CN112838266B - Composite electrolyte membrane, preparation method and application thereof, and solid-state lithium battery - Google Patents

Composite electrolyte membrane, preparation method and application thereof, and solid-state lithium battery Download PDF

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CN112838266B
CN112838266B CN202110309695.1A CN202110309695A CN112838266B CN 112838266 B CN112838266 B CN 112838266B CN 202110309695 A CN202110309695 A CN 202110309695A CN 112838266 B CN112838266 B CN 112838266B
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CN112838266A (en
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耿振
廖文俊
王中驰
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Shanghai Electric Group Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a composite electrolyte membrane, a preparation method and application thereof and a solid-state lithium battery. The composite electrolyte membrane comprises a solid electrolyte layer, wherein one side or two sides of the solid electrolyte layer are coated with polymer coatings; the solid electrolyte layer includes an inorganic solid electrolyte. The composite electrolyte membrane can reduce interface resistance, inhibit interface side reaction and relieve lithium deposition; the solid-state lithium battery based on the composite electrolyte membrane has good cycle performance and good safety.

Description

Composite electrolyte membrane, preparation method and application thereof, and solid-state lithium battery
Technical Field
The invention relates to a composite electrolyte membrane, a preparation method and application thereof, and a solid-state lithium battery.
Background
As an important electrochemical energy storage device, the lithium ion battery has been widely applied to the fields of consumer electronics, power batteries, energy storage and the like, and the market demand has been increasing year by year. With the increasing demand of lithium ion batteries, consumers have higher and higher requirements on the performance of the lithium ion batteries, the pain point problem of the lithium ion batteries is more and more prominent, and the core problem is focused on the incompatibility of energy density and safety. The energy density of the lithium ion battery is limited, and the energy density is generally considered to be about 300Wh/kg at present. And in the process of improving the energy density, the trend that the higher the energy density is, the worse the safety is shown. The reasons for this trend are mainly twofold: in one aspect, the electrode material has enhanced chemical/electrochemical activity; on the other hand, liquid organic combustible electrolyte is used in the battery.
In order to solve the problem that the energy density and the safety of the liquid lithium ion battery are incompatible, the scientific community and the industrial community transfer the sight to the solid lithium battery. The liquid organic combustible electrolyte in the battery is replaced by the safe and stable solid electrolyte, and the battery can be matched with high-specific-capacity anode and cathode materials, so that the application of the metal lithium cathode becomes possible, the energy density of the battery is obviously improved, and the safety of the battery is also considered. Therefore, the solid-state lithium battery is recognized as a new generation lithium battery technology that is closest to the industrialization.
The solid electrolyte, as a core material of the solid lithium battery, can be classified into oxides, polymers, sulfides, amorphous thin films, iodides, hydrides, and the like (Nature Reviews Materials,2016,2, 1-16). Among them, inorganic solid electrolytes represented by oxides and sulfides are considered to be one of the most promising solid electrolyte materials for practical use because of their advantages such as high ionic conductivity, high mechanical strength, and good stability, and solid lithium batteries based on inorganic solid electrolytes are considered to be one of the most promising solid battery technologies for commercial use.
However, the inorganic solid electrolyte has some problems, and thus needs to be solved so that it can be applied to a practical solid lithium battery. The specific problems are as follows: (1) The oxide material is a rigid material, has high hardness, is in solid-solid contact with the electrode and the electrode material, and has large interface resistance; (2) Part of materials are unstable in electrochemical environment, such as titanium aluminum lithium phosphate (LATP) and germanium aluminum lithium phosphate (LAGP) with a Nasicon structure, lithium Lanthanum Titanium Oxide (LLTO) with a perovskite structure, when the materials are contacted with metallic lithium, tetravalent titanium or germanium in an original crystal structure is reduced to trivalent titanium or germanium, an interfacial second phase with electron/ion mixed conductivity is formed, and the interfacial side reaction between an electrolyte and an electrode can continuously occur due to the electron conductivity of the phase, so that the performance of the battery is continuously reduced; (3) Some materials have a small ionic conductivity at grain boundaries compared to the bulk ionic conductivity, such as Lithium Lanthanum Zirconium Oxide (LLZO) in garnet structures, which causes preferential reductive deposition of lithium ions at the grain boundaries, forming lithium dendrites, further initiating short circuits within the cell.
