WO2024230010A1 - 交联聚合物固态电解质及其制备方法和应用 - Google Patents

交联聚合物固态电解质及其制备方法和应用 Download PDF

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WO2024230010A1
WO2024230010A1 PCT/CN2023/114795 CN2023114795W WO2024230010A1 WO 2024230010 A1 WO2024230010 A1 WO 2024230010A1 CN 2023114795 W CN2023114795 W CN 2023114795W WO 2024230010 A1 WO2024230010 A1 WO 2024230010A1
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cross
solid electrolyte
linked polymer
polymer solid
lithium
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French (fr)
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田雷
母可心
朱才镇
徐坚
刘会超
于佳立
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Shenzhen University
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Shenzhen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/302—General preparatory processes using carbonates and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of new energy materials, and in particular to a cross-linked polymer solid electrolyte and a preparation method and application thereof.
  • lithium-ion batteries are widely used in electronic equipment, new energy electric vehicles, large-scale energy storage and other fields.
  • Conventional lithium-ion batteries use flammable liquid electrolytes, which have potential safety hazards, especially in sudden situations such as puncture, impact, and high temperature, electrolyte leakage may occur, which may cause safety accidents; therefore, non-flammable solid electrolytes have begun to replace the use of liquid electrolytes.
  • the main purpose of the present application is to provide a cross-linked polymer solid electrolyte and a preparation method and application thereof, aiming to solve the technical problems of large impedance and low ion conductivity of conventional solid electrolytes.
  • the present application provides a method for preparing a cross-linked polymer solid electrolyte, the method for preparing the cross-linked polymer solid electrolyte comprising the following steps:
  • the quasi-solid electrolyte precursor liquid is allowed to stand to obtain a cross-linked polymer solid electrolyte.
  • the lithium salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium iodide (LiI), lithium bis(oxalatoborate) (LiBOB) and lithium hexafluoroarsenate (LiAsF6), wherein the concentration of the lithium salt is at least 0.1 mol/L and not more than 10 mol/L.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiI lithium iodide
  • LiBOB lithium bis(oxalatoborate)
  • LiAsF6 lithium hexafluoroarsenate
  • the organic solvent includes one or more of ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), toluene, N-methylpyrrolidone and 4-methyl-1,3-dioxolane.
  • DME ethylene glycol dimethyl ether
  • THF tetrahydrofuran
  • DMF N,N-dimethylformamide
  • toluene N-methylpyrrolidone
  • 4-methyl-1,3-dioxolane 4-methyl-1,3-dioxolane.
  • the cyclic ether monomer includes one or more of 1,3-dioxolane (DOL), polyethylene glycol dimethyl ether (NHD), fluoroethylene carbonate (FEC) and vinylene carbonate (VC).
  • DOL 1,3-dioxolane
  • NHS polyethylene glycol dimethyl ether
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • the initiator includes one or more of lithium hexafluorophosphate (LiPF6), tin fluoride (SnF4), magnesium trifluoromethanesulfonate (Mg(OTf)2), 1-hydroxycyclohexyl phenyl ketone, Lewis acid and aluminum trifluoromethanesulfonate (Al(OTf)3), wherein the concentration of the initiator is at least 0.1 mol/L and not more than 5 mol/L.
  • LiPF6 lithium hexafluorophosphate
  • SnF4 tin fluoride
  • Mg(OTf)2 magnesium trifluoromethanesulfonate
  • Al(OTf)3 Lewis acid and aluminum trifluoromethanesulfonate
  • the cross-linking agent includes one or more of pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, Y-glycidyl ether silyl propyl sesquioxane and trimethylolpropane triglycidyl ether, wherein the content of the cross-linking agent is at least 1 wt.% and not more than 30 wt.%.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:10 to 10:1.
  • the standing temperature of the quasi-solid electrolyte precursor liquid is at least 15° C. and not more than 60° C.
  • the standing time is at least 0.5 h and not more than 72 h.
  • the present application also provides a cross-linked polymer solid electrolyte, which is prepared by the cross-linked polymer solid electrolyte preparation method.
  • the present application also provides an application of a cross-linked polymer solid electrolyte, wherein the cross-linked polymer solid electrolyte is prepared by the above-mentioned preparation method of the cross-linked polymer solid electrolyte, and the application of the cross-linked polymer solid electrolyte in the preparation of a lithium metal battery.
