WO2021218803A1

WO2021218803A1 - Solid-state battery

Info

Publication number: WO2021218803A1
Application number: PCT/CN2021/089256
Authority: WO
Inventors: 邓永红; 刘中波; 敖小虎; 钱韫娴; 王曼
Original assignee: 深圳新宙邦科技股份有限公司
Priority date: 2020-04-26
Filing date: 2021-04-23
Publication date: 2021-11-04
Also published as: CN113555600A; CN113555600B

Abstract

In order to overcome the problem in the existing solid-state batteries that the stability of a battery is affected by cyclic degradation caused by decomposition of an electrolyte, provided is a solid-state battery, comprising a positive electrode, a negative electrode, and a solid-state electrolyte located between the positive electrode and the negative electrode. The positive electrode comprises a positive electrode active material, and the granularity D50 of the positive electrode active material is 100 nm to 200 μm; the solid-state electrolyte comprises a polymer and an electrolyte additive, and the electrolyte additive comprises a compound as represented by the structural formula 1. A synergistic effect exists between the positive electrode active material and the electrolyte additive, and can effectively promote the occurrence of a reaction between the surface of the positive electrode and the electrolyte additive as represented by the structural formula 1 to generate a compact SEI film, and the SEI film has high chemical stability and reduces direct contact between the positive electrode active material and the polymer in the electrolyte, thereby reducing decomposition of the polymer and effectively improving the chemical stability of the polymer in the solid-state electrolyte.

Description

A solid state battery

Technical field

The invention belongs to the technical field of secondary batteries, and specifically relates to a solid-state battery.

Background technique

Compared with traditional electrochemical energy devices such as lead-acid and nickel-chromium batteries, lithium-ion batteries have become the most widely used commercial storage device due to their high energy density, high working voltage, no memory effect, long cycle life and environmental friendliness. Energy system. Although traditional liquid lithium-ion batteries have good ionic conductivity and wettability, they also have safety problems such as poor thermal stability, flammability, and easy leakage. The solid electrolyte with higher energy density and excellent safety performance has become the potential best method to replace the liquid electrolyte to solve the above-mentioned problems. The polymer electrolyte uses relatively flexible organic matter, has good interface contact with the electrode material, and is compatible with existing lithium-ion battery production equipment. It is the solid-state battery system most likely to achieve large-scale applications.

At present, in the research field of high-voltage solid-state lithium battery systems, it is necessary to improve the cycle stability of the battery under high voltage. The focus of research is usually on the positive electrode material itself. For example, the method of coating the positive electrode material to reduce the occurrence of side reactions such as the decomposition of the electrolyte However, there are few studies on the internal side reaction process of polymer solid electrolyte and its suppression methods. Traditional polymer electrolytes usually use lithium bistrifluoromethanesulfonimide (LiTFSI), according to Faglioni F, Merinov BV, Goddard WA, et al. Physical Chemistry Chemical Physics, 2018, 20(41): 26098-26104 And Nie K, Wang X, Qiu J, et al. Pushing PEO Stability Up to 4.5V by Surface Coating of Cathode[J].ACS Energy Letters,2020,5(3),826-832, the oxidation of electrolyte The decomposition initially occurs near the positive electrode. The hydrogen atoms released by the polymer PEO combine with the anion of the lithium salt LiTFSI to form a strong acid HTFSI. On the one hand, HTFSI will attack PEO and cause polymer chain scission. HTFSI reduces the ion conductivity and increases the positive electrode. The surface voltage drop will aggravate the decomposition of the polymer; on the other hand, HTFSI will corrode the positive electrode _{material such as LCoO 2} and the interface between the positive electrode and the electrolyte. Therefore, the chemical (electrochemical) decomposition of polymer electrolytes under high voltage is closely related to lithium salt, and inhibiting the promotion of lithium salt on polymer decomposition can improve the chemical (electrochemical) stability of polymer electrolytes under high voltage. Vital.

Summary of the invention

Aiming at the problem of cycle degradation caused by electrolyte decomposition in existing solid-state batteries and affecting battery stability, the present invention provides a solid-state battery.

