CN116581372A - Solid electrolyte membrane of lithium ion battery, preparation method of solid electrolyte membrane and lithium ion battery - Google Patents

Solid electrolyte membrane of lithium ion battery, preparation method of solid electrolyte membrane and lithium ion battery Download PDF

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Publication number
CN116581372A
CN116581372A CN202310856955.6A CN202310856955A CN116581372A CN 116581372 A CN116581372 A CN 116581372A CN 202310856955 A CN202310856955 A CN 202310856955A CN 116581372 A CN116581372 A CN 116581372A
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solid electrolyte
layer
electrolyte membrane
lithium ion
ion battery
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CN202310856955.6A
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CN116581372B (en
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张雪
易红明
刘仲书
李峥
冯玉川
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Suzhou Qingtao New Energy S&T Co Ltd
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Suzhou Qingtao New Energy S&T 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The application provides a solid electrolyte membrane of a lithium ion battery, a preparation method thereof and the lithium ion battery. According to the application, the ultrathin, flexible, high-conductivity lithium and high-mechanical-strength halide-based solid electrolyte membrane is prepared through a mode of three-dimensional composite superposition two-dimensional composite, so that the requirement of reduction resistance of a negative electrode side can be met, meanwhile, the preparation of the ultrathin solid electrolyte membrane by a dry method is possible by means of the mechanical supporting effect of a two-dimensional layer non-woven fabric and other structures in a matrix gel layer, the mechanical strength is improved while the high conductivity is ensured, and the interface suitability and the battery cycle are improved by utilizing an asymmetric structural design.

Description

Solid electrolyte membrane of lithium ion battery, preparation method of solid electrolyte membrane and lithium ion battery
Technical Field
The application relates to the technical field of batteries, in particular to a solid electrolyte membrane of a lithium ion battery, a preparation method of the solid electrolyte membrane and the lithium ion battery.
Background
By Li 2 ZrCl 6 The halide solid electrolyte as the main body has the advantages of excellent electrical property and deformability and low raw material cost, and is very suitable for developing a new generation of solid lithium batteries with higher performance and higher safety. The halides may generally be used as solid electrolyte membrane layers for the preparation of full cells.
The solid electrolyte membrane is positioned between the positive electrode and the negative electrode of the lithium ion battery, and is mainly used for separating positive and negative active substances and preventing the two electrodes from being short-circuited due to contact. In addition, in the electrochemical reaction, a channel capable of forming excellent ion movement is required. The types of cells vary, as do the solid electrolyte membranes used. In the construction of lithium batteries, a solid electrolyte membrane is one of the key inner layer components. The performance of the solid electrolyte membrane determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the solid electrolyte membrane with excellent performance plays an important role in improving the comprehensive performance of the battery. The ideal solid electrolyte membrane needs to have characteristics of ultra-thin, high conductivity, excellent interface stability to the anode and the cathode, high machinability and the like.
However, for the halide electrolyte with excellent comprehensive performance, the solid electrolyte membrane prepared by the system currently has a certain problem, and needs to be solved. Common halide-based solid state electrolyte layers are prepared by the following methods:
1) Directly adopt Li 2 ZrCl 6 The halide solid electrolyte powder is pressed and formed to be used as a solid electrolyte layer. The electrolyte membrane obtained by the method is difficult to thin, thick and has no flexibility, so that not only is the manufacturing difficult amplified, but also the energy density of the obtained battery is greatly reduced;
2) In some researches, the electrolyte membrane is prepared by compounding halide and PTFE binder by adopting a dry method, and the method can effectively thin the electrolyte, but has limited thinning degree. The reason is that under the condition of a small amount of PTFE, the mechanical property of the film is poor after thinning, which brings great problems to battery processing, and the application of the PTFE in actual industrial production cannot be promoted; and when PTFE is added in a large amount, the mechanical property is relatively better after thinning, but the electrical conductivity is seriously reduced, so that the electrical property is deteriorated.
In addition to the above problems of preparing an ultra-thin, high mechanical strength electrolyte membrane, li 2 ZrCl 6 The system also has the problem of instability to low potential cathodes, and when used directly, the battery cycle performance can be poor when matching low potential cathodes, such as lithium metal, conventional graphite or silicon-based cathodes.
Therefore, there is a need to propose a new halide-based solid electrolyte membrane to solve the above-described problems.
Disclosure of Invention
In order to solve one or more of the above technical problems in the prior art, the embodiment of the application provides a novel solid electrolyte membrane of a lithium ion battery, a preparation method thereof and the lithium ion battery, which can not only solve the requirement of halide on the reduction resistance of a negative electrode side, but also enable the dry preparation of an ultrathin halide-based solid electrolyte membrane to be possible by means of the mechanical supporting effect of a two-dimensional layer non-woven fabric and other structures.
In order to achieve the above purpose, the technical scheme adopted by the application for solving the technical problems is as follows:
in a first aspect, the present application provides a solid electrolyte membrane for a lithium ion battery, the solid electrolyte membrane comprising a solid electrolyte layer and a matrix gel layer laminated to each other;
the solid electrolyte layer comprises a halide solid electrolyte and a binder;
the binder is a fibrous structure.
It is understood that the fibrous structure of the binder refers to a rod-shaped material having a certain aspect ratio, and it is understood that the aspect ratio and the dimensional structure of the fibers are not particularly limited in the present application, and any material of reasonable dimensional structure can be used in the present application without departing from the concept of the present application. By way of illustrative example only, and not by way of limitation of the scope of protection, the binder fibers have an aspect ratio >1.
As an embodiment, the fibrous structure of the binder is obtained by fiberization.
The present application is not particularly limited to the fiberization process, and any known fiberization process can be used in the present application without departing from the inventive concept. As an embodiment, the fiberizing process comprises a crushing process, including but not limited to one or more of jet milling or high speed dispersion for crushing; when a plurality of crushing modes are mixed for use, a mode of tandem connection can be adopted.