Disclosure of Invention
The invention provides a composite electrolyte membrane, a preparation method and application thereof and a solid lithium battery, and aims to solve the problems of high interface resistance, continuous generation of interface side reactions, formation of lithium dendrites by lithium deposition and the like of an inorganic solid electrolyte in the prior art. The composite electrolyte membrane can reduce interface resistance, inhibit interface side reaction and relieve lithium deposition; the solid lithium battery based on the composite electrolyte membrane has good cycle performance and good safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a composite electrolyte membrane, which comprises a solid electrolyte layer, wherein one side or two sides of the solid electrolyte layer are coated with a polymer coating; the solid electrolyte layer includes an inorganic solid electrolyte.
In the present invention, the thickness of the polymer coating may be 0.5 to 100. Mu.m, preferably 0.5 to 5 μm, for example 1 μm.
In the present invention, the thickness of the solid electrolyte layer may be 5 to 200. Mu.m, preferably 5 to 15 μm, for example, 14 μm.
Preferably, the thickness ratio of the polymer coating layer to the solid electrolyte layer is 1: (5 to 20), for example, 1.
In the present invention, the polymer in the polymer coating layer is preferably selected from at least one of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene, polyacrylic acid, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, thermoplastic polyurethane, polyacrylates, and polyvinyl chloride.
In the present invention, the polymer coating layer preferably further includes a lithium salt. The lithium salt may be selected from one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate. Wherein the mass ratio of the polymer and the lithium salt in the polymer coating is preferably (2-30): 1.
in the present invention, the inorganic solid electrolyte may be an inorganic solid electrolyte material that is conventional in the art, and is typically an oxide-based solid electrolyte and/or a sulfide-based solid electrolyte. The structure of the inorganic solid electrolyte may be a Nasicon structure, a perovskite structure, or a garnet structure.
The inorganic solid electrolyte is preferably selected from: li 1+p Al p Ge 2-p (PO 4 ) 3 (lithium aluminum germanium phosphate, LAGP), li 1+ m Al m Ti 2-m (PO 4 ) 3 (lithium aluminum titanium phosphate, LATP), li 3q La 2/3-q TiO 3 (lithium lanthanum titanium oxygen, LLTO)、Li 7 La 3 Zr 2 O 12 (Li-La-Zr-O, LLZO), liZr 2-r Ti r (PO 4 ) 3 、Li 4-t Ge 1-t P t S 4 、Li 7-2n-j A n La 3 Zr 2-j B j O 12 、Li 7-2n-2j A n La 3 Zr 2-j C j O 12 、Li 7 P 3 S 11 、Li 3-k D k PS 4-u O u 、Li 2.58 C 0.42 B 0.58 O 3 And Li 2 O-ZrO 2 -SiO 2 One or more of (a); wherein p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2/3, r is more than or equal to 2 and less than or equal to 0, m is more than or equal to 2, t is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, k is more than or equal to 0 and less than or equal to 3, u is more than or equal to 0 and less than or equal to 4, A is Ge and/or Al, B is Nb and/or Ta, and C is Te and/or W. The inorganic solid electrolyte also comprises a series of derivatives which are obtained by taking the materials as precursors and carrying out element replacement on lithium-containing, metal-containing, sulfur-containing and oxygen-containing positions of the precursors.
In the present invention, the particle size of the inorganic solid electrolyte is preferably 50 to 500nm, for example, 70nm.
In the present invention, the solid electrolyte layer may only include an inorganic solid electrolyte, i.e., the solid electrolyte layer is a pure inorganic solid electrolyte material; a polymer matrix may also be included.