The technical solutions adopted by the present invention to solve the above technical problems are as follows:

The present invention provides a solid state battery, including a positive electrode, a negative electrode, and a solid electrolyte located between the positive electrode and the negative electrode;

The positive electrode includes a positive electrode active material, and the particle size D50 of the positive electrode active material is 100 nm to 200 μm;

The solid electrolyte includes a polymer and an electrolyte additive, and the electrolyte additive includes a compound represented by the following structural formula:

Where R ₁ and R ₃ are each independently selected from

R _{4 is} selected from S or Se; R _{5 is} selected from C, Si, Ge, Sn, S or Se; R _{2 is} selected from carbon chain or aromatic ring with part of hydrogen or all hydrogen replaced by other elements or groups; M ₁ Selected from N, B, P, As, Sb or Bi; M _{2 is} selected from Li, Na, K, Ru, Cs, Fr, Al, Mg, Zn, Be, Ca, Sr, Ba or Ra, n is selected from 1 , 2 or 3.

Optionally, the specific surface area BET of the positive electrode active material is 0.1-20 m ² /g.

Optionally, the particle size D50 of the positive electrode active material is 200 nm-100 μm, and the specific surface area BET is 0.15-15 m ² /g.

Optionally, R _{2 is} selected from a saturated or unsaturated carbon chain of 1-4 carbons in which part of hydrogen or all hydrogens are replaced by halogen elements or halogenated hydrocarbon groups, and part of hydrogen or all hydrogen is replaced by halogen elements or halogenated hydrocarbon groups. Aromatic ring.

Optionally, R _{2 is} selected from a saturated or unsaturated carbon chain of 1-4 carbons in which part of hydrogen or all hydrogens are replaced by fluorine elements or fluorinated hydrocarbon groups, and aromatics in which part of hydrogen or all hydrogens are replaced by fluorine elements or fluorinated hydrocarbon groups. ring.

Optionally, the electrolyte additive includes one or more of the following compounds:

Optionally, the total mass of the solid electrolyte is calculated as 100%, and the content of the electrolyte additive is 1%-60%.

Optionally, the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, and carboxylate monomers. , Carbonate-based monomers, amide-based monomers, phosphazene-based monomers, copolymers composed of repeating units of at least two of the nitrile group-containing monomers, and their halogenated products, polyalkylene oxide polymers and their halogens Substitutes, polysiloxane polymers and their halogenated substances, polyolefin polymers and their halogenated substances, polyacrylate polymers and their halogenated substances, polycarboxylate polymers and their halogenated substances, polycarbonates One or more of type polymer and its halogenated substance, polyamide type polymer and its halogenated substance, polyphosphazene type polymer and its halogenated substance, nitrile group-containing polymer and its halogenated substance.

Optionally, based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 25%-90%.

Optionally, the solid electrolyte further includes a lithium salt, and the lithium salt includes LiBr, LiI, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiSCN, LiB ₁₀ Cl ₁₀ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiBF ₂ C ₂ O ₄ , LiB(C ₂ O ₄ ) ₂ , LiN(SO ₂ CF ₃ ) ₂ , LiN(SO ₂ F) ₂ , LiN(SO ₂ F)(SO ₂ CF ₃ ), LiC(SO ₂ CF ₃ ) One or more of ₃ , LiPF ₂ (C ₂ O _{4 );}

Based on the total mass of the solid electrolyte as 100%, the mass percentage of the lithium salt is 10-70%.

Optionally, the positive electrode active material includes a phosphate compound, lithium cobalt oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium manganese oxide or its solid solution, titanium oxide, vanadium oxide, manganese dioxide, two One or more of iron sulfide, titanium disulfide, molybdenum sulfide, and sulfur.

According to the solid-state battery provided by the present invention, when the compound shown in structural formula 1 is used as an electrolyte additive, the positive electrode active material with a particle size D50 of 100 nm to 200 μm is also used. The above-mentioned positive electrode active material and electrolyte additive have a synergistic effect, which can effectively promote the reaction of the positive electrode surface with the electrolyte additive shown in structural formula 1 to form a dense SEI film, and the chemical stability of the SEI film is high, reducing the positive electrode active material and electrolyte. The direct contact of the polymer, thereby reducing the decomposition of the polymer, effectively improving the chemical stability of the polymer in the solid electrolyte, thereby effectively improving the cycle stability of the battery.

Detailed ways

In order to make the technical problems, technical solutions, and beneficial effects solved by the present invention clearer and more comprehensible, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not used to limit the present invention.