The kind of the halide solid electrolyte is not particularly limited in the present application, and any known halide solid electrolyte can be used in the present application without departing from the concept of the present application.
In another embodiment, the adhesive has a shell-like structure.
The mass ratio of the binder in the solid electrolyte layer is 0.1-5 wt%;
the solid electrolyte layer has a first pore structure, the solid electrolyte layer having a porosity of < 5%;
the matrix gel layer comprises a matrix layer, and an electrolyte is introduced onto the matrix and cured in situ to form a gel layer;
the matrix layer comprises a polymer layer having a fibrous or rod-like woven structure;
The substrate layer is provided with a second pore structure, and the porosity of the substrate layer is 20% -60%;
the three-dimensional holes formed by the second hole structure of the matrix layer and the gel layer form a composite structure;
the thickness of the solid electrolyte membrane is 5-100 mu m;
the thickness h1 of the solid electrolyte layer and the thickness h2 of the matrix gel layer satisfy the value range of h1/h2 to be 2-10.
In a specific embodiment, the binder comprises at least one of polytetrafluoroethylene, styrene-butadiene rubber, ethylene-tetrafluoroethylene copolymer, or ethylene chlorotrifluoroethylene copolymer.
In a specific embodiment, the solid electrolyte membrane has a thickness of 15-50 μm.
In a specific embodiment, the second pore structure has a surface average pore size of 0.5-10 μm.
In a specific embodiment, the polymer layer comprises at least one of polyolefin, polyester, polyvinylidene fluoride based nonwoven.
In a specific embodiment, the thickness of the polymer layer is 1.5-25 μm.
In a specific embodiment, the solid electrolyte membrane is formed by rolling the solid electrolyte layer together with the matrix gel layer, after which part of the halide solid electrolyte in the solid electrolyte layer enters the second pore structure to form ion channels.
The application also provides a preparation method of the solid electrolyte membrane of the lithium ion battery, which comprises the following steps:
compounding the halide solid electrolyte with a binder to form a solid electrolyte layer;
compounding the solid electrolyte layer with a matrix layer to obtain a composite electrolyte membrane;
adding electrolyte to one side of the matrix layer of the composite electrolyte membrane, which is far away from the solid electrolyte layer, for gelation treatment to form a gel layer, wherein the matrix layer and the gel layer together form the matrix gel layer;
the binder is in a fibrous structure;
the mass ratio of the binder in the solid electrolyte layer is 0.1-5 wt%;
the solid electrolyte layer has a first pore structure, the solid electrolyte layer having a porosity of < 5%;
the matrix layer comprises a polymer layer having a fibrous or rod-like woven structure;
the substrate layer is provided with a second pore structure, and the porosity of the substrate layer is 20% -60%;
the thickness of the solid electrolyte membrane is 5-100 mu m;
the thickness h1 of the solid electrolyte layer and the thickness h2 of the matrix gel layer satisfy the value range of h1/h2 to be 2-10.
In a third aspect, the present application further provides a lithium ion battery, corresponding to the above lithium ion battery solid electrolyte membrane, comprising a positive electrode plate, a negative electrode plate, and the above lithium ion battery solid electrolyte membrane disposed between the positive electrode plate and the negative electrode plate, wherein the solid electrolyte layer of the solid electrolyte membrane is disposed close to the positive electrode plate, and the matrix gel layer is disposed close to the negative electrode plate.
In a specific embodiment, the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
In a specific embodiment, the positive electrode tab includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
The technical scheme provided by the embodiment of the application has the beneficial effects that:
the solid electrolyte membrane of the lithium ion battery, the preparation method thereof and the lithium ion battery provided by the embodiment of the application comprise a solid electrolyte layer and a matrix gel layer which are mutually laminated, wherein the solid electrolyte layer comprises a halide solid electrolyte and a binder, and the binder is of a fibrous structure. According to the application, the ultrathin, flexible, high-conductivity lithium and high-mechanical-strength halide-based solid electrolyte membrane is prepared by a mode of three-dimensional composite superposition two-dimensional composite, so that the requirement of the reduction resistance of the cathode side can be met, meanwhile, the ultrathin solid electrolyte membrane can be prepared by a dry method by means of the mechanical supporting effect of a two-dimensional layer non-woven fabric and other structures in a matrix gel layer, the high conductivity is ensured, the mechanical strength is improved, and the interface suitability and the battery cycle are improved by utilizing an asymmetric structural design.
All of the products of the present application need not have all of the effects described above.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a cross-sectional structural view of a solid electrolyte layer in a solid electrolyte membrane of a lithium ion battery according to an embodiment of the present application;
FIG. 2 is a cross-sectional structural view of a gel layer of a matrix in a solid electrolyte membrane of a lithium ion battery according to an embodiment of the present application;
fig. 3 is a cross-sectional structural view of a solid electrolyte membrane of a lithium ion battery according to an embodiment of the present application;
FIG. 4 is a schematic diagram of the aperture test method of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In view of one or more technical problems set forth in the background art described above, the present application creatively proposes a solid electrolyte membrane for a lithium ion battery, which includes a solid electrolyte layer 100 and a base gel layer 200 laminated to each other, as shown with reference to fig. 3; the solid electrolyte layer 100 includes a halide solid electrolyte and a binder; the binder is a fibrous structure.
It is understood that the fibrous structure of the binder refers to a rod-shaped material having a certain aspect ratio, and it is understood that the aspect ratio and the dimensional structure of the fibers are not particularly limited in the present application, and any material of reasonable dimensional structure can be used in the present application without departing from the concept of the present application. By way of illustrative example only, and not by way of limitation of the scope of protection, the binder fibers have an aspect ratio >1.
As an embodiment, the fibrous structure of the binder is obtained by fiberization.
