WO2021135900A1 - Solid electrolyte and solid lithium-ion battery - Google Patents

Solid electrolyte and solid lithium-ion battery Download PDF

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Publication number
WO2021135900A1
WO2021135900A1 PCT/CN2020/136014 CN2020136014W WO2021135900A1 WO 2021135900 A1 WO2021135900 A1 WO 2021135900A1 CN 2020136014 W CN2020136014 W CN 2020136014W WO 2021135900 A1 WO2021135900 A1 WO 2021135900A1
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Prior art keywords
solid electrolyte
lithium
solid
polymer
negative electrode
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PCT/CN2020/136014
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French (fr)
Chinese (zh)
Inventor
邓永红
钱韫娴
刘中波
褚艳丽
敖小虎
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深圳新宙邦科技股份有限公司
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Publication of WO2021135900A1 publication Critical patent/WO2021135900A1/en

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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of secondary batteries, and specifically relates to a solid electrolyte and a solid lithium ion battery.
  • lithium-ion batteries 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 current lithium ion battery system with graphite as the negative electrode has been optimized for mass production for many years, and the energy density has been difficult to exceed 300Wh/kg, which is difficult to meet the market's requirements for high cruising range.
  • lithium metal anode batteries with high theoretical energy density such as Li-S and Li-O 2 systems, high nickel, high voltage ternary cathode materials equipped with silicon, silicon carbon anode lithium ion batteries have come into sight.
  • the traditional organic liquid electrolyte is easy to decompose on the surface of the lithium metal, resulting in a shortened battery life; at the same time, the liquid electrolyte cannot effectively inhibit the growth of lithium dendrites, which will cause short circuits of the battery, thermal runaway and even fire And explosion problems, on the other hand, the volume expansion of electrode materials in use, etc., all pose challenges to battery design.
  • 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 solid-state battery 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.
  • polymer electrolytes use relatively flexible organic substances, and the interface contact between the electrode and the electrolyte in the lithium battery is relatively good, but there is a problem that the ion conductivity is low and the lithium dendrites cannot be suppressed.
  • the metal lithium negative electrode has defects or unevenness or poor interface contact during the preparation process, it will cause the generation of lithium dendrites, resulting in degradation and failure of the battery cycle performance, and a decline in the yield rate.
  • the present invention provides a solid electrolyte and a solid lithium ion battery.
  • the present invention provides a solid electrolyte including a polymer and an additive, and the additive includes a compound represented by the following structural formula 1:
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms.
  • the additives are dispersed on the surface and inside of the solid electrolyte.
  • the group containing 1 to 5 carbon atoms is selected from a hydrocarbon group, a fluorinated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a cyano-substituted hydrocarbon group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, methyl, ethyl, trimethylsiloxy, cyano or trifluoromethyl .
  • the compound represented by structural formula 1 is selected from one or more of the following compounds:
  • the mass percentage of the compound represented by Structural Formula 1 is 0.01-20%.
  • the mass percentage of the compound represented by Structural Formula 1 is 0.01-10%.
  • the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, and carboxylate monomers. , Polymers obtained by polymerization of at least one of carbonate monomers, amide monomers, and nitrile monomers, and halogenated compounds thereof;
  • the mass percentage of the polymer is 10-90%.
  • the solid electrolyte further includes a lithium salt
  • 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 );
  • the mass percentage of the lithium salt is 10-80%.
  • the solid electrolyte further includes an inorganic filler
  • the inorganic filler includes LiF, LiCl, Li 2 CO 3 , SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , MgO, Li 7 La 3 Zr 2 O 12 , Li x La 3 Zr y A 2-y O 12 , sulfide, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 2.88 PO 3.73 N 0.14 , One or more of montmorillonite, kaolin and diatomite, wherein A is one of Ta, Al, and Nb, 6 ⁇ x ⁇ 7, 0.5 ⁇ y ⁇ 2;
  • the mass percentage of the inorganic filler is 0-40%.
  • the solid electrolyte further includes a solvent, and the solvent includes one or more of carbonate, carboxylate, and fluorinated solvent;
  • the mass percentage of the solvent is 0-10%.
  • the present invention provides a solid-state lithium ion battery, including a positive electrode, a negative electrode, and the solid electrolyte as described above, the solid electrolyte being located between the positive electrode and the negative electrode.
  • the negative electrode includes a negative electrode active material
  • the negative electrode active material includes lithium titanate, carbon material, Li X Fe 2 O 3 , Li y WO 2 , lithium metal, lithium alloy, silicon-based alloy, and tin-based alloy , One or more of metal oxides, conductive polymers, and Li-Co-Ni-based materials, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.
  • the negative electrode active material is lithium metal.
  • the compound represented by structural formula 1 is added to the polymer, and the compound can be uniformly dispersed and compositely fixed in the polymer.
  • the battery is formed only at the interface of the solid electrolyte.
  • the compound shown in structural formula 1 can react with the negative electrode to form a uniform interface layer on the surface of the negative electrode.
  • the interface layer has the characteristics of conducting lithium ions, so that the migration rate of lithium ions at the interface tends to be uniform and reduces the migration rate
  • the gradient is conducive to uniform insertion/deposition of lithium, and the compound represented by structural formula 1 inside the solid electrolyte is in an unreacted state.
  • the interface layer formed by the reaction between the compound shown in Structural Formula 1 and the negative electrode has a certain mechanical strength, which can inhibit the formation of lithium dendrites.
  • the compound represented by the structural formula 1 inside the solid electrolyte if lithium dendrites are generated during the charging and discharging of the battery, when the lithium dendrites enter the solid electrolyte, they will interact with the structural formula 1 inside the solid electrolyte.
  • the compound reaction further generates a passivation film with high mechanical strength, which imposes resistance on the lithium dendritic sites, thereby further inhibiting the growth of lithium dendrites and improving the cycle performance of the solid-state lithium ion battery.
  • An embodiment of the present invention provides a solid electrolyte, including a polymer and an additive, and the additive includes a compound represented by the following structural formula 1:
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms.
  • the compound represented by structural formula 1 is added to the polymer, which can be uniformly dispersed and compounded in the polymer. Unlike traditional liquid electrolytes, only the compound represented by structural formula 1 at the interface of the solid electrolyte can be formed during battery formation. It reacts with the negative electrode to form a uniform interface layer on the surface of the negative electrode.
  • the interface layer has the characteristics of conducting lithium ions, so that the migration rate of lithium ions at the interface tends to be uniform, which reduces the migration rate gradient and facilitates the uniform insertion of lithium.
  • Deposited, and the compound represented by Structural Formula 1 inside the solid electrolyte is in an unreacted state.
  • the interface layer formed by the reaction between the compound shown in Structural Formula 1 and the negative electrode has a certain mechanical strength, which can inhibit the formation of lithium dendrites.
  • the compound represented by the structural formula 1 inside the solid electrolyte if lithium dendrites are generated during the charging and discharging of the battery, when the lithium dendrites enter the solid electrolyte, they will interact with the structural formula 1 inside the solid electrolyte.
  • the compound reaction further generates a passivation film with high mechanical strength, which imposes resistance on the lithium dendritic sites, thereby further inhibiting the growth of lithium dendrites and improving the cycle performance of the solid-state lithium ion battery.
  • the additives are dispersed on the surface and inside of the solid electrolyte.
  • the group containing 1-5 carbon atoms is selected from the group consisting of a hydrocarbyl group, a fluorinated hydrocarbyl group, an oxygen-containing hydrocarbyl group, a silicon-containing hydrocarbyl group, or a cyano-substituted hydrocarbyl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently selected from hydrogen, fluorine, methyl, ethyl, trimethylsiloxy, cyano, or trifluoro methyl.
  • the compound represented by Structural Formula 1 is selected from one or more of the following compounds:
  • the mass percentage of the compound represented by Structural Formula 1 is 0.01-20%.
  • the mass percentage of the compound represented by the structural formula 1 is 0.01-10%.
  • the mass percentage of the compound represented by the structural formula 1 is 0.05-10%.