The embodiment of the present invention provides a solid state battery, including a positive electrode, a negative electrode, and a solid electrolyte located between the positive electrode and the negative electrode;

Where R ₁ and R ₃ are each independently selected from

When the compound shown in Structural Formula 1 is used as an electrolyte additive, and a positive electrode active material with a particle size D50 of 100 nm to 200 μm is used at the same time, the inventors have found through a large number of experiments that when the solid electrolyte is attached to the positive electrode, the positive electrode active material and the electrolyte additive There is a synergistic effect, which can effectively promote the reaction of the positive electrode surface with the electrolyte additive shown in structural formula 1 to form a dense SEI film, and the SEI film has high chemical stability, reducing the direct contact between the positive electrode active material and the polymer in the electrolyte, thereby Reducing the decomposition of the polymer effectively improves the chemical stability of the polymer in the solid electrolyte, thereby effectively improving the cycle stability of the battery.

If the particle size D50 of the positive electrode active material is greater than 200μm, it is not conducive to the formation of a dense interfacial layer on the surface of the positive electrode by the electrolyte additive; if the particle size of the positive electrode active material D50 is less than 100nm, the particles of the positive electrode active material are too small and easy to agglomerate, which affects the uniformity of the interface SEI film , Thereby affecting the cycle performance of the battery and increasing the production cost.

In some embodiments, the specific surface area BET of the positive active material is 0.1-20 m ² /g.

When the specific surface area BET of the positive electrode active material is within the above range, it will further optimize the SEI film formed on the surface of the positive electrode. If the specific surface area BET of the positive electrode active material is too large, it will affect the electron conduction in the positive electrode. ; If the specific surface area BET of the positive electrode active material is too small, the adsorptivity is weak, affecting the continuity of the interface layer.

In a preferred embodiment, the particle size D50 of the positive electrode active material is 200 nm-100 μm, and the specific surface area BET is 0.15-15 m ² /g.

In a specific embodiment, the particle size D50 of the positive electrode active material can be selected to be 300nm, 500nm, 700nm, 900nm, 3.5μm, 5μm, 11μm, 24μm, 32μm, 50μm, 53μm, 73μm, 94μm or 150μm; BET specific surface area of active material is chosen to be ^{^{^{^{0.15m 2 /g,0.3m 2 /g,0.8m 2 /g,1.1m 2}}}} /g,2.4m 2 /g,4.23m 2 /g,5.4m 2 / g ^{^{^{, 7.3m 2 /g,9.1m 2 /g,9.9m 2 /g,11.6m}}} 2 /g,12.1m 2 /g,13.9m 2 / g or 14.9m ² / g.

In some embodiments, R _{2 is} selected from a saturated or unsaturated carbon chain of 1-4 carbons in which part of hydrogen or all hydrogens are replaced by halogen elements or halogenated hydrocarbon groups, and part of hydrogen or all hydrogens are substituted by halogen elements or halogenated hydrocarbon groups. Hydrocarbyl substituted aromatic ring.

If the carbon chain is too long, the stability of the compound represented by structural formula 1 is likely to decrease, thereby affecting its function in the solid electrolyte.

In a more preferred embodiment, R _{2 is} selected from a saturated or unsaturated carbon chain of 1-4 carbons in which part of hydrogen or all hydrogens are replaced by fluorine or fluorinated hydrocarbon groups, and part of hydrogen or all hydrogen is replaced by fluorine or fluorinated hydrocarbon groups. Aromatic ring.

In a more preferred embodiment, the electrolyte additive includes one or more of the following compounds:

It should be noted that the above are some of the compounds claimed in the present invention, but they are not limited thereto, and should not be understood as limiting the present invention.

In some embodiments, based on the total mass of the solid electrolyte being 100%, the content of the electrolyte additive is 1%-60%.

In a specific embodiment, the electrolyte additive content is 2%, 3%, 5%, 8%, 12%, 18%, 23%, 26%, 31%, 39%, 42%, 44%, 52%, 56% or 60%.