The present application is not particularly limited in the type of halide solid state electrolyte, and any known halide solid state electrolyte can be used in the present application without departing from the spirit of the present application, by way of illustrative example only, and not by way of limitation of the scope of protection, the particles of the halide may be selected from one or more halide-based materials from the group consisting of: li (Li) 2 ZrCl 6 、Li 3 InCl 6 、Li 3 YCl 6 、Li 3 ErCl 6 And combinations of halides in which they are doped at the Li, non-Li metal, cl sites. In one variation, the one or more halide-based materials may have a weight ratio of greater than or equal to about 10 -8 S/cm to less than or equal to about 10 -1 S/cm ionic conductivity. In some combinations, the non-Li metal sites in the above-described halide solid state electrolytes may be doped with different metal elements including, but not limited to, mg, zn, lanthanoid, nb, etc., and the Li metal sites may be doped with Na, K elements, it being understood that the halide solid state electrolytes of the present application include doped or undoped cases. In certain combinations, the halogen is one or more halogens or a combination thereof with an oxygen element.
The present application is not particularly limited in the kind of binder, and any known binder can be used in the present application without departing from the concept of the present application, and the binder may be one or more of poly (tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, ethylene-tetrafluoroethylene copolymer (ETFE), or ethylene chlorotrifluoroethylene copolymer (ETCFE), by way of illustrative example only, and not limiting the scope of protection. As a preferred embodiment, the binder has a simple fiberization process, and by way of illustration only and not limitation of the scope of protection, the binder includes one or more of Polytetrafluoroethylene (PTFE), styrene-butadiene rubber, ethylene-tetrafluoroethylene copolymer (ETFE), or ethylene chlorotrifluoroethylene copolymer (ETCFE).
It is understood that the fibrillation process is a known process in which the PTFE material is regularly aligned in a direction under the action of directional shear forces to form fibers.
The present application is not particularly limited to the fiberization process, and any known fiberization process can be used in the present application without departing from the inventive concept. As an embodiment, the fiberizing process comprises a crushing process, including but not limited to one or more of jet milling or high speed dispersion for crushing; when a plurality of crushing modes are mixed for use, a mode of tandem connection can be adopted.
It is understood that under conditions that meet fibrosis, the fibrosis should be performed under conditions of low shear force as much as possible. The high shear mixing process has an adverse effect on the surface morphology of the active material; it will be appreciated that the damage to the active substance by shear forces is related to the material system of the active substance. Such damage may define that the analytical statistical properties of the active substance change as a result of undergoing a mixing process involving high shear forces. The analytical statistical properties include one or more of average particle size, density, gram volume, surface area, or surface chemistry.
In the battery, the solid electrolyte layer is arranged close to the positive electrode of the lithium ion battery, the matrix gel layer is arranged close to the negative electrode of the lithium ion battery, and the solid electrolyte layer is a three-dimensional composite structure formed by halide solid electrolyte and a binder and can be used for matching the positive electrode; the gel layer of the matrix comprises a matrix layer and a gel layer formed by introducing electrolyte on the matrix and curing in situ, has strong reduction resistance and can be used for matching a low-potential negative electrode. In this way, the solid electrolyte membrane is enabled to satisfy better affinity to the electrode.
The present application has no particular requirement on the binder content, and conventional adjustment of the binder content without departing from the concept of the present application should still be regarded as being within the scope of the present application, and it is understood that too low a binder content in the solid electrolyte layer results in no adhesion and no molding, and too high a binder content results in a decrease in electrical conductivity, energy density, and other properties. Therefore, by way of illustration only and not limitation of the scope of protection, the mass ratio of the defined binder in the solid electrolyte layer in the embodiments of the present application may be 0.1wt% to 5wt%, and the proper binder content satisfies both the requirement of adhesion and the requirement of electrical conductivity.
In a specific embodiment, referring to fig. 1, the solid electrolyte layer has a first pore structure. Preferably, the porosity of the solid electrolyte layer is < 5%, thereby ensuring high conductivity.
In an embodiment of the application, the matrix gel layer comprises a matrix layer and a gel layer formed by introducing electrolyte on the matrix and curing in situ.
Specifically, the base layer is a polymer layer having a fibrous or rod-like woven structure, whereby high mechanical strength can be maintained at an ultra-thin thickness. The substrate layer in the embodiment of the application is preferably made of a high polymer material, and the high polymer material is a chemically inert material, and is easy to form, good in flexibility, easy to form a film, good in liquid retention and low in cost. In the embodiment of the application, the specific material of the substrate layer is not limited, and any known polymer material can be used as the substrate layer of the application without departing from the concept of the application. The polymer material used in the present application is preferably polymer fiber. For example, at least one of polyolefin, polyester, polytetrafluoroethylene, polyvinylidene fluoride, comonomer modified polyvinylidene fluoride, cellulose, hemicellulose, and lignin. Preferably, the polymer layer in the embodiment of the present application is at least one of polyolefin, polyester, polyvinylidene fluoride non-woven fabric, and further preferably, the polymer layer is a polyolefin non-woven fabric.
Preferably, the thickness of the polymer layer is any value in the range of 1.5 to 25 μm, such as 1.5 μm, 3 μm, 5 μm, 7 μm, 10 μm, 13 μm, 15 μm, 17 μm, 25 μm, etc.
As a preferred embodiment, referring to fig. 2, in the embodiment of the present application, the base layer has a second pore structure. The second pore structure on the matrix layer is too compact, and is not good for absorbing liquid to form gel, and is not good for contact with the interface after lamination and compounding with the solid electrolyte layer, and the mechanical property is reduced when the porosity is too large, so that the porosity of the matrix layer is limited to be 20% -60% in the embodiment of the application, and the problems of the two aspects are solved.
Preferably, the surface average pore diameter of the second pore structure is any value in the range of 0.5 to 10. Mu.m, such as 0.5. Mu.m, 1. Mu.m, 1.5. Mu.m, 2. Mu.m, 2.5. Mu.m, 3. Mu.m, 3.5. Mu.m, 4. Mu.m, 4.5. Mu.m, 5. Mu.m, 6. Mu.m, 7. Mu.m, 8. Mu.m, 9. Mu.m, 10. Mu.m, etc. The solid electrolyte layer and the matrix gel layer are compounded to form a two-dimensional composite structure.