  • the polymer is a polar polymer.
  • the polar groups on the polymer chain dissolve and dissociate the lithium salt through the action of Lewis acid-base, and the lithium ions are transported through the movement of the polymer chain.
  • the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, carboxylate monomers, carbonate monomers, amides A polymer obtained by polymerizing at least one of a type monomer and a nitrile type monomer, and a halogenated product thereof;
  • the mass percentage of the polymer is 10-90%.
  • the solid electrolyte further includes a lithium salt
  • 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 ).
  • the mass percentage of the lithium salt is 10-80%.
  • the solid electrolyte further includes inorganic fillers, and the inorganic fillers include LiF, LiCl, Li 2 CO 3 , SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , MgO, Li 7 La 3 Zr 2 O 12 , Li x La 3 Zr y A 2-y O 12 , sulfide, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 2.88 PO 3.73 N 0.14 , one or more of montmorillonite, kaolin and diatomite, where A is one of Ta, Al, and Nb, 6 ⁇ x ⁇ 7, 0.5 ⁇ y ⁇ 2;
  • inorganic fillers By adding inorganic fillers to the solid electrolyte, the mechanical properties of the solid electrolyte can be further improved and the growth of lithium dendrites can be inhibited. At the same time, inorganic fillers can reduce the crystallinity of the polymer and increase the mobility of the polymer chain, thereby increasing the migration speed of lithium ions in the polymer, bringing higher ionic conductivity to the solid electrolyte, and helping to reduce the electrical conductivity. Polarization in chemical processes.
  • the mass percentage of the inorganic filler is 0-40%.
  • the median particle diameter D50 of the inorganic filler is 5 nm to 5 ⁇ m.
  • the solid electrolyte further includes a porous skeleton, and the polymer is supported on the porous skeleton.
  • the porous framework is selected from bacterial cellulose membranes.
  • the solid electrolyte further includes a solvent, and the solvent includes one or more of carbonate, carboxylate, and fluorinated solvent;
  • the mass percentage of the solvent is 0-10%.
  • the present invention provides a solid-state lithium ion battery, including a positive electrode, a negative electrode, and the solid electrolyte as described above, the solid electrolyte being located between the positive electrode and the negative electrode.
  • the cathode includes a cathode active material
  • the positive electrode active material comprises LiNi x Co y Mn z L ( 1-xyz) O 2, LiCo x 'L (1-x') O 2, LiNi x "L 'y' Mn (2 -x" -y ') O 4, Li z' MPO 4 in at least one of; wherein, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe ; 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x+y+z ⁇ 1, 0 ⁇ x' ⁇ 1, 0.3 ⁇ x” ⁇ 0.6, 0.01 ⁇ y' ⁇ 0.2;L'is Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe; 0.5 ⁇ z' ⁇ 1, and M is at least one of Fe, Mn, and Co.
  • the positive electrode active material is selected from one or more of lithium cobalt oxide, nickel cobalt aluminum, nickel cobalt manganese, lithium iron manganese phosphate, lithium manganate, and lithium iron phosphate.
  • the positive electrode further includes a positive electrode binder and a positive electrode conductive agent.
  • the negative electrode includes a negative electrode active material
  • the negative electrode active material includes lithium titanate (LTO), carbon material, Li X Fe 2 O 3 , Li y WO 2 , lithium metal, lithium alloy, silicon-based One or more of alloys, tin-based alloys, metal oxides, conductive polymers, and Li-Co-Ni-based materials, where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1.
  • the negative active material is lithium metal.
  • the carbon material includes non-graphitized carbon and graphitized carbon.
  • the metal oxide includes SnO, SnO 2 , PbO, Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 One or more of O 4 , Bi 2 O 5 and titanium oxide
  • the conductive polymer includes polyacetylene.
  • the negative electrode further includes a negative electrode binder and a negative electrode conductive agent.
  • the solid-state lithium ion battery adopts the solid electrolyte as described above, it has better cycle stability and can effectively avoid battery short circuit and increase in polarization voltage caused by lithium dendrites.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including the following operation steps:
  • the additive used is compound 1. Dissolve 1.0 g of polyethylene oxide (PEO) with a weight average molecular weight of 60W and 0.41 g of LiN(SO 2 CF 3 ) 2 in 5 g of acetonitrile, then add 0.029 g of compound 1 and stir until The solid is completely dissolved. The obtained polymer solution was placed on a coating machine, automatically scraped with a doctor blade, dried in vacuum at room temperature for 8 hours, and then dried in vacuum at 80° C. for 12 hours to obtain a polymer solid electrolyte of 40 ⁇ m. The content of compound 1 in the electrolyte accounts for 2% of the total weight of the electrolyte.
  • PEO polyethylene oxide
  • LiN(SO 2 CF 3 ) 2 LiN(SO 2 CF 3 ) 2
  • Positive electrode Mix LiFePO 4 active material, conductive carbon black, and the above polymer electrolyte in a mass ratio of 80:10:10, add cyclohexanone, and stir until the mixture is uniform. The slurry obtained above was evenly coated on the aluminum foil, dried at 80°C until there was no obvious liquid, and then dried at 100°C under vacuum for 12 hours.
  • Negative electrode Lithium metal is used as the negative electrode.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • Polypropylene carbonate (PPC) was used instead of polyethylene oxide (PEO) in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • LiCF 3 SO 3 is used instead of the lithium salt LiN(SO 2 CF 3 ) 2 in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • the solid electrolyte solution Place it in a polytetrafluoroethylene template for drying, volatilize at room temperature for 4 hours, and then vacuum dry at 60°C for 6 hours to obtain a solid polymer electrolyte.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • a bacterial cellulose membrane is obtained.
  • the porosity of the bacterial cellulose membrane is calculated to be 85 vol% by Archimedes method, and the solid electrolyte solution is infiltrated In the bacterial cellulose membrane, volatilize the solvent at room temperature and then infiltrate the solid electrolyte solution, repeat the operation until the pores are completely filled with polymer, and then vacuum dry at 60°C for 6 hours to obtain a solid electrolyte.
  • the average thickness of the solid electrolyte membrane is 52 ⁇ m.
  • This embodiment is used to describe the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 3. The difference lies in:
  • LiFe 0.5 Mn 0.5 PO 4 was used instead of the positive electrode active material LiFePO 4 in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • the structural formula is Compound 3 of replaces Compound 1 in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • the structural formula is Compound 4 of replaces Compound 1 in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • the structural formula is Compound 8 of replaces Compound 1 in Example 1.
  • This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
  • the structural formula is The compound 9 replaces the additive in Example 1.
  • This comparative example is used to compare and illustrate the preparation method of the solid-state electrolyte and solid-state lithium-ion battery disclosed in the present invention, including most of the operation steps in Example 1, and the difference lies in:
  • This comparative example is used to compare and illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in Example 6, and the difference lies in:
  • the solid-state lithium ion batteries prepared in the foregoing Examples 1-10 and Comparative Examples 1 and 2 were subjected to a charge-discharge cycle test on a blue power tester, and the test temperature was 60°C.
  • the solid-state lithium ion batteries of Examples 1 to 5, 7 to 10 and Comparative Example 1 were charged to 3.8V at a current of 0.2C, then charged at a constant voltage until the current dropped to 0.20mA, and then discharged at a constant current of 0.2C to 2.8V, cycle 200 weeks;
  • the battery prepared by the solid polymer electrolyte of the present invention has an average Coulombic efficiency of 98.2% or more at 0.2C cycle at 60°C, and LiFePO 4 is used as the positive electrode.
  • the capacity retention rate of 0.2C cycle is above 80% and the number of cycle cycles is above 456 weeks, indicating that the addition of additives plays an important role in inhibiting the formation of lithium dendrites and extending the life of solid-state lithium-ion batteries.