In some embodiments, the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylic ester monomers, and carboxylic acid esters. A copolymer composed of at least two of monomers, carbonate-based monomers, amide-based monomers, phosphazene-based monomers, and nitrile group-containing monomers as repeating units and their halogenated products, polyalkylene oxide polymers, and Its halogenated substances, polysiloxane polymers and their halogenated substances, polyolefin polymers and their halogenated substances, polyacrylate polymers and their halogenated substances, polycarboxylate polymers and their halogenated substances, polyolefins One or more of carbonate polymers and their halogenated substances, polyamide polymers and their halogenated substances, polyphosphazene polymers and their halogenated substances, nitrile group-containing polymers and their halogenated substances.

In a more preferred embodiment, the polymer includes polyethylene oxide (PEO), polypropylene carbonate (PPC), polymethacrylate (PMMA), polytrimethylene carbonate (PTMC), benzene One or more of copolymer of ethylene and ethylene oxide (PS-PEO), polycaprolactone (PCL), and polyacrylonitrile (PAN).

In some embodiments, based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 25%-90%.

In some embodiments, the solid electrolyte further includes a lithium salt, and the lithium salt includes LiBr, LiI, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiSCN, LiB ₁₀ Cl ₁₀ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiBF ₂ C ₂ O ₄ , LiB(C ₂ O ₄ ) ₂ , LiN(SO ₂ CF ₃ ) ₂ , LiN(SO ₂ F) ₂ , LiN(SO ₂ F)(SO ₂ CF ₃ ), LiC(SO ₂ CF ₃ ) ₃ , one or more of _{LiPF 2} (C ₂ O _{4 );}

In some embodiments, the positive active material includes a phosphate compound, lithium cobalt oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium manganese oxide or a solid solution thereof, titanium oxide, vanadium oxide, manganese dioxide , One or more of iron disulfide, titanium disulfide, molybdenum sulfide and sulfur.

In some preferred embodiments, the positive electrode active material is selected from lithium iron phosphate (LiFePO ₄ ), lithium cobalt oxide (LiCoO ₂ ), or lithium nickel manganese cobalt oxide (Li(Ni _0.6 Co _0.2 Mn _0.2 )O ₂ ) One or more of.

In some embodiments, the positive electrode further includes a positive electrode current collector, and the positive electrode active material is coated on the positive electrode current collector to form a positive electrode material layer.

In some embodiments, the positive electrode material layer further includes a positive electrode binder and a positive electrode conductive agent.

In some embodiments, the negative electrode includes a negative active material, and the negative active material includes one or more of carbon materials, metals and metal alloys, lithium-containing oxides, and silicon-containing materials.

The present invention will be further illustrated by the following examples.

Example 1

This embodiment is used to illustrate the solid-state battery and the preparation method thereof disclosed in the present invention, including the following operation steps:

Example 1 uses the electrolyte additive LiHFDF with the following structure.

Electrolyte preparation: Dissolve 1.0 g polymer (polyethylene oxide, PEO, Mw=1000,000) and 0.43 g electrolyte additive LiHFDF in 5 g acetonitrile to obtain a solution. The solution was coated, vacuum-dried at room temperature for 8 hours, and then vacuum-dried at 80°C for 12 hours, and cut into disks with a diameter of 18 mm as the electrolyte (SPE) of the button battery.

_{Preparation of solid-state lithium batteries: LiFePO 4} (LFP) with a particle size D50 of 3.5 μm and a specific surface area of 15.7 m2/g is used as the positive electrode active material, and the LFP, conductive carbon black, and the above polymer electrolyte are used in a ratio of 80:10:10 Mix by mass ratio, add cyclohexanone, apply the mixed slurry on the carbon-coated aluminum foil, dry at 80℃ until there is no obvious liquid, then vacuum dry at 100℃ for 12h, and cut into 12mm diameter discs as buckles. The positive electrode of the type battery, the positive electrode, the electrolyte, and the lithium metal negative electrode with a diameter of 16mm are prepared into the LFP|SPE|Li button battery.

D50 test method:

A test sample was prepared by ultrasonically dispersing the positive electrode active material in ethanol, and the sample was placed in a laser particle size analyzer, and the particle size and distribution of the sample were automatically collected to obtain the D50 value of the positive electrode active material.

BET test method:

The positive electrode active material was dried in an oven at 105° C. for 3 hours, and then placed in a sample tube after cooling. The nitrogen adsorption method was tested with a BET specific surface area tester to obtain the specific surface area value of the positive electrode active material.

Examples 2-24

Examples 2-24 are used to illustrate the solid-state battery and its preparation method disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:

The polymers, electrolyte additives and positive electrode materials as shown in Examples 2-24 in Table 1 were used.