Wherein the polymer matrix may be a polymer which is non-conductive and non-reactive with the inorganic solid electrolyte, as is conventional in the art, preferably selected from one or more of polyethylene, polypropylene (PP), polyvinylidene fluoride or polyimide. The thickness of the polymer matrix is preferably 5-200 μm, for example 12 μm.
When the solid electrolyte layer further includes a polymer matrix, the inorganic solid electrolyte is coated on one or both sides of the polymer matrix.
When the solid electrolyte layer further comprises a polymer matrix, the solid electrolyte layer may further comprise a binder. The binder may be conventional in the art for binding the inorganic solid-state electrolyte and the polymer matrix.
The invention also provides a preparation method of the composite electrolyte membrane, which comprises the following steps: coating the slurry A on one side or two sides of the solid electrolyte layer, and drying to obtain a polymer coating; wherein the slurry A comprises a polymer and an organic solvent; the solid electrolyte layer includes an inorganic solid electrolyte.
In the present invention, the polymer is preferably selected from at least one of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene, polyacrylic acid, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, thermoplastic polyurethane, polyacrylate, and polyvinyl chloride.
In the present invention, the organic solvent may be conventional in the art, and may be one that dissolves the polymer, for example, acetonitrile or N-methylpyrrolidone (NMP). The organic solvent may be used in an amount sufficient to dissolve the polymer.
In the present invention, the slurry a preferably further includes a lithium salt. The lithium salt may be selected from one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide, lithium perchlorate, lithium bis oxalate borate, lithium difluoro oxalate borate and lithium trifluoromethanesulfonate. Wherein the mass ratio of the polymer to the lithium salt is preferably (2 to 30): 1, e.g. 5.
In the present invention, the thickness of the polymer coating is preferably 0.5 to 100. Mu.m, for example, 1 μm.
In the present invention, the coating may be performed by conventional methods in the art, and preferably by spray coating, extrusion coating, transfer coating or microgravure coating.
In the present invention, the manner and conditions for the drying may be conventional in the art, and the organic solvent may be removed. The drying temperature is preferably 50-120 ℃, and the drying time is preferably 2-24h.
In the present invention, the thickness of the solid electrolyte layer is preferably 5 to 200. Mu.m, for example, 14 μm.
In the present invention, the inorganic solid electrolyte may be an inorganic solid electrolyte material that is conventional in the art, and is typically an oxide-based solid electrolyte and/or a sulfide-based solid electrolyte. The structure of the inorganic solid electrolyte may be a Nasicon structure, a perovskite structure, or a garnet structure.
The inorganic solid electrolyte is preferably selected from: li 1+p Al p Ge 2-p (PO 4 ) 3 (lithium aluminum germanium phosphate, LAGP), li 1+ m Al m Ti 2-m (PO 4 ) 3 (lithium aluminum titanium phosphate, LATP), li 3q La 2/3-q TiO 3 (LiLa TiOx, LLTO), li 7 La 3 Zr 2 O 12 (LiLa Zr O, LLZO), liZr 2-r Ti r (PO 4 ) 3 、Li 4-t Ge 1-t P t S 4 、Li 7-2n-j A n La 3 Zr 2-j B j O 12 、Li 7-2n-2j A n La 3 Zr 2-j C j O 12 、Li 7 P 3 S 11 、Li 3-k D k PS 4-u O u 、Li 2.58 C 0.42 B 0.58 O 3 And Li 2 O-ZrO 2 -SiO 2 One or more of (a); wherein p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2/3, r is more than or equal to 2 and less than or equal to 0, m is more than or equal to 2, t is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, k is more than or equal to 0 and less than or equal to 3, u is more than or equal to 0 and less than or equal to 4, A is Ge and/or Al, B is Nb and/or Ta, and C is Te and/or W. The inorganic solid electrolyte also comprises a series of derivatives which are obtained by taking the materials as precursors and carrying out element replacement on lithium-containing, metal-containing, sulfur-containing and oxygen-containing positions of the precursors.