  • the present application discloses a cross-linked polymer solid electrolyte and a preparation method and application thereof, wherein a lithium salt is dissolved in an organic solvent to obtain a liquid electrolyte; a cyclic ether monomer, an initiator and a cross-linking agent are added to the liquid electrolyte and stirred until uniform, thereby obtaining a quasi-solid electrolyte precursor liquid; the quasi-solid electrolyte precursor liquid is allowed to stand to allow the quasi-solid precursor liquid to gradually solidify, thereby obtaining a cross-linked polymer solid electrolyte with low impedance and high ionic conductivity; in the present application, the addition of the initiator causes the cyclic ether monomer to undergo in-situ ring-opening polymerization to form a linear polymer, and the added cross-linking agent is connected to the cyclic ether monomer through the ring opening, thereby further causing the linear polymer to cross-link to form a huge three-dimensional hybrid cross-linked network, thereby
  • the preparation method is simple and can utilize the existing liquid electrolyte production process without increasing equipment investment, so it has prospects for industrialization. It reduces hydrogen bonds through cross-linking, thereby increasing the activity of polymer chain segments, improving the ionic conductivity of the solid electrolyte, and significantly reduces the impedance of the electrolyte through the synergistic effect between the components, so that the solid electrolyte can be discharged at a high rate like a liquid electrolyte, and the solid electrolyte maintains good interface contact with the battery electrodes, thereby improving the safety and cycle stability of the battery.
  • FIG1 is a schematic flow chart of a method for preparing a cross-linked polymer solid electrolyte according to an embodiment of the present application
  • FIG2 is an AC impedance test diagram of the embodiment and the comparative example of the present application.
  • FIG3 is a test diagram of the relationship between ionic conductivity and temperature in Example 1 of the present application.
  • FIG4 is a test diagram of the relationship between ionic conductivity and temperature in Example 2 of the present application.
  • FIG5 is a test diagram of the relationship between ionic conductivity and temperature of Example 3 of the present application.
  • FIG6 is a graph showing the stability performance of symmetrical batteries prepared in Example 1 and Comparative Example 1 of the present application;
  • FIG7 is a graph showing the stability performance test of the symmetrical batteries prepared in Example 2 and Comparative Example 1 of the present application;
  • FIG8 is a graph showing the stability performance test of the symmetrical batteries prepared in Example 3 and Comparative Example 1 of the present application;
  • FIG9 is a cycle performance test diagram of the battery prepared in Example 1 of the present application.
  • FIG10 is a cycle performance test diagram of the battery prepared in Example 2 of the present application.
  • FIG11 is a cycle performance test diagram of the battery prepared in Example 3 of the present application.
  • FIG12 is a first cycle charge and discharge test diagram of the battery prepared in Example 1 of the present application.
  • FIG13 is a graph showing the lithium ion migration number of Comparative Example 1 of the present application.
  • FIG14 is a graph showing the lithium ion migration number of Example 1 of the present application.
  • FIG15 is a graph showing the lithium ion migration number of Example 2 of the present application.
  • FIG16 is a graph showing the lithium ion migration number of Example 3 of the present application.
  • FIG17 is a linear sweep voltammogram of Examples 1-3 of the present application.
  • FIG18 is a schematic diagram of the polymer network structure of Example 1 of the present application.
  • FIG19 is a schematic diagram of the polymer network structure of Example 2 of the present application.
  • Figure 20 is a schematic diagram of the polymer network structure of Example 3 of the present application.
  • the meaning of "and/or” appearing in the full text includes three parallel solutions. Taking “A and/or B” as an example, it includes solution A, solution B, or a solution that satisfies both A and B.
  • the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in this field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by this application. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.
  • Lithium-ion batteries are used in all aspects of people's lives, such as mobile phones, computers, electric vehicles, and various power tools.
  • the safety risks and endurance issues of lithium-ion batteries have prompted people to seek new batteries with high safety and high specific energy.
  • Conventional lithium-ion batteries mostly use electrolytes, using organic ether or organic ester electrolytes to dissolve lithium salts, and achieve safe and long cycles of lithium-ion batteries by adding film-forming protective agents.
  • carbonates are a type of organic solvent with a high dielectric constant and a wide electrochemical window, and are currently one of the most widely used lithium-ion battery solvents.
  • organic solvents include: diethyl carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, etc.
  • this type of organic solvent is easy to volatilize and flammable, and there are great safety hazards; at the same time, the addition of organic electrolytes increases the overall proportion of inactive substances in the battery, resulting in a decrease in the overall specific energy of the lithium-ion battery, and a large amount of organic ester or organic ether electrolytes are prone to short circuits inside the battery, which can easily cause fires and cause serious safety accidents.
  • non-flammable solid electrolytes have begun to replace liquid electrolytes.