In a specific embodiment, the gel layer is formed by introducing an electrolyte solution on the basis of the matrix layer and curing it in situ, whereby a high electrical conductivity and a good interface with the electrode material can be ensured.
It will be appreciated that the present application is not particularly limited in the manner of gel, and any known gel electrolyte that can be applied in the environment of a battery system can be used in the present application without departing from the concept of the present application, and the manner of gel can be, by way of example only and not limitation of the scope of protection, polymerization by initiating formation of self-polymerization by small molecule ethers under heating or chemical reaction conditions, or polymerization by introducing polymerization monomers/cross-linker/initiator heating, or simultaneous formation of gel by swelling behavior of polymer polymers after introducing electrolyte/polymer polymers/solvent into matrix layer to dry the solvent. Preferably, the self-polymerization is carried out by adopting a small molecular ether composite electrolyte, and the small molecular ether can adopt dioxolane.
Any known electrolyte may be used as the electrolyte in the present application without departing from the concept of the present application. By way of example and not limitation, the electrolyte includes a non-limiting electrolyteAn aqueous liquid electrolyte solution including an organic solvent and a lithium salt dissolved in the organic solvent; the kind of the lithium salt and the solvent for dissolving the lithium salt is not particularly limited in the present application, and any known lithium salt and solvent can be used in the present application without departing from the concept of the present application. As illustrative examples, lithium salts that may be used include: lithium hexafluorophosphate (LiPF) 6 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium perchlorate (LiClO) 4 ) Lithium tetrachloroaluminate (LiAlCl) 4 ) Lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorooxalato borate (LiBF) 2 (C 2 O 4 ) (LiODFB), lithium tetraphenylborate (LiB (C) 6 H 5 ) 4 ) Lithium bis (oxalato) borate (LiB (C) 2 O 4 ) 2 ) Lithium tetrafluorooxalate phosphate (LiPF) 4 (C 2 O 4 ) (LiFeP), lithium nitrate (LiNO) 3 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium bis (trifluoromethanesulfonyl imide) (LITFSI) (LiN (CF) 3 SO 2 ) 2 ) Lithium bis (fluorosulfonyl imide) (LiN (FSO) 2 ) 2 ) (LIFSI) and combinations thereof. In certain variations, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) Lithium bis (trifluoromethanesulfonyl imide) (LiTFSI) (LiN (CF) 3 SO 2 ) 2 ) Lithium bis (fluorosulfonyl imide) (LiN (FSO) 2 ) 2 ) (LiFSI), lithium fluoroalkylphosphonate (LiFAP), lithium phosphate (Li) 3 PO 4 ) And combinations thereof. Solvents that may be used include, but are not limited to, n-butyl ether, n-pentyl ether, isopentyl ether, anisole, phenetole, propyl sulfide, butyl sulfide, polyethylene glycol dimethyl ether, or non-ether organics with a polarity less than diethyl ether, and combinations thereof.
In a specific embodiment, the total thickness of the solid electrolyte layer and the matrix gel layer (i.e., the thickness of the solid electrolyte membrane) is 5 to 100 μm, preferably 15 to 50 μm, more preferably 15 to 20 μm.
In a specific embodiment, the thickness h1 of the solid electrolyte layer and the thickness h2 of the matrix gel layer satisfy a value range of h1/h2 of 2-10, for example, h1/h2 may be 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.
It will be appreciated that the addition of additives of known function and kind according to the requirements of the actual use of the gel electrolyte should be considered within the scope of the present application. For example, a flame retardant is added into a solid electrolyte membrane of a lithium ion battery to improve the flame retardant safety performance of the battery. In the present application, there is no limitation on the manner of adding the relevant additives to the solid electrolyte membrane of the lithium ion battery, and any known method of adding flame retardants to inorganic membranes can be used in the present application without departing from the concept of the present application, including, but not limited to, directly mixing the components of the solid electrolyte membrane of the lithium ion battery with flame retardants, etc.
It is understood that the structure of the solid electrolyte membrane of the lithium ion battery may include various aspects, such as thickness, pore structure size, addition manner of flame retardant, composition of electrolyte layer, etc., and any factors that cause the flame retardance, safety, electrochemical performance, etc. of the solid electrolyte membrane of the lithium ion battery to be changed are understood as the structure herein.
In practical use, there are different heat distributions and heat accumulation inside the battery, and thus it is advantageous to provide a lithium ion battery solid electrolyte membrane having different performances according to the heat distribution phenomenon inside the battery for the overall performance of the battery. For example, a lithium ion battery solid electrolyte membrane with higher safety performance is arranged in a region with more serious heat accumulation, and a lithium ion battery solid electrolyte membrane with lower safety performance is arranged in a part with less heat accumulation.
Preferably, the structure of the solid electrolyte membrane of the lithium ion battery corresponds to the internal safety distribution of the battery.
It can be understood that the safety distribution in the battery refers to the distribution points of risks at different positions in the battery, namely, the places where the risks easily occur, the solid electrolyte membrane structure of the lithium ion battery with better safety performance is arranged, and the corresponding places where the risk points are low, the solid electrolyte membrane of the lithium ion battery with low safety performance is arranged so as to meet the requirements of other performances of the battery.
Corresponding to the above-mentioned solid electrolyte membrane of lithium ion battery, the embodiment of the present application further provides a method for preparing the solid electrolyte membrane of lithium ion battery, wherein the relevant content of the solid electrolyte membrane of lithium ion battery can be referred to in the foregoing, and is not described in detail herein. The preparation method comprises the following steps:
s100, mixing a halide solid electrolyte with a binder;
specifically, a halide solid electrolyte powder and a binder are weighed according to a certain mass ratio and subjected to fiberization in a fiberizing device to form a binder fiberized mixture.