In the present invention, the particle size of the inorganic solid electrolyte is preferably 50 to 500nm.
In the present invention, the solid electrolyte layer may only include an inorganic solid electrolyte, i.e., the solid electrolyte layer is a pure inorganic solid electrolyte material; a polymer matrix may also be included.
Wherein the polymer matrix may be a polymer which is non-conducting to electrons or ions and which does not react with the inorganic solid-state electrolyte, as is conventional in the art, preferably selected from one or more of polyethylene, polypropylene (PP), polyvinylidene fluoride or polyimide.
In the present invention, the solid electrolyte layer may be prepared by a method conventional in the art.
When the solid electrolyte layer includes only an inorganic solid electrolyte, the method of preparing the solid electrolyte layer may include: and pressing the inorganic solid electrolyte into a tablet.
When the solid electrolyte layer further includes a polymer matrix, the method for producing the solid electrolyte layer preferably includes: coating the slurry B on one side or two sides of a polymer matrix and then drying; wherein the slurry B comprises an inorganic solid electrolyte, a binder and a solvent.
Wherein the binder may be conventional in the art for binding the inorganic solid-state electrolyte and the polymer matrix. The solvent may be an aqueous solvent or an oily solvent (e.g., acetonitrile or NMP) conventional in the art for dispersing the inorganic solid electrolyte.
Wherein, the drying mode and conditions can be conventional in the field, and the solvent can be removed.
The invention also provides a composite electrolyte membrane prepared by the preparation method of the composite electrolyte membrane.
The invention also provides an application of the composite electrolyte membrane in a solid lithium battery.
The present invention further provides a solid lithium battery including the composite electrolyte membrane.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the composite electrolyte membrane of the invention improves the performance of the solid electrolyte layer by coating a polymer coating on one side or both sides of the solid electrolyte layer, specifically: (1) The polymer coating is relatively soft, so that the solid-solid contact problem between the electrolyte and the electrode can be improved, and the interface resistance is reduced; (2) The polymer coating can prevent the electrolyte from being reduced in an electrochemical environment, so that interface side reaction is inhibited; (3) The polymer coating is coated on the surface of electrolyte to play a role of a buffer layer, so that the concentration distribution of lithium ions is more uniform, and the problem of metal lithium deposition caused by the difference of the ionic conductivity of a crystal boundary and a bulk phase is solved. The solid lithium battery based on the composite electrolyte membrane has good cycle performance and high safety.
Drawings
Fig. 1 is a schematic view of a composite electrolyte membrane of the present invention.
Fig. 2 is a photograph of a PVDF-uncoated LATP electrolyte membrane (a) and a PVDF-coated LATP electrolyte membrane (b) after cycling for 500 weeks at a charge-discharge rate of 2.5A in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Example 1
(1) Preparation of solid electrolyte layer
Mixing the LATP nano material with NMP to obtain slurry B; coating the slurry B on two sides of a PP (polypropylene) substrate (with the thickness of 12 mu m), and drying to form a LATP layer with the thickness of 1 mu m on the two sides of the PP substrate; thus obtaining a solid electrolyte layer (with a thickness of 14 μm); wherein the particle size of the LATP nano material is 70nm.
(2) Preparation of composite electrolyte Membrane
Mixing PVDF and NMP to obtain slurry A; spraying the slurry A on two sides of the solid electrolyte layer obtained in the step (1) (namely, spraying the slurry A on the LATP layer), and drying to form PVDF layers with the thickness of 1 mu m on two sides of the solid electrolyte layer; thus, a composite electrolyte membrane (thickness: 16 μm) was obtained, and the structure was as shown in FIG. 1.
Example 2
(1) Preparing a solid electrolyte layer: same as in step (1) of example 1.
(2) Preparation of composite electrolyte Membrane
Mixing PVDF, liTFSI and NMP to obtain slurry A, wherein the mass ratio of PVDF to LiTFSI is 5; spraying the slurry A on two sides of the solid electrolyte layer obtained in the step (1) (namely, spraying the slurry A on the LATP layer), drying, and forming PVDF layers with the thickness of 1 mu m on two sides of the solid electrolyte layer; thus, a composite electrolyte membrane (thickness: 16 μm) was obtained, and the structure was as shown in FIG. 1.