  • Example 6 and Comparative Example 2 it can be seen from the test results of Example 6 and Comparative Example 2 that when different cathode materials, such as LiFe 0.5 Mn 0.5 PO 4, are used as the cathode material, the cycle performance of the solid-state lithium-ion battery is also significantly improved, indicating that the solid-state battery provided by the present invention
  • the electrolyte is suitable for different cathode material systems. Comparing Example 1 and Example 5, it can be found that when a porous framework is introduced into the electrolyte, the cycle capacity retention rate of the battery is increased over 80%. This is because the introduction of the porous framework increases the mechanical strength of the electrolyte and reduces The glass transition problem of the electrolyte more effectively inhibits the growth of negative electrode dendrites.

Abstract

In order to solve the problem of lithium dendrites in existing solid electrolytes, the present invention provides a solid electrolyte, comprising a polymer and an additive, the additive comprising a compound represented by the following structural formula 1: structural formula 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms. In addition, also disclosed is a solid lithium-ion battery including the solid electrolyte. The solid electrolyte provided by the present invention can inhibit the growth of lithium dendrites during charge and discharge, thereby improving cycle performance.

Description

一种固态电解质及固态锂离子电池Solid electrolyte and solid lithium ion battery 技术领域Technical field
本发明属于二次电池技术领域，具体涉及一种固态电解质及固态锂离子电池。The invention belongs to the technical field of secondary batteries, and specifically relates to a solid electrolyte and a solid lithium ion battery.
背景技术Background technique
相比于铅酸、镍铬电池等传统电化学能源器件，锂离子电池因具有能量密度高、工作电压高、无记忆效应、循环寿命长和环境友好等优点，已是运用最广泛的商业储能体系。虽然传统的液态锂离子电池具备良好的离子导电率和浸润性，但同时也存在着热稳定性差、易燃、易漏液等安全问题。当前石墨为负极的锂离子电池体系经过多年量产优化，能量密度已经很难超过300Wh/kg，难以满足市场对高续航里程的要求。因此高理论能量密度的锂金属负极电池，如Li-S及Li-O 2体系等，高镍、高电压三元正极材料配备硅、硅碳负极锂离子电池进入视线。然而，一方面传统的有机系液态电解液容易在锂金属表面的分解，导致电池寿命的缩短；同时液态电解液无法有效抑制锂枝晶的生长，进而带来电池的短路，热失控甚至引起火灾及***的问题，另一方面电极材料在使用中的体积膨胀等问题都对电池的设计提出了挑战。 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 current lithium ion battery system with graphite as the negative electrode has been optimized for mass production for many years, and the energy density has been difficult to exceed 300Wh/kg, which is difficult to meet the market's requirements for high cruising range. Therefore, lithium metal anode batteries with high theoretical energy density, such as Li-S and Li-O 2 systems, high nickel, high voltage ternary cathode materials equipped with silicon, silicon carbon anode lithium ion batteries have come into sight. However, on the one hand, the traditional organic liquid electrolyte is easy to decompose on the surface of the lithium metal, resulting in a shortened battery life; at the same time, the liquid electrolyte cannot effectively inhibit the growth of lithium dendrites, which will cause short circuits of the battery, thermal runaway and even fire And explosion problems, on the other hand, the volume expansion of electrode materials in use, etc., all pose challenges to battery design.
具有更高的能量密度和优异的安全性能的固态电解质成为代替液态电解质解决上述解决问题的潜在最佳方法。聚合物固态电池与电极材料界面接触良好，同时兼容现有的锂离子电池生产设备，是最有可能实现规模化应用的固态电池体系。但聚合物电解质使用相对柔性的有机物，锂电池中电极与电解质的界面接触相对较好，但存在离子电导率低，不能抑制锂枝晶的问题。当制备过程金属锂负极存在缺陷或不均匀或界面接触不好时，均会引起锂枝晶的产生，造成电池循环性能衰减及失效，同时良品率下降。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 solid-state battery 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. However, polymer electrolytes use relatively flexible organic substances, and the interface contact between the electrode and the electrolyte in the lithium battery is relatively good, but there is a problem that the ion conductivity is low and the lithium dendrites cannot be suppressed. When the metal lithium negative electrode has defects or unevenness or poor interface contact during the preparation process, it will cause the generation of lithium dendrites, resulting in degradation and failure of the battery cycle performance, and a decline in the yield rate.
因此，亟需开发一种能够耐受金属锂的缺陷，提升电池良品率和寿命的聚合物固态电解质。Therefore, there is an urgent need to develop a polymer solid electrolyte that can withstand the defects of metallic lithium and improve the yield and life of the battery.
发明内容Summary of the invention
针对现有固态电解质存在锂枝晶生长导致电池循环性能衰减及失效的问题，本发明提供了一种固态电解质及固态锂离子电池。Aiming at the problem of lithium dendrite growth in the existing solid electrolyte that causes degradation and failure of battery cycle performance, the present invention provides a solid electrolyte and a solid lithium ion battery.
本发明解决上述技术问题所采用的技术方案如下：The technical solutions adopted by the present invention to solve the above technical problems are as follows:
一方面，本发明提供了一种固态电解质，包括聚合物和添加剂，所述添加剂包括以下结构式1所示的化合物：In one aspect, the present invention provides a solid electrolyte including a polymer and an additive, and the additive includes a compound represented by the following structural formula 1:
Figure PCTCN2020136014-appb-000001
Figure PCTCN2020136014-appb-000001
其中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟或含1-5个碳原子基团。 Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms.
可选的，所述添加剂分散于固态电解质的表面和内部。Optionally, the additives are dispersed on the surface and inside of the solid electrolyte.
可选的，所述含1-5个碳原子的基团选自烃基、氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。Optionally, the group containing 1 to 5 carbon atoms is selected from a hydrocarbon group, a fluorinated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a cyano-substituted hydrocarbon group.
可选的，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟、甲基、乙基、三甲基硅氧基、氰基或三氟甲基。 Optionally, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, methyl, ethyl, trimethylsiloxy, cyano or trifluoromethyl .
可选的，所述结构式1所示的化合物选自于如下所示化合物中的一种或多种：Optionally, the compound represented by structural formula 1 is selected from one or more of the following compounds:
Figure PCTCN2020136014-appb-000002
Figure PCTCN2020136014-appb-000002
Figure PCTCN2020136014-appb-000003
Figure PCTCN2020136014-appb-000003
可选的，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.01～20％。Optionally, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by Structural Formula 1 is 0.01-20%.
可选的，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.01～10％。Optionally, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by Structural Formula 1 is 0.01-10%.
可选的，所述聚合物为极性聚合物，所述聚合物包括环氧烷烃类单体、硅氧烷类单体、烯烃类单体、丙烯酸酯类单体、羧酸酯类单体、碳酸酯类单体、酰胺类单体、腈类单体中的至少一种聚合得到的聚合物及其卤代物；Optionally, the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, and carboxylate monomers. , Polymers obtained by polymerization of at least one of carbonate monomers, amide monomers, and nitrile monomers, and halogenated compounds thereof;
以所述固态电解质的总质量为100％计，所述聚合物的质量百分含量为10-90％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 10-90%.
可选的，所述固态电解质还包括有锂盐，所述锂盐包括LiBr、LiI、LiClO 4、LiBF 4、LiPF 6、LiSCN、LiB 10Cl 10、LiCF 3SO 3、LiCF 3CO 2、LiBF 2C 2O 4、LiB(C 2O 4) 2、LiN(SO 2CF 3) 2、LiN(SO 2F) 2、LiN(SO 2F)(SO 2CF 3)、LiC(SO 2CF 3) 3、LiPF 2(C 2O 4)中的一种或多种； 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 );
以所述固态电解质的总质量为100％计，所述锂盐的质量百分含量为10-80％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the lithium salt is 10-80%.