S200: the mixture prepared in the step S100 is subjected to dry film forming to prepare a solid electrolyte layer;
s300, compounding the solid electrolyte layer and the matrix layer to obtain a composite electrolyte membrane;
and S400, adding electrolyte to the side, away from the solid electrolyte layer, of the matrix layer of the composite electrolyte membrane to carry out gelation treatment to form a gel layer, wherein the matrix layer and the gel layer jointly form the matrix gel layer.
According to the application, the matrix gel layer is arranged on one side of the solid electrolyte layer, so that the mechanical supporting effect of the matrix with the woven structure in the matrix gel layer on the halide solid electrolyte is utilized, the overall mechanical property of the solid electrolyte membrane is improved, and the problems of membrane rupture and the like caused by too low membrane thickness during the dry preparation of the halide solid electrolyte membrane are solved; meanwhile, electrolyte introduced in the whole preparation process remains in the gel electrolyte layer to be used as a plasticizer, so that the overall high conductivity of the electrolyte membrane and good suitability for a negative electrode interface can be ensured.
It is understood that the fiberization process is a known process in which the fiberizable binder material is regularly aligned in a certain direction under the action of directional shear forces to form fibers.
The present application is not particularly limited to the fiberization process, and any known fiberization process can be used in the present application without departing from the inventive concept. As an embodiment, the fiberizing process comprises a crushing process, including but not limited to one or more of jet milling or high speed dispersion for crushing; when a plurality of crushing modes are mixed for use, a mode of tandem connection can be adopted.
It is understood that under conditions that meet fibrosis, the fibrosis should be performed under conditions of low shear force as much as possible. The high shear mixing process has an adverse effect on the surface morphology of the active material; it will be appreciated that the damage to the active substance by shear forces is related to the material system of the active substance. Such damage may define that the analytical statistical properties of the active substance change as a result of undergoing a mixing process involving high shear forces. The analytical statistical properties include one or more of average particle size, density, gram volume, surface area, or surface chemistry.
The application prepares the halide solid electrolyte membrane (i.e. the solid electrolyte layer) by a dry method of fiberization, thereby avoiding the use of solvents.
Preferably, the preparation method further comprises premixing.
Premixing is to mix the halide solid electrolyte and the binder before fiberizing under high shear force, and mixing is performed under low shear force in order to uniformly disperse the halide solid electrolyte and the binder.
Specifically, the halide electrolyte membrane (i.e., solid electrolyte layer) obtained in the above step is bonded to a base film (i.e., base layer) having a woven structure.
As an embodiment, the base layer has a second pore structure, the porosity of which may be 20 to 60%, and the surface average pore diameter of which is 0.5 to 10 μm.
As an implementation mode, the application carries out thermal compounding on the solid electrolyte layer and the matrix layer by hot rolling on a constant-speed roll squeezer after the solid electrolyte layer and the matrix layer are attached, the roll temperature is 40-90 ℃, and the film thickness of the composite electrolyte film is 15-50 mu m.
It is understood that the gelation treatment refers to the introduction of an electrolyte into the matrix layer network to solidify in situ to form a gel electrolyte that fills the pore structure of the matrix to form the ion conductive pathways.
As an embodiment, the step S400 further includes mixing and stirring the polymerizable monomer, the crosslinking agent, the organic solvent and the initiator to form a solution as a precursor of the gel electrolyte, or mixing the solution with the polymer/the organic solvent which swells with the electrolyte to form a gel as a precursor of the gel electrolyte.
As one embodiment, the gelation treatment is to crosslink the polymerizable monomer to form a gel electrolyte.
It will be appreciated that the method of gelation treatment is not particularly limited, and any known method of crosslinking curing can be used in the present application without departing from the spirit of the present application, and the manner of crosslinking curing may be one or more of thermal curing, photo curing, and ultrasonic curing, by way of illustration only, and not limitation of the scope of protection.
The application also provides a lithium ion battery, which comprises a positive pole piece, a negative pole piece and a lithium ion battery solid electrolyte membrane arranged between the positive pole piece and the negative pole piece, wherein the relevant content of the lithium ion battery solid electrolyte membrane can be referred to as described above; the solid electrolyte layer of the solid electrolyte membrane is arranged close to the positive electrode plate, and the matrix gel layer is arranged close to the negative electrode plate.
In a preferred embodiment of the present application, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, and the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
In the lithium ion battery in the embodiment of the application, a lamination or winding design can be adopted in the battery, and it can be understood that, due to the adoption of the lamination or winding design in the battery, two sides of a current collector (including a positive current collector and a negative current collector) can be coated on two sides, namely, two sides of the current collector are respectively provided with an active material layer.
The application has no special requirements on the composition and structure of the positive electrode plate and the negative electrode plate, and any known positive electrode active material, negative electrode active material, current collector and corresponding accessory structures and compositions can be used in the application on the basis of not departing from the concept of the application.
The following is a brief description of the materials and structures of the positive electrode, the negative electrode, and the like, which are merely illustrative examples, and not intended to limit the scope of protection in any way.
The negative electrode tab is formed of a lithium host material capable of functioning as a negative electrode of a lithium ion battery. For example, the anode may contain an anode active material capable of functioning as an anode electrode of a battery. The anode active material layer may be composed of various anode active materials. In certain embodiments, the negative electrode may further include an electrolyte, such as the halide electrolyte particles indicated previously.