Example 3
(1) Preparation of solid electrolyte layer
Mixing the LLZO nano material with NMP to obtain slurry B; coating the slurry B on two sides of a PE matrix (with the thickness of 12 mu m), and drying to form LLZO layers with the thickness of 1 mu m on the two sides of the PE matrix; thus obtaining a solid electrolyte layer (with a thickness of 14 μm); wherein the particle size of the LLZO nano material is 70nm.
(2) Preparation of composite electrolyte Membrane
Mixing PAN and NMP to obtain slurry A; spraying the slurry A on two sides of the solid electrolyte layer obtained in the step (1) (namely spraying the slurry A on the LLZO layer), drying, and forming PAN layers with the thickness of 1 mu m on two sides of the solid electrolyte layer; thus, a composite electrolyte membrane (thickness: 16 μm) was obtained, and the structure was as shown in FIG. 1.
Example 4
(1) Preparation of solid electrolyte layer
Pressing the LAGP nano material into a tablet with the thickness of 14 mu m to obtain a solid electrolyte layer; wherein the particle size of the LAGP nano material is 70nm.
(2) Preparation of composite electrolyte Membrane
Mixing PI and NMP to obtain slurry A; spraying the slurry A on two sides of the solid electrolyte layer obtained in the step (1) (namely spraying the slurry A on the LAGP layer), and drying to form PI layers with the thickness of 1 mu m on two sides of the solid electrolyte layer; thus, a composite electrolyte membrane (thickness: 16 μm) was obtained, and the structure was as shown in FIG. 1.
Comparative example 1
A solid electrolyte layer was prepared according to the procedure (1) of example 1 without coating a PVDF polymer coating, and directly used as an electrolyte membrane.
Effects of the embodiment
1. Assembled solid state lithium battery
Using NCM622 positive electrodeMaterial, double-sided coating on aluminum current collector, with double-sided density of 440g/m 2 Compacted density of 3.5g/cm 3 Obtaining a positive plate; adopts Si/C composite cathode material with specific capacity of 450mAh/g, and is coated on the two sides of copper current collector, and the density of the two sides is 190g/m 2 Compacted density of 1.6g/cm 3 Obtaining a negative plate; respectively adopting the electrolyte membranes prepared in the examples 1-4 and the comparative example 1, and assembling the electrolyte membranes and the electrode plates together in a lamination mode according to the sequence of the electrolyte membranes, the negative electrode plates, the electrolyte membranes and the positive electrode plates to prepare electrode cores; then packaging with an aluminum plastic film, injecting liquid, forming and grading to prepare the solid lithium battery.
2. Electrochemical Performance test
The solid lithium battery is subjected to electrochemical performance test, and the capacity retention rate is shown in table 1 after 500 weeks of circulation at a charge-discharge rate of 2.5A.
TABLE 1
Figure BDA0002989226650000081
In the above table, "/" indicates the absence of this component.
As can be seen from table 1, the LATP electrolyte membrane protected with a PVDF coating (i.e., the composite electrolyte membrane of the present invention) exhibited better cycle performance, with a capacity retention rate of 90% after 500 cycles at a charge-discharge rate of 2.5A, with the composite electrolyte membrane of example 1 compared to the LATP electrolyte membrane protected with an uncoated PVDF in comparative example 1. The solid lithium batteries using the composite electrolyte membranes of examples 2 and 3 also exhibited excellent cycle performance. When the solid electrolyte layer includes only an inorganic solid electrolyte (example 4), the cycle performance of the solid lithium battery is relatively poor.
In addition, the PVDF-uncoated LATP electrolyte membrane of comparative example 1 was severely reduced and the material structure was destroyed by visual observation (see fig. 2 a), whereas the PVDF-coating-protected LATP electrolyte membrane of example 1 (i.e., the composite electrolyte membrane of the present invention) had good LATP protection and was not significantly reduced (see fig. 2 b).