可选的，所述固态电解质还包括有无机填料，所述无机填料包括LiF、LiCl、Li 2CO 3、SiO 2、Al 2O 3、TiO 2、ZrO 2、MgO、Li 7La 3Zr 2O 12、Li xLa 3Zr yA 2-yO 12、硫化物、Li 1.3Al 0.3Ti 1.7(PO 4) 3、Li 1.5Al 0.5Ge 1.5(PO 4) 3、Li 2.88PO 3.73N 0.14、蒙脱土、高岭 土和硅藻土中的一种或多种，其中，A为Ta，Al，Nb中一种，6≤x≤7，0.5≤y≤2； Optionally, the solid electrolyte further includes an inorganic filler, and the inorganic filler includes LiF, LiCl, Li 2 CO 3 , SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , MgO, Li 7 La 3 Zr 2 O 12 , Li x La 3 Zr y A 2-y O 12 , sulfide, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 2.88 PO 3.73 N 0.14 , One or more of montmorillonite, kaolin and diatomite, wherein A is one of Ta, Al, and Nb, 6≤x≤7, 0.5≤y≤2;
以所述固态电解质的总质量为100％计，所述无机填料的质量百分含量为0～40％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the inorganic filler is 0-40%.
可选的，所述固态电解质还包括有溶剂，所述溶剂包括碳酸酯、羧酸酯、氟代溶剂中的一种或多种；Optionally, the solid electrolyte further includes a solvent, and the solvent includes one or more of carbonate, carboxylate, and fluorinated solvent;
以所述固态电解质的总质量为100％计，所述溶剂的质量百分含量为0～10％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the solvent is 0-10%.
另一方面，本发明提供了一种固态锂离子电池，包括正极、负极和如上所述的固态电解质，所述固态电解质位于所述正极和所述负极之间。In another aspect, the present invention provides a solid-state lithium ion battery, including a positive electrode, a negative electrode, and the solid electrolyte as described above, the solid electrolyte being located between the positive electrode and the negative electrode.
可选的，所述负极包括负极活性材料，所述负极活性材料包括钛酸锂、碳材料、Li XFe 2O 3、Li yWO 2、锂金属、锂合金、硅系合金、锡系合金、金属氧化物、导电聚合物、Li-Co-Ni基材料中的一种或多种，其中，0≤x≤1，0≤y≤1。 Optionally, the negative electrode includes a negative electrode active material, and the negative electrode active material includes lithium titanate, carbon material, Li X Fe 2 O 3 , Li y WO 2 , lithium metal, lithium alloy, silicon-based alloy, and tin-based alloy , One or more of metal oxides, conductive polymers, and Li-Co-Ni-based materials, where 0≤x≤1, 0≤y≤1.
可选的，所述负极活性材料为锂金属。Optionally, the negative electrode active material is lithium metal.
根据本发明提供的固态电解质，在聚合物中加入有结构式1所示的化合物，化合物能够均匀分散并复合固定于所述聚合物中，与传统液态电解质不同，电池化成时仅有位于固态电解质界面的结构式1所示的化合物能够与负极发生反应，从而在负极表面形成均匀的界面层，该界面层具有传导锂离子的特性，使得锂离子在界面处迁移速率趋向于均一化，降低了迁移速率梯度，有利于锂的均匀嵌入/沉积，而固态电解质内部的结构式1所示的化合物处于未反应状态。同时结构式1所示的化合物与负极反应生成的界面层具有一定的机械强度，能够对锂枝晶的生成起到抑制作用。另一方面，固态电解质内部的结构式1所示的化合物，在电池充放电的过程中，若生成锂枝晶，锂枝晶在进入固态电解质内部时，会与固态电解质内部的结构式1所示的化合物反应进一步生成机械强度高的钝化膜，对锂枝晶位点施加阻力，从而进一步抑制锂枝晶的生长，提升固态锂离子电池的循环性能。According to the solid electrolyte provided by the present invention, the compound represented by structural formula 1 is added to the polymer, and the compound can be uniformly dispersed and compositely fixed in the polymer. Unlike the traditional liquid electrolyte, the battery is formed only at the interface of the solid electrolyte. The compound shown in structural formula 1 can react with the negative electrode to form a uniform interface layer on the surface of the negative electrode. The interface layer has the characteristics of conducting lithium ions, so that the migration rate of lithium ions at the interface tends to be uniform and reduces the migration rate The gradient is conducive to uniform insertion/deposition of lithium, and the compound represented by structural formula 1 inside the solid electrolyte is in an unreacted state. At the same time, the interface layer formed by the reaction between the compound shown in Structural Formula 1 and the negative electrode has a certain mechanical strength, which can inhibit the formation of lithium dendrites. On the other hand, the compound represented by the structural formula 1 inside the solid electrolyte, if lithium dendrites are generated during the charging and discharging of the battery, when the lithium dendrites enter the solid electrolyte, they will interact with the structural formula 1 inside the solid electrolyte. The compound reaction further generates a passivation film with high mechanical strength, which imposes resistance on the lithium dendritic sites, thereby further inhibiting the growth of lithium dendrites and improving the cycle performance of the solid-state lithium ion battery.
具体实施方式Detailed ways
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。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.
本发明的一实施例提供了一种固态电解质，包括聚合物和添加剂，所述添加剂包括以下结构式1所示的化合物：An embodiment of the present invention provides a solid electrolyte, including a polymer and an additive, and the additive includes a compound represented by the following structural formula 1:
Figure PCTCN2020136014-appb-000004
Figure PCTCN2020136014-appb-000004
其中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟或含1-5个碳原子基团。 Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms.
在聚合物中加入有结构式1所示的化合物，该化合物能够均匀分散并复合于所述聚合物中，与传统液态电解质不同，电池化成时仅有位于固态电解质界面的结构式1所示的化合物能够与负极发生反应，从而在负极表面形成均匀的界面层，该界面层具有传导锂离子的特性，使得锂离子在界面处迁移速率趋向于均一化，降低了迁移速率梯度，利于锂的均匀嵌入/沉积，而固态电解质内部的结构式1所示的化合物处于未反应状态。同时结构式1所示的化合物与负极反应生成的界面层具有一定的机械强度，能够对锂枝晶的生成起到抑制作用。另一方面，固态电解质内部的结构式1所示的化合物，在电池充放电的过程中，若生成锂枝晶，锂枝晶在进入固态电解质内部时，会与固态电解质内部的结构式1所示的化合物反应进一步生成机械强度高的钝化膜，对锂枝晶位点施加阻力，从而进一步抑制锂枝晶的生长，提升固态锂离子电池的循环性能。The compound represented by structural formula 1 is added to the polymer, which can be uniformly dispersed and compounded in the polymer. Unlike traditional liquid electrolytes, only the compound represented by structural formula 1 at the interface of the solid electrolyte can be formed during battery formation. It reacts with the negative electrode to form a uniform interface layer on the surface of the negative electrode. The interface layer has the characteristics of conducting lithium ions, so that the migration rate of lithium ions at the interface tends to be uniform, which reduces the migration rate gradient and facilitates the uniform insertion of lithium. Deposited, and the compound represented by Structural Formula 1 inside the solid electrolyte is in an unreacted state. At the same time, the interface layer formed by the reaction between the compound shown in Structural Formula 1 and the negative electrode has a certain mechanical strength, which can inhibit the formation of lithium dendrites. On the other hand, the compound represented by the structural formula 1 inside the solid electrolyte, if lithium dendrites are generated during the charging and discharging of the battery, when the lithium dendrites enter the solid electrolyte, they will interact with the structural formula 1 inside the solid electrolyte. The compound reaction further generates a passivation film with high mechanical strength, which imposes resistance on the lithium dendritic sites, thereby further inhibiting the growth of lithium dendrites and improving the cycle performance of the solid-state lithium ion battery.
在一些实施例中，所述添加剂分散于固态电解质的表面和内部。In some embodiments, the additives are dispersed on the surface and inside of the solid electrolyte.
在一些实施例中，所述含1-5个碳原子的基团选自烃基、氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。In some embodiments, the group containing 1-5 carbon atoms is selected from the group consisting of a hydrocarbyl group, a fluorinated hydrocarbyl group, an oxygen-containing hydrocarbyl group, a silicon-containing hydrocarbyl group, or a cyano-substituted hydrocarbyl group.
在一些实施例中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟、甲基、乙基、三甲基硅氧基、氰基或三氟甲基。 In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently selected from hydrogen, fluorine, methyl, ethyl, trimethylsiloxy, cyano, or trifluoro methyl.