The kind of the negative electrode active material is not particularly limited in the present application, and any known negative electrode active material can be used in the present application without departing from the concept of the present application. In one embodiment, the negative electrode active material comprises lithium metal and/or a lithium alloy. In other embodiments, the anode is a silicon-based anode active material that includes silicon, such as a silicon alloy, silicon oxide, or a combination thereof, which may also be mixed with graphite in some cases. In other embodiments, the anode may include a carbonaceous-based anode active material comprising one or more of graphite, graphene, carbon Nanotubes (CNTs), and combinations thereof. In yet other embodiments, the anode includes one or more anode active materials that accept lithium, such as lithium titanium oxide (Li 4 Ti 5 O 12 ) One or more transition metals (e.g., tin (Sn)), one or more metal oxides (e.g., vanadium oxide (V) 2 O 5 ) Tin oxide (SnO), titanium dioxide (TiO) 2 ) Titanium niobium oxide (TixNbyOz, where 0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.24, and 0.ltoreq.z.ltoreq.64), metal alloys(s)Such as copper-tin alloy (Cu 6 Sn 5 ) And one or more metal sulfides such as iron sulfide (FeS).
Optionally, the negative active material in the negative electrode sheet may be doped with one or more conductive agents that provide an electron conduction path and/or at least one polymeric binder material that improves the structural integrity of the negative electrode. For example, alternatively, the binder may be: poly (tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile-butadiene rubber (NBR), styrene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof. The conductive agent may include carbon-based materials, powdered nickel or other metal particles, or conductive polymers. The carbon-based material may include, for example, particles of carbon black, graphite, superP, acetylene black (such as KETCHENTM black or denktatm black), carbon fibers and nanotubes, graphene, and the like. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, poly (3, 4-ethylenedioxythiophene) polysulfstyrene, and the like.
The negative electrode sheet may include greater than or equal to about 50wt% to less than or equal to about 97wt% of a negative electrode active material, alternatively greater than or equal to about 0wt% to less than or equal to about 60wt% of a solid state electrolyte, alternatively greater than or equal to about 0wt% to less than or equal to about 15wt% of a conductive material, and alternatively greater than or equal to about 0wt% to less than or equal to about 10wt% of a binder.
The positive electrode sheet is formed from a plurality of positive electrode active particles comprising one or more transition metal cations, such as manganese (Mn), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), vanadium (V), and combinations thereof. In some embodiments, the positive electrode active material layer further includes an electrolyte, such as a plurality of electrolyte particles. The positive electrode active material layer has a thickness of greater than or equal to about 1 μm to less than or equal to about 1000 μm.
The positive electrode active material layer is one of a layered oxide cathode, a spinel cathode and a polyanion cathodeA kind of module is assembled in the module and the module is assembled in the module. For example, a layered oxide cathode (e.g., a rock salt layered oxide) comprises one or more lithium-based positive electrode active materials selected from the group consisting of: liCoO 2 (LCO)，LiNi x Mn y Co 1-x-y O 2 (wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1), and LiNi 1-x-y Co x Al y O 2 (wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1), and LiNi x Mn 1-x O 2 (wherein 0.ltoreq.x.ltoreq.1), and Li 1+x MO 2 (wherein M is one of Mn, ni, co and Al and 0.ltoreq.x.ltoreq.1). The spinel cathode comprises one or more lithium-based positive electrode active materials selected from the group consisting of: liMn 2 O 4 (LMO) and LiNi x Mn 1.5 O 4 . Olivine-type cathodes comprising one or more positive lithium-based electroactive substances LiMPO 4 (wherein M is at least one of Fe, ni, co and Mn). The polyanionic cation comprises, for example, a phosphate such as LiV 2 (PO 4 ) 3 And/or silicates such as life io 4 。
In one embodiment, one or more lithium-based positive electrode active materials may optionally be coated (e.g., by LiNbO 3 And/or Al 2 O 3 ) And/or may be doped (e.g., by magnesium (Mg)). Further, in certain embodiments, one or more lithium-based positive electrode active materials may optionally be mixed with one or more conductive materials that provide an electron conduction path and/or at least one polymeric binder material that improves the structural integrity of the positive electrode. For example, the positive electrode active material layer may include greater than or equal to about 30wt% to less than or equal to about 98 wt% of one or more lithium-based positive electrode active materials; greater than or equal to about 0wt% to less than or equal to about 30wt% of a conductive agent; and greater than or equal to about 0wt% to less than or equal to about 20wt% of a binder, and in certain aspects, optionally greater than or equal to about 1wt% to less than or equal to about 20wt% of a binder.
The positive electrode active material layer may be optionally mixed with a binder as follows: such as Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof. The conductive agent may include a carbon-based material, powdered nickel or other metal particles, or a conductive polymer. Carbon-based materials may include, for example, carbon black, graphite, acetylene black (e.g., KETCHENTM black or denktatm black), carbon fibers and particles of nanotubes, graphene, and the like. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.
The positive electrode current collector (including the first and second positive electrode current collectors) may facilitate the flow of electrons between the positive electrode and an external circuit. The positive current collector may comprise a metal, such as a metal foil, a metal grid or mesh, or a metal mesh. For example, the positive electrode current collector may be formed of aluminum, stainless steel, and/or nickel or any other suitable conductive agent known to those skilled in the art.
The present application is further described below with reference to examples and comparative examples.
Example 1
1) Positive electrode side Li 2 ZrCl 6 +PTFE dry film preparation
Li is mixed with 2 ZrCl 6 Powder and PTFE are weighed according to the mass ratio of 99.5:0.5, fully mixed and sheared in an air flow mill, the air inlet pressure of the air flow mill is 0.6MPa, and the shearing time is 1min. Subsequently, the mixture was repeatedly ground into a dough shape in a mortar. The dough mixture was rolled multiple times on a roll press at a roll temperature of 80 ℃ to give a 31 μm thick dry halide electrolyte membrane with a porosity of 3%.
2) And (3) carrying out two-dimensional compounding on the film obtained in the step 1) and a matrix film (namely a matrix layer).
Li obtained by a dry method 2 ZrCl 6 The PTFE three-dimensional composite film was bonded to a polyolefin nonwoven fabric having a woven structure, wherein the nonwoven fabric had a porosity of 50% and a surface average pore size of 8 μm. And (3) carrying out hot rolling on a roll squeezer for thermal compounding after lamination, wherein the roll temperature is 80 ℃, and the film thickness of the obtained composite electrolyte film is 40 mu m.