Comparative example 1～5

This comparative example 1 is used to compare and illustrate the solid-state battery and the preparation method thereof disclosed in the present invention, including most of the operation steps in Example 1. The difference lies in:

The polymers, electrolyte additives and positive electrode materials as shown in Comparative Examples 1 to 5 in Table 1 were used.

Performance Testing

The following performance tests were performed on the electrolytes and solid-state lithium batteries prepared in the foregoing Examples 1-24 and Comparative Examples 1-5:

Cyclic performance test of solid-state lithium battery: Carry out the cyclic charge-discharge test of the solid-state lithium battery prepared in Examples 1-24 and Comparative Examples 1-5 in a charge-discharge instrument, cycle for 300 weeks, according to the formula "capacity retention rate = 300th week The discharge capacity of the battery/the discharge capacity of the first week×100%", the capacity retention rate of the battery was calculated.

Fill in Table 1 with the test results obtained.

Table 1

Comparing Example 1 with Comparative Example 1, Example 5 and Comparative Example 2, Example 11 and Comparative Example 5, it can be found that the cycle performance of the solid-state battery using an electrolyte containing 20% LiHFDF is better than that of using 20% LiTFSI. Solid state battery with electrolyte. On the one hand, the anionic ring structure of LiHFDF increases the degree of negative charge delocalization and promotes the dissociation of the lithium salt. On the other hand, when the electrolyte containing LiHFDF is attached to the positive electrode, it can form a stable positive electrode interface. , Thereby improving the cycle performance of the battery. For a solid-state battery using a 3.8V LFP positive electrode, the stability of the polymer is less affected by voltage, so the difference in capacity retention between Example 1 and Comparative Example 1 is relatively inconspicuous. The capacity retention data of Comparative Example 5 and Comparative Example 2, Example 11 and Comparative Example 5 show that for the solid-state battery using 4.1V NMC622, 4.2V LCO positive electrode, LiHFDF is used as the electrolyte additive of the solid electrolyte, which is more prominent. The improvement effect indicates that the compound shown in structural formula 1 has a synergistic effect with high-voltage nickel-cobalt-manganese ternary cathode materials and lithium cobalt oxide cathode materials within a certain particle size D50 range, and can effectively improve the cycle performance of high-voltage batteries.

It can be seen from Examples 2 to 4 that changing the structure of the lithium salt or the ratio of the lithium salt still has an improvement effect on the cycle performance of the battery.

Comparing Example 5 with Comparative Example 3, using the same electrolyte, that is, using 20% LiHFDF salt, it was found that _{the NMC622 active material with a D 50} of 250 μm and a specific surface area ^{of 0.02 m 2} /g was used, due to the larger size of the positive electrode active material. It is not conducive to the formation of a dense interface layer on the positive electrode side, and the cycle capacity retention rate of the battery is only 27%. The battery cycle capacity retention rate of Comparative Example 4 is 35%, which is mainly due to the fact that the active material is too small in size and prone to agglomeration, which affects the diffusion and charge transfer process inside the positive electrode, thereby affecting the battery cycle performance. It shows that the D ₅₀ and specific surface area of the positive electrode active material are closely related to the cycle performance of the solid-state lithium battery. Comparing Example 5, Comparative Example 4, and Comparative Example 3, it can be found that the ^{positive electrode active material with a suitable particle size (100nm-200μm) and specific surface area (0.1-20m 2} /g) and the structured electrolyte salt The solid electrolyte synergistically promotes the improvement of the cycle stability of solid-state lithium batteries.

Examples 5-7 show that for batteries using different polymers as solid electrolytes, the compound shown in Structural Formula 1 and the positive electrode active material with a certain particle size range and specific surface area can improve the cycle performance of the battery.

Compared with Comparative Example 5, Examples 8-11 have significant improvement effects on the cycle performance, indicating that the solid electrolyte using the electrolyte salt can improve the cycle stability of a high-voltage lithium battery.

Examples 12-24 show that under the condition of a certain particle size range and specific surface area of the positive electrode active material, for the combination of different polymers and different structures of the electrolyte additive, the capacity retention rate of the battery is better than that of PEO-20% LiTFSI. The battery indicates that the solid electrolyte and positive electrode active material provided by the present invention have significant advantages in improving electrolyte stability and improving battery cycle stability.