在一些实施例中，所述结构式1所示的化合物选自于如下所示化合物中的一种或多种：In some embodiments, the compound represented by Structural Formula 1 is selected from one or more of the following compounds:
Figure PCTCN2020136014-appb-000005
Figure PCTCN2020136014-appb-000005
Figure PCTCN2020136014-appb-000006
Figure PCTCN2020136014-appb-000006
需要说明的是，以上是本发明所要求保护的部分化合物，但不限于此，不应理解为对本发明的限制。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.
在一些实施例中，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.01～20％。In some embodiments, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by Structural Formula 1 is 0.01-20%.
在优选的实施例中，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.01～10％。In a preferred embodiment, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by the structural formula 1 is 0.01-10%.
在更优选的实施例中，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.05～10％。In a more preferred embodiment, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by the structural formula 1 is 0.05-10%.
若所述结构式1所示的化合物的含量过少，则不足以与固态锂离子电池的电化学过程中产生的锂枝晶反应，抑制锂枝晶的效果较差，难以改善固态锂离子电池的性能；若所述结构式1所示的化合物的含量过多，位于固态电解质界面的化合物与负极发生反应生成的界面层沉积厚度过大，过厚的界面层的锂离 子传导性能降低，锂离子在界面层的迁移阻力增大，固态锂离子电池在充放电过程中的极化严重，不利于固态锂离子电池的循环稳定性提高，且电池的内阻增大，初始容量降低。If the content of the compound represented by the structural formula 1 is too small, it will not be enough to react with the lithium dendrites generated in the electrochemical process of the solid-state lithium-ion battery, and the effect of inhibiting the lithium dendrites is poor, and it is difficult to improve the performance of the solid-state lithium-ion battery. Performance; if the content of the compound represented by the structural formula 1 is too much, the deposition thickness of the interface layer formed by the reaction between the compound at the solid electrolyte interface and the negative electrode is too large, the lithium ion conductivity of the too thick interface layer is reduced, and the lithium ion is in The migration resistance of the interface layer increases, and the polarization of the solid-state lithium-ion battery during charging and discharging is serious, which is not conducive to the improvement of the cycle stability of the solid-state lithium-ion battery, and the internal resistance of the battery increases and the initial capacity decreases.
在一些实施例中，所述聚合物为极性聚合物。In some embodiments, the polymer is a polar polymer.
通过聚合物链上的极性基团通过路易斯酸碱作用溶解、解离锂盐，锂离子通过聚合物链的运动进行传输。The polar groups on the polymer chain dissolve and dissociate the lithium salt through the action of Lewis acid-base, and the lithium ions are transported through the movement of the polymer chain.
在一些实施例中，所述聚合物包括环氧烷烃类单体、硅氧烷类单体、烯烃类单体、丙烯酸酯类单体、羧酸酯类单体、碳酸酯类单体、酰胺类单体、腈类单体中的至少一种聚合得到的聚合物及其卤代物；In some embodiments, the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, acrylate monomers, carboxylate monomers, carbonate monomers, amides A polymer obtained by polymerizing at least one of a type monomer and a nitrile type monomer, and a halogenated product thereof;
以所述固态电解质的总质量为100％计，所述聚合物的质量百分含量为10-90％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 10-90%.
在一些实施例中，所述固态电解质还包括有锂盐，所述锂盐包括LiBr、LiI、LiClO 4、LiBF 4、LiPF 6、LiSCN、LiB 10Cl 10、LiCF 3SO 3、LiCF 3CO 2、LiBF 2C 2O 4、LiB(C 2O 4) 2、LiN(SO 2CF 3) 2、LiN(SO 2F) 2、LiN(SO 2F)(SO 2CF 3)、LiC(SO 2CF 3) 3、LiPF 2(C 2O 4)中的一种或多种。 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 ).
以所述固态电解质的总质量为100％计，所述锂盐的质量百分含量为10-80％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the lithium salt is 10-80%.
在一些实施例中，所述固态电解质还包括有无机填料，所述无机填料包括LiF、LiCl、Li 2CO 3、SiO 2、Al 2O 3、TiO 2、ZrO 2、MgO、Li 7La 3Zr 2O 12、Li xLa 3Zr yA 2-yO 12、硫化物、Li 1.3Al 0.3Ti 1.7(PO 4) 3、Li 1.5Al 0.5Ge 1.5(PO 4) 3、Li 2.88PO 3.73N 0.14、蒙脱土、高岭土和硅藻土中的一种或多种，其中，A为Ta，Al，Nb中一种，6≤x≤7，0.5≤y≤2； In some embodiments, the solid electrolyte further includes inorganic fillers, and the inorganic fillers include LiF, LiCl, Li 2 CO 3 , SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , MgO, Li 7 La 3 Zr 2 O 12 , Li x La 3 Zr y A 2-y O 12 , sulfide, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 2.88 PO 3.73 N 0.14 , one or more of montmorillonite, kaolin and diatomite, where A is one of Ta, Al, and Nb, 6≤x≤7, 0.5≤y≤2;
通过在所述固态电解质中加入无机填料，能够进一步改善固态电解质的机械性能，抑制锂枝晶的生长。同时，无机填料可降低聚合物的结晶度，提高聚合物的链段移动能力，从而提升锂离子在聚合物中的迁移速度，为固态电解质带来更高的离子电导率，有助于降低电化学过程中的极化。By adding inorganic fillers to the solid electrolyte, the mechanical properties of the solid electrolyte can be further improved and the growth of lithium dendrites can be inhibited. At the same time, inorganic fillers can reduce the crystallinity of the polymer and increase the mobility of the polymer chain, thereby increasing the migration speed of lithium ions in the polymer, bringing higher ionic conductivity to the solid electrolyte, and helping to reduce the electrical conductivity. Polarization in chemical processes.
以所述固态电解质的总质量为100％计，所述无机填料的质量百分含量为0～40％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the inorganic filler is 0-40%.
所述无机填料的重量含量过高时，固态电解质的机械强度受到影响，成膜性变差。When the weight content of the inorganic filler is too high, the mechanical strength of the solid electrolyte is affected, and the film-forming properties deteriorate.
所述无机填料的中值粒径D50为5nm～5μm。The median particle diameter D50 of the inorganic filler is 5 nm to 5 μm.
在一些实施例中，所述固态电解质还包括多孔骨架，所述聚合物负载于所述多孔骨架上。In some embodiments, the solid electrolyte further includes a porous skeleton, and the polymer is supported on the porous skeleton.
在一些实施例中，所述多孔骨架选自细菌纤维素膜。In some embodiments, the porous framework is selected from bacterial cellulose membranes.
在一些实施例中，所述固态电解质还包括有溶剂，所述溶剂包括碳酸酯、羧酸酯、氟代溶剂中的一种或多种；In some embodiments, the solid electrolyte further includes a solvent, and the solvent includes one or more of carbonate, carboxylate, and fluorinated solvent;
以所述固态电解质的总质量为100％计，所述溶剂的质量百分含量为0～10％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the solvent is 0-10%.
另一方面，本发明提供了一种固态锂离子电池，包括正极、负极和如上所述的固态电解质，所述固态电解质位于所述正极和所述负极之间。In another aspect, the present invention provides a solid-state lithium ion battery, including a positive electrode, a negative electrode, and the solid electrolyte as described above, the solid electrolyte being located between the positive electrode and the negative electrode.
在一些实施例中，所述正极包括正极活性材料，所述正极活性材料包括LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种；其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe；0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2；L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。 In some embodiments, the cathode includes a cathode active material, the positive electrode active material comprises LiNi x Co y Mn z L ( 1-xyz) O 2, LiCo x 'L (1-x') O 2, LiNi x "L 'y' Mn (2 -x" -y ') O 4, Li z' MPO 4 in at least one of; wherein, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe ; 0≤x≤1, 0≤y≤1, 0≤z≤1, 0＜x+y+z≤1, 0<x'≤1, 0.3≤x”≤0.6, 0.01≤y'≤0.2;L'is Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe; 0.5≤z'≤1, and M is at least one of Fe, Mn, and Co.