3) And adding electrolyte to one side of the matrix layer of the composite electrolyte membrane to carry out gelation treatment.
Small molecular liquid of dioxolane, liFSI and LiPF 6 Mixing and stirring n-butyl ether to obtain a solution serving as a precursor of the gel electrolyte, injecting the precursor solution into one side of the non-woven fabric, heating at 60 ℃ for 4 hours, and then chemically crosslinking to form the gel electrolyte, thereby completing the preparation of the integral composite membrane.
Example 2
1) Positive electrode side Li 2 ZrCl 5.5 0 0.25 +PTFE dry film preparation
Li is mixed with 2 ZrCl 5.5 0 0.25 Powder and PTFE are weighed according to the mass ratio of 99.5:0.5, fully mixed and sheared in an air flow mill, the air inlet pressure of the air flow mill is 0.6MPa, and the shearing time is 1min. Subsequently, the mixture was repeatedly ground into a dough shape in a mortar. The dough mixture was rolled multiple times on a roll press at a roll temperature of 80 ℃ to give a 25 μm thick dry halide electrolyte membrane with a porosity of 2.6%.
2) Two-dimensional compounding the film obtained in step 1) with a matrix film (i.e. matrix layer)
Li obtained by a dry method 2 ZrCl 5.5 0 0.25 The PTFE three-dimensional composite film was bonded to a polyolefin nonwoven fabric having a woven structure, wherein the nonwoven fabric had a porosity of 50% and a surface average pore size of 8 μm. And (3) carrying out hot rolling on a roll squeezer for thermal compounding after lamination, wherein the roll temperature is 80 ℃, and the film thickness of the composite electrolyte film is 32 mu m.
3) Adding electrolyte to one side of the matrix layer of the composite electrolyte membrane for gelation treatment
Small molecular liquid of dioxolane, liDFOB and LiPF 6 And mixing and stirring the isoamyl ether to obtain a solution serving as a precursor of the gel electrolyte, injecting the precursor solution into one side of the non-woven fabric, heating the non-woven fabric at the temperature of 60 ℃ for 4 hours, and then chemically crosslinking the non-woven fabric to form the gel electrolyte, thereby completing the preparation of the integral composite membrane.
Example 3
1) Positive electrode side Li 2 ZrCl 5.5 0 0.25 +PTFE dry film preparation
Li is mixed with 2 ZrCl 5.5 0 0.25 Powder and PTFE are weighed according to the mass ratio of 99.5:0.5, fully mixed and sheared in an air flow mill, the air inlet pressure of the air flow mill is 0.6MPa, and the shearing time is 1min. Subsequently, the mixture was repeatedly ground into a dough shape in a mortar. The dough mixture was rolled multiple times on a roll press at a roll temperature of 80 ℃ to give a 25 μm thick dry halide electrolyte membrane with a porosity of 2.6%.
2) Two-dimensional compounding the film obtained in step 1) with a matrix film (i.e. matrix layer)
Li obtained by a dry method 2 ZrCl 5.5 0 0.25 The PTFE three-dimensional composite membrane was bonded to a polyvinylidene fluoride nonwoven fabric having a woven structure, wherein the nonwoven fabric had a porosity of 50% and a surface average pore diameter of 5 μm. And (3) carrying out hot rolling on a roll squeezer for thermal compounding after lamination, wherein the roll temperature is 80 ℃, and the film thickness of the composite electrolyte film is 32 mu m.
3) Adding electrolyte to one side of the matrix film for gelation treatment
PEO, liWSI, isoamyl ether and dioxane are mixed and stirred into a solution to be used as a precursor of the gel electrolyte, the precursor solution is injected to one side of the non-woven fabric, and the polymer swelling gel electrolyte is formed after drying for 8 hours in a vacuum oven at 80 ℃, so that the preparation of the integral composite membrane is completed.
Comparative example 1:
20mg of Li 2 ZrCl 6 The powder was put into a tabletting mold having a diameter of 10mm, compressed into tablets under a pressure of 375MPa in a glove box, and taken out after demoulding to obtain Li having a thickness of about 550 μm 2 ZrCl 6 And (3) a sheet.
Comparative example 2:
Li 2 ZrCl 6 +PTFE dry film
Li is mixed with 2 ZrCl 6 Powder and PTFE are weighed according to the mass ratio of 99.5:0.5, fully mixed and sheared in an air flow mill, the air inlet pressure of the air flow mill is 0.6MPa, and the shearing time is 1min. Subsequently, the mixture was repeatedly ground into a dough shape in a mortar. The dough mixture was rolled multiple times on a roll press at a roll temperature of 80℃to give a 40 μm thick dry halide electrolyte membrane with a porosity of 2.9%.
Comparative example 3
Polyolefin-based gel electrolyte membrane
Small molecular liquid of dioxolane, liFSI and LiPF 6 Mixing and stirring n-butyl ether to obtain a solution serving as a precursor of the gel electrolyte, injecting the precursor solution into a polyolefin non-woven fabric, heating at 60 ℃ for 4 hours, and then chemically crosslinking to form the gel electrolyte, wherein the thickness of the obtained electrolyte membrane is 25 mu m.
Test method
Pore size was measured using SEM:
A. selecting 5 positions of a matrix sample, wherein the magnification is 500 times;
B. for one position, as shown in fig. 4, a triangle area is shown as 1 in the figure, and the aperture is the average value of the lengths of three central lines of the triangle; the quadrilateral area is 2, and the aperture is the average value of the length of the connecting line of the midpoints of the opposite sides. In fig. 4, the surface average pore diameter of the second pore structure of the matrix layer=the average value of all the triangular and quadrangular pore diameters;
C. the pore diameter measuring method in other 4 positions is the same as that of the previous method;
D. the surface average pore size of the second pore structure of the final matrix layer sample was the average of the average pore sizes in 5 locations.