Comparing the test data of Examples 1 to 4 and 18, 19, it can be seen that as the content of the compound represented by structural formula 1 in the electrolyte increases, the capacity retention rate of the battery first increases and then decreases, especially when the mass content of the compound represented by structural formula 1 When it is between 15% and 40%, the cycle performance of the battery has reached a better improvement effect.

Comparing the test data of Examples 1, 20-24, it can be seen that as the particle size D50 of the positive electrode active material increases and the specific surface area BET of the positive electrode active material decreases, the capacity retention rate of the battery first increases and then decreases. Yes, when the particle size D50 of the positive electrode active material is ^{between 3.5-50 μm and the specific surface area BET is between 4.23-15.7 m 2} /g, the cycle capacity of the battery has achieved a better retention effect.

The above descriptions are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included in the protection of the present invention. Within range.

Claims

A solid-state battery, characterized by comprising a positive electrode, a negative electrode, and a solid electrolyte located between the positive electrode and the negative electrode;

The positive electrode includes a positive electrode active material, and the particle size D50 of the positive electrode active material is 100 nm to 200 μm;

The solid electrolyte includes a polymer and an electrolyte additive, and the electrolyte additive includes a compound represented by the following structural formula:

Where R 1 and R 3 are each independently selected from
R 4 is selected from S or Se; R 5 is selected from C, Si, Ge, Sn, S or Se; R 2 is selected from carbon chain or aromatic ring with part of hydrogen or all hydrogen replaced by other elements or groups; M 1 Selected from N, B, P, As, Sb or Bi; M 2 is selected from Li, Na, K, Ru, Cs, Fr, Al, Mg, Zn, Be, Ca, Sr, Ba or Ra, n is selected from 1 , 2 or 3.
The solid-state battery according to claim 1, wherein the specific surface area BET of the positive electrode active material is 0.1-20 m 2 /g.
The solid-state battery according to claim 1, wherein the particle size D50 of the positive electrode active material is 200 nm to 100 μm, and the specific surface area BET is 0.15 to 15 m 2 /g.
The solid-state battery according to claim 1, wherein R 2 is selected from a saturated or unsaturated carbon chain of 1-4 carbons in which part of hydrogen or all hydrogen is replaced by halogen elements or halogenated hydrocarbon groups, part of hydrogen or all An aromatic ring in which hydrogen is substituted by a halogen element or a halogenated hydrocarbon group.
The solid-state battery according to claim 4, wherein the electrolyte additive includes one or more of the following compounds:
The solid-state battery according to claim 1, characterized in that, based on the total mass of the solid electrolyte as 100%, the content of the electrolyte additive is 1%-60%.
The solid-state battery according to claim 1, wherein the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, and acrylates. Copolymers composed of repeating units and their halogenated substances Polyalkylene oxide polymers and their halogenated products, polysiloxane polymers and their halogenated products, polyolefin polymers and their halogenated products, polyacrylate polymers and their halogenated products, polycarboxylates Polymers and their halogenated substances, polycarbonate polymers and their halogenated substances, polyamide polymers and their halogenated substances, polyphosphazene polymers and their halogenated substances, nitrile-containing polymers and their halogenated substances One or more.
The solid-state battery according to claim 1 or 7, characterized in that, based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 25%-90%.
The solid-state battery according to claim 1, wherein the solid-state electrolyte further includes a lithium salt, and the lithium salt includes LiBr, LiI, LiClO 4 , LiBF 4 , LiPF 6 , LiSCN, LiB 10 Cl 10 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiBF 2 C 2 O 4 , LiB(C 2 O 4 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiN(SO 2 F)(SO 2 CF 3 ), LiC(SO 2 CF 3 ) 3 , LiPF 2 (C 2 O 4 ) one or more;

Based on the total mass of the solid electrolyte as 100%, the mass percentage of the lithium salt is 10-70%.
The solid-state battery according to claim 1, wherein the positive electrode active material comprises a phosphate compound, lithium cobalt oxide, lithium nickel oxide, lithium nickel manganese cobalt oxide, lithium manganese oxide or its solid solution, oxide One or more of titanium, vanadium oxide, manganese dioxide, iron disulfide, titanium disulfide, molybdenum sulfide, and sulfur.