具体的，所述正极活性材料选自钴酸锂、镍钴铝、镍钴锰、磷酸铁锰锂、锰酸锂、磷酸铁锂中的一种或多种。Specifically, the positive electrode active material is selected from one or more of lithium cobalt oxide, nickel cobalt aluminum, nickel cobalt manganese, lithium iron manganese phosphate, lithium manganate, and lithium iron phosphate.
在一些实施例中，所述正极还包括正极粘结剂和正极导电剂。In some embodiments, the positive electrode further includes a positive electrode binder and a positive electrode conductive agent.
在一些实施例中，所述负极包括负极活性材料，所述负极活性材料包括钛酸锂(LTO)、碳材料、Li XFe 2O 3、Li yWO 2、锂金属、锂合金、硅系合金、锡系合金、金属氧化物、导电聚合物、Li-Co-Ni基材料中的一种或多种，其中，0≤x≤1，0≤y≤1。 In some embodiments, the negative electrode includes a negative electrode active material, and the negative electrode active material includes lithium titanate (LTO), carbon material, Li X Fe 2 O 3 , Li y WO 2 , lithium metal, lithium alloy, silicon-based One or more of alloys, tin-based alloys, metal oxides, conductive polymers, and Li-Co-Ni-based materials, where 0≤x≤1 and 0≤y≤1.
在一些优选的实施例中，所述负极活性材料为锂金属。In some preferred embodiments, the negative active material is lithium metal.
所述碳材料包括非石墨化碳和石墨化碳。The carbon material includes non-graphitized carbon and graphitized carbon.
所述金属氧化物包括SnO、SnO 2、PbO、Pb 2O 3、Pb 3O 4、Sb 2O 3、Sb 2O 4、Sb 2O 5、GeO、GeO 2、Bi 2O 3、Bi 2O 4、Bi 2O 5和钛氧化物中的一种或多种 The metal oxide includes SnO, SnO 2 , PbO, Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 One or more of O 4 , Bi 2 O 5 and titanium oxide
所述导电聚合物包括聚乙炔。The conductive polymer includes polyacetylene.
在一些实施例中，所述负极还包括负极粘结剂和负极导电剂。In some embodiments, the negative electrode further includes a negative electrode binder and a negative electrode conductive agent.
所述固态锂离子电池由于采用了如上所述的固态电解质，具有较好的循环稳定性，能够有效避免锂枝晶引起的电池短路和极化电压提高。Since the solid-state lithium ion battery adopts the solid electrolyte as described above, it has better cycle stability and can effectively avoid battery short circuit and increase in polarization voltage caused by lithium dendrites.
以下通过实施例对本发明进行进一步的说明。The present invention will be further illustrated by the following examples.
实施例1Example 1
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括以下的操作步骤：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including the following operation steps:
聚合物固态电解质的制备：Preparation of polymer solid electrolyte:
采用的添加剂为化合物1，将1.0g重均分子量为60W的聚环氧乙烷(PEO)、0.41g LiN(SO 2CF 3) 2溶解于5g乙腈中，再加入0.029g化合物1，搅拌至固体完全溶解。将所得聚合物溶液置于涂布机上，用刮刀自动刮涂，常温真空干燥8h，再于80℃真空下干燥12h，得到40μm的聚合物固态电解质。电解质中的化合物1含量占电解质总重量的2％。 The additive used is compound 1. Dissolve 1.0 g of polyethylene oxide (PEO) with a weight average molecular weight of 60W and 0.41 g of LiN(SO 2 CF 3 ) 2 in 5 g of acetonitrile, then add 0.029 g of compound 1 and stir until The solid is completely dissolved. The obtained polymer solution was placed on a coating machine, automatically scraped with a doctor blade, dried in vacuum at room temperature for 8 hours, and then dried in vacuum at 80° C. for 12 hours to obtain a polymer solid electrolyte of 40 μm. The content of compound 1 in the electrolyte accounts for 2% of the total weight of the electrolyte.
固态锂离子电池的制备：Preparation of solid-state lithium-ion batteries:
正极：将LiFePO 4活性材料、导电炭黑、上述聚合物电解质以80:10:10的质量比混合，加入环己酮，搅拌至混合均匀。将上述所得的浆料均匀地涂敷在铝箔上，先在80℃下烘干至无明显液体，再于100℃真空下干燥12h。 Positive electrode: Mix LiFePO 4 active material, conductive carbon black, and the above polymer electrolyte in a mass ratio of 80:10:10, add cyclohexanone, and stir until the mixture is uniform. The slurry obtained above was evenly coated on the aluminum foil, dried at 80°C until there was no obvious liquid, and then dried at 100°C under vacuum for 12 hours.
负极：采用锂金属作为负极。Negative electrode: Lithium metal is used as the negative electrode.
固态锂离子电池的制备：按照负极壳-弹片-垫片-负极-聚合物固态电解质-正极-正极壳的顺序组装2032扣式电池。Preparation of solid-state lithium-ion battery: Assemble 2032 button batteries in the order of negative electrode shell-shrapnel-gasket-negative electrode-polymer solid electrolyte-positive electrode-positive electrode shell.
实施例2Example 2
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用聚碳酸丙烯酯(PPC)替代实施例1中的聚环氧乙烷(PEO)。Polypropylene carbonate (PPC) was used instead of polyethylene oxide (PEO) in Example 1.
实施例3Example 3
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用LiCF 3SO 3替代实施例1中的锂盐LiN(SO 2CF 3) 2。 LiCF 3 SO 3 is used instead of the lithium salt LiN(SO 2 CF 3 ) 2 in Example 1.
实施例4Example 4
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
所述“聚合物固态电解质的制备”操作中，往聚合物溶液中加入0.1656g纳米氧化铝，纳米氧化铝尺寸为8～12nm，d50＝10nm，并进行超声分散，超声分散后，固态电解质溶液置于聚四氟乙烯模板中干燥，常温挥发4h，再60℃真空干燥6h，得到固态聚合物电解质。In the "preparation of polymer solid electrolyte" operation, 0.1656 g of nano alumina is added to the polymer solution, the size of the nano alumina is 8-12nm, d50=10nm, and ultrasonic dispersion is performed. After ultrasonic dispersion, the solid electrolyte solution Place it in a polytetrafluoroethylene template for drying, volatilize at room temperature for 4 hours, and then vacuum dry at 60°C for 6 hours to obtain a solid polymer electrolyte.
实施例5Example 5
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
所述“聚合物固态电解质的制备”操作中，在固态电解质溶液配置完成后，获取细菌纤维素膜，该细菌纤维素膜的孔隙率通过阿基米德法计算为85vol％，固态电解质溶液浸润到细菌纤维素膜中，常温挥发溶剂后再浸润该固态电解质溶液，重复该操作至孔隙完全被聚合物填充后，60℃真空干燥6h，得到固态电解质，固态电解质膜的平均厚度为52μm。In the "preparation of polymer solid electrolyte" operation, after the configuration of the solid electrolyte solution is completed, a bacterial cellulose membrane is obtained. The porosity of the bacterial cellulose membrane is calculated to be 85 vol% by Archimedes method, and the solid electrolyte solution is infiltrated In the bacterial cellulose membrane, volatilize the solvent at room temperature and then infiltrate the solid electrolyte solution, repeat the operation until the pores are completely filled with polymer, and then vacuum dry at 60°C for 6 hours to obtain a solid electrolyte. The average thickness of the solid electrolyte membrane is 52 μm.
实施例6Example 6
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例3中大部分操作步骤，其不同之处在于：This embodiment is used to describe the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 3. The difference lies in:
采用LiFe 0.5Mn 0.5PO 4替代实施例1中的正极活性材料LiFePO 4。 LiFe 0.5 Mn 0.5 PO 4 was used instead of the positive electrode active material LiFePO 4 in Example 1.
实施例7Example 7
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用结构式为
Figure PCTCN2020136014-appb-000007
的化合物3替换实施例1中的化合物1。 The structural formula is
Figure PCTCN2020136014-appb-000007
Compound 3 of replaces Compound 1 in Example 1.