2) Tensile strength test method:
the sample cuts the rectangular shape sample that width is 25mm, and length is not less than 150mm, and the initial distance between the anchor clamps sets up to 100 + -5 mm, puts into anchor clamps upper and lower both ends in proper order with the spline both ends, presss from both sides tight anchor clamps, and the in-process guarantees spline and anchor clamps in same vertical direction, and the atress is even, does not have obvious tensile deformation, after the preparation is accomplished, carries out tensile strength test with 250 + -10 mm/min's speed.
3) The battery cycle retention test method comprises the following steps:
preparation of the battery:
A. preparing a dry positive electrode: LCO: li (Li) 2 ZrCl 5.5 0 0.25 Powder: vgcf=57:40:3, 1% PTFE was added, and after high-speed shearing fiberization, hot rolling was performed at 100 ℃, with a thickness controlled to 100 to 110 μm.
B. And (3) a negative electrode: lithium sheet.
C. And (3) battery assembly: and cutting the positive electrode and the negative electrode into phi 8 films, cutting the composite film into phi 10 films, sequentially laminating the positive electrode, the solid electrolyte film and the negative electrode, and pressurizing and assembling to obtain the battery for testing.
Battery cycle performance test:
the assembled battery was charged and discharged in a voltage range of 3-4.2V, the first two turns were subjected to 0.05C magnification, 0.1C magnification was applied from the 3 rd turn to the 30 rd turn, and the cycle retention rate was recorded, and the cycle retention rate=the discharge capacity at the 30 th turn/the discharge capacity at the 3 rd turn.
According to the experimental data, on one hand, the solid electrolyte membrane provided by the application has strong reduction resistance, can be used for matching a low-potential negative electrode, ensures high conductivity and improves the cycle performance of a battery by arranging the matrix gel layer to comprise a matrix layer and the gel layer formed by introducing electrolyte on the matrix layer and in-situ curing; on the other hand, the mechanical supporting effect of the structure such as non-woven fabrics of the matrix layer can be utilized to enable the dry preparation of the ultrathin solid electrolyte membrane to be possible, and meanwhile, the mechanical strength can be improved.
In the description of the present application, it should be understood that the terms "vertical," "parallel," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present application and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present application. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.

Claims (9)

1. A solid electrolyte membrane of a lithium ion battery, characterized in that the solid electrolyte membrane comprises a solid electrolyte layer and a matrix gel layer laminated to each other;
the solid electrolyte layer comprises a halide solid electrolyte and a binder;
the binder is in a fibrous structure;
the mass ratio of the binder in the solid electrolyte layer is 0.1-5 wt%;
the solid electrolyte layer has a first pore structure, the solid electrolyte layer having a porosity of < 5%;
the matrix gel layer comprises a matrix layer, and an electrolyte is introduced onto the matrix and cured in situ to form a gel layer;
the matrix layer comprises a polymer layer having a fibrous or rod-like woven structure;
the substrate layer is provided with a second pore structure, and the porosity of the substrate layer is 20% -60%;
the thickness of the solid electrolyte membrane is 5-100 mu m;
the thickness h1 of the solid electrolyte layer and the thickness h2 of the matrix gel layer satisfy the value range of h1/h2 to be 2-10.
2. The solid electrolyte membrane of a lithium ion battery according to claim 1, wherein the binder comprises at least one of polytetrafluoroethylene, styrene-butadiene rubber, ethylene-tetrafluoroethylene copolymer, or ethylene chlorotrifluoroethylene copolymer.
3. The solid electrolyte membrane for a lithium ion battery according to claim 1 or 2, wherein the thickness of the solid electrolyte membrane is 15-50 μm.
4. The solid electrolyte membrane of a lithium ion battery according to claim 1 or 2, wherein the surface average pore diameter of the second pore structure is 0.5 to 10 μm.
5. The solid electrolyte membrane of a lithium ion battery according to claim 1 or 2, wherein the polymer layer comprises at least one of polyolefin, polyester, polyvinylidene fluoride based nonwoven.
6. The solid electrolyte membrane of a lithium ion battery according to claim 1 or 2, wherein the thickness of the polymer layer is 1.5-25 μm.
7. The solid electrolyte membrane of a lithium ion battery according to claim 1 or 2, wherein the solid electrolyte membrane is formed by rolling the solid electrolyte layer together with the matrix gel layer, and a part of halide solid electrolyte in the solid electrolyte layer enters the second pore structure after rolling to form ion channels.
8. A production method for producing the lithium ion battery solid electrolyte membrane according to any one of claims 1 to 7, characterized by comprising:
compounding the halide solid electrolyte with a binder to form a solid electrolyte layer;
compounding the solid electrolyte layer with a matrix layer to obtain a composite electrolyte membrane;
adding electrolyte to one side of the matrix layer of the composite electrolyte membrane, which is far away from the solid electrolyte layer, for gelation treatment to form a gel layer, wherein the matrix layer and the gel layer together form the matrix gel layer;
the binder is in a fibrous structure;
the mass ratio of the binder in the solid electrolyte layer is 0.1-5 wt%;
the solid electrolyte layer has a first pore structure, the solid electrolyte layer having a porosity of < 5%;
the matrix layer comprises a polymer layer having a fibrous or rod-like woven structure;
the substrate layer is provided with a second pore structure, and the porosity of the substrate layer is 20% -60%;
the thickness of the solid electrolyte membrane is 5-100 mu m;
the thickness h1 of the solid electrolyte layer and the thickness h2 of the matrix gel layer satisfy the value range of h1/h2 to be 2-10.
9. A lithium ion battery, characterized by comprising a positive electrode plate, a negative electrode plate and the lithium ion battery solid electrolyte membrane according to any one of claims 1 to 7 arranged between the positive electrode plate and the negative electrode plate, wherein the solid electrolyte layer of the solid electrolyte membrane is arranged close to the positive electrode plate, and the matrix gel layer is arranged close to the negative electrode plate.
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