Claims (30)

1. A composite electrolyte membrane comprising a solid electrolyte layer coated on one or both sides with a polymer coating; the solid electrolyte layer comprises an inorganic solid electrolyte and a polymer matrix, and the inorganic solid electrolyte is coated on two sides of the polymer matrix;
the thickness of the polymer coating is 0.5 to 5 mu m;
the thickness of the solid electrolyte layer is 5 to 15 mu m.
2. The composite electrolyte membrane according to claim 1,
the polymer in the polymer coating is selected from at least one of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyacrylic acid, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, thermoplastic polyurethane, polyacrylate and polyvinyl chloride;
and/or, the polymer coating further comprises a lithium salt.
3. The composite electrolyte membrane according to claim 1, wherein the polymer coating has a thickness of 1 μm.
4. The composite electrolyte membrane according to claim 2, wherein the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate.
5. The composite electrolyte membrane according to claim 2, wherein the mass ratio of the polymer to the lithium salt in the polymer coating is (2 to 30): 1.
6. the composite electrolyte membrane according to claim 1,
the thickness ratio of the polymer coating layer to the solid electrolyte layer is 1: (5 to 20);
and/or the particle size of the inorganic solid electrolyte is 50-500nm.
7. The composite electrolyte membrane according to claim 1, wherein the inorganic solid electrolyte is an oxide-based solid electrolyte and/or a sulfide-based solid electrolyte.
8. The composite electrolyte membrane according to claim 1, wherein the structure of the inorganic solid electrolyte is a Nasicon structure, a perovskite structure, or a garnet structure.
9. The composite electrolyte membrane according to claim 1, wherein the inorganic solid electrolyte is selected from the group consisting of: li 1+ p Al p Ge 2-p (PO 4 ) 3 、Li 1+m Al m Ti 2-m (PO 4 ) 3 、Li 3q La 2/3-q TiO 3 、Li 7 La 3 Zr 2 O 12 、LiZr 2-r Ti r (PO 4 ) 3 、Li 4- t Ge 1-t P t S 4 、Li 7-2n-j A n La 3 Zr 2-JBj O 12 、Li 7-2n-2j A n La 3 Zr 2- j C j O 12 、Li 7 P 3 S 11 、Li 3-k D k PS 4-u O u 、Li 2.58 C 0.42 B 0.58 O 3 And Li 2 O-ZrO 2 -SiO 2 One or more of (a); wherein p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2/3, r is more than or equal to 2 and less than or equal to 0, m is more than or equal to 2, t is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, k is more than or equal to 0 and less than or equal to 3, u is more than or equal to 0 and less than or equal to 4, A is Ge and/or Al, B is Nb and/or Ta, and C is Te and/or W.
10. The composite electrolyte membrane according to claim 6,
the thickness ratio of the polymer coating layer to the solid electrolyte layer is 1;
and/or the particle size of the inorganic solid electrolyte is 70nm.
11. The composite electrolyte membrane according to claim 10, wherein the thickness of the solid electrolyte layer is 14 μm.
12. The composite electrolyte membrane according to claim 1, wherein the polymer matrix is a polymer that is non-conductive to electrons or ions and does not react with the inorganic solid electrolyte.
13. The composite electrolyte membrane according to claim 12, wherein the polymer matrix is selected from one or more of polyethylene, polypropylene, polyvinylidene fluoride, and polyimide.
14. The composite electrolyte membrane according to claim 1, wherein the solid electrolyte layer further comprises a binder.
15. A method of making a composite electrolyte membrane, comprising: coating the slurry A on one side or two sides of the solid electrolyte layer, and drying to obtain a polymer coating; wherein the slurry A comprises a polymer and an organic solvent; the solid electrolyte layer comprises an inorganic solid electrolyte and a polymer matrix, and the inorganic solid electrolyte is coated on two sides of the polymer matrix.