实施例8Example 8
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用结构式为
Figure PCTCN2020136014-appb-000008
的化合物4替换实施例1中的化合物1。 The structural formula is
Figure PCTCN2020136014-appb-000008
Compound 4 of replaces Compound 1 in Example 1.
实施例9Example 9
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用结构式为
Figure PCTCN2020136014-appb-000009
的化合物8替换实施例1中的化合物1。 The structural formula is
Figure PCTCN2020136014-appb-000009
Compound 8 of replaces Compound 1 in Example 1.
实施例10Example 10
本实施例用于说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This embodiment is used to illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in embodiment 1, and the difference lies in:
采用结构式为
Figure PCTCN2020136014-appb-000010
的化合物9替换实施例1中的添加剂。 The structural formula is
Figure PCTCN2020136014-appb-000010
The compound 9 replaces the additive in Example 1.
对比例1Comparative example 1
本对比例用于对比说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例1中大部分操作步骤，其不同之处在于：This comparative example is used to compare and illustrate the preparation method of the solid-state electrolyte and solid-state lithium-ion battery disclosed in the present invention, including most of the operation steps in Example 1, and the difference lies in:
所述“聚合物固态电解质的制备”操作中，往聚合物溶液中不加入结构式1所示化合物。In the "preparation of polymer solid electrolyte" operation, the compound represented by structural formula 1 is not added to the polymer solution.
对比例2Comparative example 2
本对比例用于对比说明本发明公开的固态电解质及固态锂离子电池的制备方法，包括实施例6中大部分操作步骤，其不同之处在于：This comparative example is used to compare and illustrate the preparation method of the solid electrolyte and solid lithium ion battery disclosed in the present invention, including most of the operation steps in Example 6, and the difference lies in:
所述“聚合物固态电解质的制备”操作中，往聚合物溶液中不加入结构式1所示化合物。In the "preparation of polymer solid electrolyte" operation, the compound represented by structural formula 1 is not added to the polymer solution.
性能测试Performance Testing
对上述实施例1～10和对比例1、2制备得到的固态电解质及固态锂离子电池行如下性能测试：The following performance tests were performed on the solid electrolytes and solid lithium ion batteries prepared in the foregoing Examples 1-10 and Comparative Examples 1 and 2:
在蓝电测试仪上对上述实施例1～10和对比例1、2制备得到的固态锂离子电池进行充放电的循环测试，测试温度为60℃。其中实施例1～5、7～10和对比例1的固态锂离子电池以0.2C的电流充电至3.8V，再恒压充电至电流下降至0.20mA，再以0.2C的电流恒流放电至2.8V，循环200周；实施例6和对比例2的固态锂离子电池以0.2C的电流充电至4.2V，再恒压充电至电流下降至0.20mA，再以0.2C的电流放电至3.0V，循环200周，根据公式“容量保持率＝第300周的放电容量/第1周的放电容量×100％”，计算出电池的容量保持率。根据公式“库伦效率＝每一周的放电容量/每一周的充电容量×100％”，计算出电池的首圈库伦效率，以及循环N周的平均库伦效率＝N周库伦效率的总和/N，The solid-state lithium ion batteries prepared in the foregoing Examples 1-10 and Comparative Examples 1 and 2 were subjected to a charge-discharge cycle test on a blue power tester, and the test temperature was 60°C. Among them, the solid-state lithium ion batteries of Examples 1 to 5, 7 to 10 and Comparative Example 1 were charged to 3.8V at a current of 0.2C, then charged at a constant voltage until the current dropped to 0.20mA, and then discharged at a constant current of 0.2C to 2.8V, cycle 200 weeks; the solid-state lithium-ion batteries of Example 6 and Comparative Example 2 were charged to 4.2V at a current of 0.2C, then charged at a constant voltage until the current dropped to 0.20mA, and then discharged at a current of 0.2C to 3.0V , Cycle for 200 weeks, and calculate the capacity retention rate of the battery according to the formula "capacity retention rate=discharge capacity in the 300th week/discharge capacity in the first week×100%". According to the formula "Coulomb efficiency=discharge capacity per week/charge capacity per week×100%", calculate the first cycle coulomb efficiency of the battery and the average coulomb efficiency during N cycles = the sum of N cycles coulomb efficiency/N,
得到的测试结果填入表1。Fill in Table 1 with the test results obtained.
表1Table 1
Figure PCTCN2020136014-appb-000011
Figure PCTCN2020136014-appb-000011
Figure PCTCN2020136014-appb-000012
Figure PCTCN2020136014-appb-000012
对比表1中对比例1和实施例1的测试结果可以看出，当固态电解质中添加2wt％的化合物1作为添加剂后，虽然实施例1的首周库伦效率低于对比例1，但是其循环平均库伦效率要远高于对比例1，这主要是因为添加剂在首周参与了负极表面发生电化学反应，在金属锂表面生成一层新的界面层。对比例1在循环120周时发生短路，这是由于金属锂枝晶生长刺穿电解质引起短路，而实施例1在循环480周后容量保持率在80％以上。同样实施例6与对比例2的数据也同样验证了上述结论。Comparing the test results of Comparative Example 1 and Example 1 in Table 1, it can be seen that when 2wt% of Compound 1 is added as an additive to the solid electrolyte, although the first week Coulomb efficiency of Example 1 is lower than that of Comparative Example 1, its cycle The average Coulombic efficiency is much higher than that of Comparative Example 1. This is mainly because the additive has participated in the electrochemical reaction on the surface of the negative electrode in the first week, forming a new interface layer on the surface of the lithium metal. In Comparative Example 1, a short circuit occurred during 120 cycles of cycling, which was caused by the growth of metal lithium dendrites piercing the electrolyte, and the capacity retention rate of Example 1 was over 80% after cycling for 480 weeks. Similarly, the data of Example 6 and Comparative Example 2 also verify the above conclusion.
对比实施例1～实施例10的电池性能结果可以看出，采用本发明所述的固态聚合物电解质制备的电池在60℃时0.2C循环平均库伦效率为98.2％以上，以LiFePO 4为正极的电池，0.2C循环的容量保持率在80％以上循环周数在456周以上，说明添加剂的加入对于抑制锂枝晶的生成，延长固态锂离子电池的寿命具有重要作用。从实施例6和对比例2的测试结果可以看出，采用不同正极材料，如LiFe 0.5Mn 0.5PO 4作为正极材料时，固态锂离子电池的循环性能同样具有显著提高，说明本发明提供的固态电解质适用于不同的正极材料体系。对比实施例1和实施例5可以发现电解质中引入多孔骨架时，电池循环容量保持率在80％以上的循环周数有所提升，这是由于多孔骨架的引入提升了电解质的机械强度，降低了电解质的玻璃化转变问题，更有效的抑制了负极枝晶生长。 Comparing the battery performance results of Examples 1 to 10, it can be seen that the battery prepared by the solid polymer electrolyte of the present invention has an average Coulombic efficiency of 98.2% or more at 0.2C cycle at 60°C, and LiFePO 4 is used as the positive electrode. For the battery, the capacity retention rate of 0.2C cycle is above 80% and the number of cycle cycles is above 456 weeks, indicating that the addition of additives plays an important role in inhibiting the formation of lithium dendrites and extending the life of solid-state lithium-ion batteries. It can be seen from the test results of Example 6 and Comparative Example 2 that when different cathode materials, such as LiFe 0.5 Mn 0.5 PO 4, are used as the cathode material, the cycle performance of the solid-state lithium-ion battery is also significantly improved, indicating that the solid-state battery provided by the present invention The electrolyte is suitable for different cathode material systems. Comparing Example 1 and Example 5, it can be found that when a porous framework is introduced into the electrolyte, the cycle capacity retention rate of the battery is increased over 80%. This is because the introduction of the porous framework increases the mechanical strength of the electrolyte and reduces The glass transition problem of the electrolyte more effectively inhibits the growth of negative electrode dendrites.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。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 (10)

  1. 一种固态电解质，其特征在于，包括聚合物和添加剂，所述添加剂包括以下结构式1所示的化合物：A solid electrolyte, characterized in that it comprises a polymer and an additive, and the additive comprises a compound represented by the following structural formula 1:
    Figure PCTCN2020136014-appb-100001
    Figure PCTCN2020136014-appb-100001
    其中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟或含1-5个碳原子基团。 Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, or a group containing 1-5 carbon atoms.
