FIGS. 2 to 4. As can be seen from fig. 2 to 4, the solid-state lithium battery of the present invention can realize normal charging and discharging at room temperature, and has a high withstand voltage capability, so that the multilayer structure composite electrolyte of the present invention can be applied to a high-nickel ternary positive electrode material system, which is helpful for increasing the energy density of the lithium battery.

Claims (29)

1. A multilayer structure composite electrolyte characterized by: the solid electrolyte cathode comprises a solid electrolyte base layer and a solid electrolyte cathode facing layer arranged on one surface of the solid electrolyte layer;
the solid electrolyte base layer is formed by in-situ polymerization of a first polymerization monomer, lithium salt and an initiator serving as main raw materials on a porous support material; the first polymerization monomer comprises a polymerization monomer A and an unsaturated carbonate monomer;
the solid electrolyte negative electrode facing layer is formed by in-situ polymerization of a second polymerization monomer, an acrylate prepolymer, a lithium salt and an initiator serving as main raw materials on one surface of the solid electrolyte base layer;
the molecular weight of the acrylate prepolymer is 100-50000;
the second polymerized monomer comprises a polymerized monomer B and an unsaturated carbonate monomer;
the polymerized monomer A and the polymerized monomer B are independently selected from compounds shown in formula I and/or compounds shown in formula II;
Figure FDA0003843294750000011
in the formula I, R 1 H, benzene ring or C1-C4 alkyl, and m is an integer more than or equal to 1;
in the formula II, R 2 Is H or-CH 3 ，R 3 H, benzene ring or C1-C4 alkyl, n is an integer more than or equal to 1;
the unsaturated carbonate monomer in the first polymerization monomer and the unsaturated carbonate monomer in the second polymerization monomer are independently selected from one or two of chain unsaturated carbonate monomers and cyclic unsaturated carbonate monomers;
the chain unsaturated carbonate monomer has a structure shown in a formula III or one or any combination of ethylene carbonate:
Figure FDA0003843294750000012
in the formula III, R 4 Is H or-CH 3 ，R 5 H, benzene ring or C1-C4 alkyl;
the cyclic unsaturated carbonate monomer is one or any combination of vinylene carbonate or propylene carbonate.
2. The multilayer structure composite electrolyte according to claim 1, characterized in that: the acrylate prepolymer is selected from one or any combination of polyether acrylate prepolymer, polyester acrylate prepolymer, polyurethane acrylate prepolymer and epoxy acrylate prepolymer.
3. The multilayer structure composite electrolyte according to claim 1, characterized in that: the second polymeric monomer further comprises a vinyl monomer; the vinyl monomer in the second polymerized monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid; the vinyl monomer in the second polymerization monomer accounts for less than 10% of the total mass of the polymerization monomer B and the unsaturated carbonate monomer.
4. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the second polymerization monomer, the mass ratio of the polymerization monomer B to the unsaturated carbonate monomer is 1.
5. The multilayer structure composite electrolyte according to claim 1, characterized in that: the raw material for forming the negative electrode facing layer of the solid electrolyte layer also comprises an antioxidant, and the antioxidant accounts for less than 5% of the total mass of the second polymerization monomer and the acrylate prepolymer.
6. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the raw materials of the solid electrolyte base layer, the lithium salt accounts for 10-50% of the total mass of the first polymerization monomer and the lithium salt.
7. The multilayer structure composite electrolyte according to claim 1, characterized in that: the first polymerized monomer further comprises a vinyl monomer; the vinyl monomer in the first polymerization monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid; the vinyl monomer in the first polymerization monomer accounts for less than 10% of the total mass of the polymerization monomer A and the unsaturated carbonate monomer.
8. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the first polymerization monomer, the mass ratio of the polymerization monomer A to the unsaturated carbonate monomer is 1.
9. The multilayer structure composite electrolyte according to claim 1, characterized in that: the raw material for forming the solid electrolyte base layer also comprises an antioxidant, and the antioxidant in the raw material for forming the solid electrolyte base layer accounts for less than 5% of the mass of the first polymerized monomer.
10. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the raw materials of the negative electrode facing layer of the solid electrolyte, the lithium salt accounts for 10-50% of the total mass of the second polymeric monomer, the acrylate prepolymer and the lithium salt.
11. The multilayer structure composite electrolyte according to claim 1, characterized in that: the molecular weight of the acrylate prepolymer is 500-20000.
12. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the raw materials for forming the solid electrolyte negative electrode facing layer, the acrylic ester prepolymer accounts for less than 20% of the total mass of the second polymerization monomer and the acrylic ester prepolymer.
13. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the formula I, m is more than or equal to 5 and less than or equal to 30.
14. The multilayer structure composite electrolyte according to claim 1, characterized in that: in the formula II, n is more than or equal to 5 and less than or equal to 30.
15. The multilayer structure composite electrolyte according to any one of claims 1 to 14, characterized in that: the solid electrolyte anode facing layer is arranged on the other side of the solid electrolyte base layer;
the solid electrolyte anode facing layer is formed by in-situ polymerization of a third polymerization monomer, a polycarbonate polymer, a fast ion conductor, a lithium salt and an initiator serving as main raw materials on the other surface of the solid electrolyte base layer;
the third polymerized monomer comprises a polymerized monomer C and an unsaturated carbonate monomer;
the polymerized monomer C is independently selected from one or two of a compound shown in a formula I and a compound shown in a formula II.
16. The multilayer structure composite electrolyte according to claim 15, characterized in that: in the raw materials for forming the positive electrode facing layer of the solid electrolyte, lithium salt accounts for 10-50% of the total mass of the third polymerized monomer, the polycarbonate polymer and the lithium salt.
17. The multilayer structure composite electrolyte according to claim 15, characterized in that: the third polymeric monomer further comprises a vinyl monomer; the vinyl monomer in the third polymerized monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid; the vinyl monomer in the third polymerized monomer accounts for less than 10 percent of the total mass of the polymerized monomer C and the unsaturated carbonate monomer.
18. The multilayer structure composite electrolyte according to claim 15, characterized in that: in the third polymerization monomer, the mass ratio of the polymerization monomer C to the unsaturated carbonate monomer is 1.
19. The multilayer structure composite electrolyte according to claim 15, characterized in that: the raw material for forming the solid electrolyte anode facing layer also comprises an antioxidant, and the antioxidant in the raw material for forming the solid electrolyte anode facing layer accounts for less than 5% of the total mass of the third polymerization monomer, the polycarbonate polymer and the fast ion conductor.
20. The multilayer structure composite electrolyte according to claim 15, characterized in that: the polycarbonate polymer is selected from one or any combination of polyethylene carbonate, polypropylene carbonate, polyfluorinated ethylene carbonate, polyethylene carbonate and polyethylene ethylene carbonate.
21. The multilayer structure composite electrolyte according to claim 15, characterized in that: the molecular weight of the polycarbonate polymer is 200-50000.
22. The multilayer structure composite electrolyte according to claim 15, characterized in that: the polycarbonate polymer accounts for less than 40% of the total mass of the third polymerization monomer, the carbonate polymer and the fast ion conductor.
23. The multilayer structure composite electrolyte according to claim 15, characterized in that: the fast ion conductor accounts for less than 50% of the total mass of the third polymerization monomer, the carbonate polymer and the fast ion conductor.
24. A solid state lithium battery comprising a basic cell, characterized in that: the basic battery cell comprises a positive plate, a negative plate and the multilayer-structure composite electrolyte of claim 1 arranged between the positive plate and the negative plate, wherein the solid electrolyte negative electrode of the multilayer-structure composite electrolyte faces the negative plate.
25. The lithium solid state battery of claim 24, wherein: the positive plate comprises a positive current collector and a positive active material layer; the positive active material layer is obtained by coating and drying positive slurry containing a positive active material, a binder, a conductive agent, a polymer electrolyte and a solvent;
the polymer electrolyte is obtained by polymerizing a fourth polymerization monomer and lithium salt under the action of an initiator by ultraviolet irradiation;
the fourth polymerized monomer comprises a polymerized monomer D and an unsaturated carbonate monomer;
the polymerized monomer D is independently selected from one or two of a compound shown in a formula I and a compound shown in a formula II.
26. The solid state lithium battery of claim 25, wherein: the fourth polymerized monomer further comprises a vinyl monomer; the vinyl monomer in the fourth polymerization monomer is selected from one or any combination of styrene, acrylonitrile, acrolein and acrylic acid, and the vinyl monomer in the fourth polymerization monomer accounts for less than 10% of the total mass of the polymerization monomer D and the unsaturated carbonate monomer.
27. The lithium solid state battery of claim 25, wherein: in the fourth polymerization monomer, the mass ratio of the polymerization monomer D to the unsaturated carbonate monomer is 1.
28. The solid state lithium battery of claim 25, wherein: the positive electrode slurry also contains an antioxidant, and the antioxidant accounts for less than 5% of the mass of the polymer electrolyte.
29. The lithium solid state battery of claim 25, wherein: the polymer electrolyte in the anode slurry accounts for 10-30% of the total mass of the anode active material, the binder, the conductive agent and the polymer electrolyte.
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