16. The method for producing a composite electrolyte membrane according to claim 15, wherein the polymer is at least one selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyacrylic acid, polyimide, polyetherimide, polyamide, polytetrafluoroethylene, thermoplastic polyurethane, polyacrylates, and polyvinyl chloride;
and/or the organic solvent is acetonitrile or N-methyl pyrrolidone;
and/or, the slurry A further comprises a lithium salt;
and/or the thickness of the polymer coating is 0.5-100 μm;
and/or the coating mode is spray coating, extrusion coating, transfer coating or micro-gravure coating;
and/or the drying temperature is 50-120 ℃, and the drying time is 2-24h.
17. The method for producing a composite electrolyte membrane according to claim 16, characterized in that the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate.
18. The method for producing a composite electrolyte membrane according to claim 16, wherein the mass ratio of the polymer to the lithium salt is (2 to 30): 1.
19. the method of producing a composite electrolyte membrane according to claim 16, characterized in that the thickness of the polymer coating layer is 1 μm.
20. The production method of a composite electrolyte membrane according to claim 15, characterized in that the thickness of the solid electrolyte layer is 5 to 200 μm;
and/or the particle size of the inorganic solid electrolyte is 50-500nm.
21. The method of producing a composite electrolyte membrane according to claim 15, characterized in that the inorganic solid electrolyte is an oxide-based solid electrolyte and/or a sulfide-based solid electrolyte.
22. The method of producing a composite electrolyte membrane according to claim 15, wherein the structure of the inorganic solid electrolyte is a Nasicon structure, a perovskite structure, or a garnet structure.
23. The method for producing a composite electrolyte membrane according to claim 15, characterized in that the inorganic solid electrolyte is selected from: li 1+p Al p Ge 2-p (PO 4 ) 3 、Li 1+m Al m Ti 2-m (PO 4 ) 3 、Li 3q La 2/3-q TiO 3 、Li 7 La 3 Zr 2 O 12 、LiZr 2-r Ti r (PO 4 ) 3 、Li 4-t Ge 1-t P t S 4 、Li 7-2n-j A n La 3 Zr 2-JBj O 12 、Li 7-2n-2j A n La 3 Zr 2- j C j O 12 、Li 7 P 3 S 11 、Li 3-k D k PS 4- u O u 、Li 2.58 C 0.42 B 0.58 O 3 And Li 2 O-ZrO 2 -SiO 2 One or more of (a); wherein p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2/3, r is more than or equal to 2 and less than or equal to 0, m is more than or equal to 2, t is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, k is more than or equal to 0 and less than or equal to 3, u is more than or equal to 0 and less than or equal to 4, A is Ge and/or Al, B is Nb and/or Ta, and C is Te and/or W.
24. The production method of a composite electrolyte membrane according to claim 20, characterized in that the thickness of the solid electrolyte layer is 14 μm;
and/or the particle size of the inorganic solid electrolyte is 70nm.
25. The method for producing a composite electrolyte membrane according to claim 15, characterized in that the polymer matrix is a polymer that does not conduct electrons or ions and does not react with the inorganic solid electrolyte.
26. The method of producing a composite electrolyte membrane according to claim 15, wherein the polymer matrix is selected from one or more of polyethylene, polypropylene, polyvinylidene fluoride, and polyimide.
27. The method for producing a composite electrolyte membrane according to claim 15, characterized in that the method for producing a solid electrolyte layer comprises: coating the slurry B on two sides of the polymer matrix and then drying; wherein the slurry B comprises the inorganic solid electrolyte, a binder and a solvent; the solvent is an aqueous solvent or an oily solvent.
28. The method for producing a composite electrolyte membrane according to claim 27, wherein the solvent is acetonitrile or N-methylpyrrolidone.
29. Use of the composite electrolyte membrane according to any one of claims 1 to 14 in a solid state lithium battery.
30. A solid lithium battery comprising the composite electrolyte membrane according to any one of claims 1 to 14.
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