  2. 根据权利要求1所述的固态电解质，其特征在于，所述添加剂分散于固态电解质的表面和内部。The solid electrolyte according to claim 1, wherein the additive is dispersed on the surface and inside of the solid electrolyte.
  3. 根据权利要求1所述的固态电解质，其特征在于，所述含1-5个碳原子的基团选自烃基、氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。The solid electrolyte according to claim 1, wherein the group containing 1 to 5 carbon atoms is selected from the group consisting of a hydrocarbyl group, a fluorinated hydrocarbyl group, an oxygen-containing hydrocarbyl group, a silicon-containing hydrocarbyl group, or a cyano-substituted hydrocarbyl group.
  4. 根据权利要求1所述的固态电解质，其特征在于，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢、氟、甲基、乙基、三甲基硅氧基、氰基或三氟甲基。 The solid electrolyte according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from hydrogen, fluorine, methyl, ethyl, trimethyl silicon Oxy, cyano or trifluoromethyl.
  5. 根据权利要求1所述的固态电解质，其特征在于，所述结构式1所示的化合物选自于如下所示化合物中的一种或多种：The solid electrolyte according to claim 1, wherein the compound represented by the structural formula 1 is selected from one or more of the following compounds:
    Figure PCTCN2020136014-appb-100002
    Figure PCTCN2020136014-appb-100002
    Figure PCTCN2020136014-appb-100003
    Figure PCTCN2020136014-appb-100003
  6. 根据权利要求1-5任一项所述的固态电解质，其特征在于，以所述固态电解质的总质量为100％计，所述结构式1所示的化合物的质量百分含量为0.01～20％。The solid electrolyte according to any one of claims 1 to 5, characterized in that, based on the total mass of the solid electrolyte as 100%, the mass percentage of the compound represented by structural formula 1 is 0.01-20% .
  7. 根据权利要求6所述的固态电解质，其特征在于，所述聚合物为极性聚合物，所述聚合物包括环氧烷烃类单体、硅氧烷类单体、烯烃类单体、丙烯酸酯类单体、羧酸酯类单体、碳酸酯类单体、酰胺类单体、腈类单体中的至少一种聚合得到的聚合物及其卤代物；The solid electrolyte according to claim 6, wherein the polymer is a polar polymer, and the polymer includes alkylene oxide monomers, siloxane monomers, olefin monomers, and acrylates. A polymer obtained by polymerization of at least one of a type monomer, a carboxylic acid ester type monomer, a carbonate type monomer, an amide type monomer, and a nitrile type monomer, and a halogenated substance thereof;
    以所述固态电解质的总质量为100％计，所述聚合物的质量百分含量为10-90％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the polymer is 10-90%.
  8. 根据权利要求7所述的固态电解质，其特征在于，所述固态电解质还包括有溶剂，所述溶剂包括碳酸酯、羧酸酯、氟代溶剂中的一种或多种；8. The solid electrolyte according to claim 7, wherein the solid electrolyte further comprises a solvent, and the solvent comprises one or more of carbonate, carboxylate, and fluorinated solvent;
    以所述固态电解质的总质量为100％计，所述溶剂的质量百分含量为0～10％。Based on the total mass of the solid electrolyte as 100%, the mass percentage of the solvent is 0-10%.
  9. 一种固态锂离子电池，其特征在于，包括正极、负极和如权利要求1～8任意一项所述的固态电解质，所述固态电解质位于所述正极和所述负极之间。A solid-state lithium ion battery, characterized by comprising a positive electrode, a negative electrode, and the solid electrolyte according to any one of claims 1 to 8, and the solid electrolyte is located between the positive electrode and the negative electrode.
  10. 根据权利要求9所述的固态锂离子电池，其特征在于，所述负极包括负极活性材料，所述负极活性材料包括钛酸锂、碳材料、Li XFe 2O 3、Li yWO 2、锂金属、锂合金、硅系合金、锡系合金、金属氧化物、导电聚合物、Li-Co-Ni基材料中的一种或多种，其中，0≤x≤1，0≤y≤1； The solid-state lithium ion battery according to claim 9, wherein the negative electrode comprises a negative electrode active material, and the negative electrode active material comprises lithium titanate, carbon material, Li X Fe 2 O 3 , Li y WO 2 , lithium One or more of metals, lithium alloys, silicon-based alloys, tin-based alloys, metal oxides, conductive polymers, and Li-Co-Ni-based materials, where 0≤x≤1, 0≤y≤1;
    优选地，所述负极活性材料为锂金属。Preferably, the negative electrode active material is lithium metal.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117913351A (en) * 2024-03-19 2024-04-19 蜂巢能源科技股份有限公司 All-solid-state battery and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07165751A (en) * 1993-03-31 1995-06-27 Nippon Oil Co Ltd Organic solvent and electrolytic solution
JP2000260467A (en) * 1999-03-08 2000-09-22 Sanyo Chem Ind Ltd Non-aqueous electrolyte liquid and secondary battery using it
US20020102464A1 (en) * 2000-12-06 2002-08-01 Hiroshi Yoshida Polymer gel electrolyte, secondary cell, and electrical double-layer capacitor
JP2015092476A (en) * 2013-10-04 2015-05-14 旭化成株式会社 Nonaqueous electrolyte, electrolyte for lithium ion secondary batteries and nonaqueous electrolyte battery
CN107591557A (en) * 2016-07-08 2018-01-16 深圳新宙邦科技股份有限公司 A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3557477B2 (en) * 1995-04-25 2004-08-25 昭和電工株式会社 Polymer solid electrolyte, battery and solid electric double layer capacitor using the same, method for producing them, and polymer solid electrolyte material
JP5233024B2 (en) * 2001-07-02 2013-07-10 パイオトレック株式会社 Solid lithium battery
KR100657225B1 (en) * 2003-09-05 2006-12-14 주식회사 엘지화학 Electrolyte solvent for improving safety of battery and lithium secondary battery comprising the same
JPWO2016039118A1 (en) * 2014-09-09 2017-05-25 ダイキン工業株式会社 Electrolyte and novel fluorinated phosphate ester
US10497968B2 (en) * 2016-01-04 2019-12-03 Global Graphene Group, Inc. Solid state electrolyte for lithium secondary battery
CN109273760A (en) * 2018-09-30 2019-01-25 淮安新能源材料技术研究院 A kind of lithium ion cell electrode piece and coating method with solid-state electrolyte layer
CN109768320B (en) * 2018-12-19 2021-05-07 南方科技大学 All-solid-state polymer electrolyte, preparation method thereof and all-solid-state lithium ion battery
CN110137566B (en) * 2019-05-21 2021-06-08 哈尔滨工业大学 Method for inhibiting lithium dendrite on solid electrolyte interface and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07165751A (en) * 1993-03-31 1995-06-27 Nippon Oil Co Ltd Organic solvent and electrolytic solution
JP2000260467A (en) * 1999-03-08 2000-09-22 Sanyo Chem Ind Ltd Non-aqueous electrolyte liquid and secondary battery using it
US20020102464A1 (en) * 2000-12-06 2002-08-01 Hiroshi Yoshida Polymer gel electrolyte, secondary cell, and electrical double-layer capacitor
JP2015092476A (en) * 2013-10-04 2015-05-14 旭化成株式会社 Nonaqueous electrolyte, electrolyte for lithium ion secondary batteries and nonaqueous electrolyte battery
CN107591557A (en) * 2016-07-08 2018-01-16 深圳新宙邦科技股份有限公司 A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery using the electrolyte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117913351A (en) * 2024-03-19 2024-04-19 蜂巢能源科技股份有限公司 All-solid-state battery and preparation method thereof

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