  • conventional solid electrolytes have large impedance and low ion conductivity (about 10-7S cm-1). When used in batteries, they cause a large number of internal microcracks to form in the later stages of the battery cycle due to the continuous expansion and contraction of the positive and negative electrodes, resulting in rapid battery failure and poor cycle stability.
  • the present application proposes a cross-linked polymer solid electrolyte and a preparation method and application thereof, wherein a lithium salt is dissolved in an organic solvent to obtain a liquid electrolyte; a cyclic ether monomer, an initiator and a cross-linking agent are then added to the liquid electrolyte and stirred until uniform; the addition of the initiator causes the monomer to undergo in-situ ring-opening polymerization to form a linear polymer, and the addition of the cross-linking agent further causes the linear polymer to cross-link into a three-dimensional network polymer, thereby obtaining a quasi-solid electrolyte precursor liquid; the quasi-solid electrolyte precursor liquid is then allowed to stand, so that the quasi-solid precursor liquid gradually solidifies to obtain a cross-linked polymer solid electrolyte; the preparation method has a simple process and can utilize the existing liquid electrolyte production process without increasing equipment investment, and has industrial prospects; hydrogen bonds are reduced by cross-linking, thereby increasing
  • a first aspect of an embodiment of the present application provides a method for preparing a cross-linked polymer solid electrolyte, the preparation method comprising the following steps:
  • Step S10 dissolving lithium salt in an organic solvent to obtain a liquid electrolyte
  • the lithium salt is added into the organic solvent and stirred until the lithium salt is completely dissolved to obtain a liquid electrolyte.
  • the lithium salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium iodide (LiI), lithium bis(oxalatoborate) (LiBOB) and lithium hexafluoroarsenate (LiAsF 6 ), wherein the concentration of the lithium salt is at least 0.1 mol/L and not more than 10 mol/L.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiI lithium iodide
  • LiBOB lithium bis(oxalatoborate)
  • LiAsF 6 lithium hexafluoroarsenate
  • the metal salt can be adaptively modified, and the lithium salt can be replaced with the metal salt of the corresponding metal battery; for sodium ion batteries, the lithium salt can be replaced with the sodium salt, and so on.
  • the organic solvent includes: one or more of ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), 1,2-dimethoxypropane (DMP), toluene, N-methylpyrrolidone and 4-methyl-1,3-dioxolane.
  • DME ethylene glycol dimethyl ether
  • THF tetrahydrofuran
  • DMF N,N-dimethylformamide
  • DMP 1,2-dimethoxypropane
  • toluene N-methylpyrrolidone
  • 4-methyl-1,3-dioxolane 4-methyl-1,3-dioxolane.
  • the organic solvent includes one or more of ethylene glycol dimethyl ether (DME) and 1,2-dimethoxypropane (DMP).
  • DME ethylene glycol dimethyl ether
  • DMP 1,2-dimethoxypropane
  • Step S20 adding a cyclic ether monomer, an initiator and a cross-linking agent into the liquid electrolyte and stirring until uniform, to obtain a quasi-solid electrolyte precursor liquid;
  • Cyclic ether monomers, initiators and cross-linking agents are added into the liquid electrolyte and stirred until uniform to obtain a quasi-solid electrolyte precursor liquid.
  • the cyclic ether monomer includes: one or more of 1,3-dioxolane (DOL), polyethylene glycol dimethyl ether (NHD), fluoroethylene carbonate (FEC) and vinylene carbonate (VC).
  • DOL 1,3-dioxolane
  • NHS polyethylene glycol dimethyl ether
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • the cyclic ether monomer includes: 1,3-dioxolane (DOL).
  • DOL 1,3-dioxolane
  • the initiator includes one or more of lithium hexafluorophosphate (LiPF 6 ), tin fluoride (SnF 4 ), magnesium trifluoromethanesulfonate (Mg(OTf) 2 ), 1-hydroxycyclohexyl phenyl ketone, Lewis acid and aluminum trifluoromethanesulfonate (Al(OTf) 3 ), wherein the concentration of the initiator is at least 0.1 mol/L and not more than 5 mol/L.
  • LiPF 6 lithium hexafluorophosphate
  • SnF 4 tin fluoride
  • Mg(OTf) 2 magnesium trifluoromethanesulfonate
  • Al(OTf) 3 Lewis acid and aluminum trifluoromethanesulfonate
  • the initiator includes: lithium hexafluorophosphate (LiPF 6 ).
  • the cross-linking agent includes: one or more of pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, Y-glycidyl ether silyl propyl sesquioxane and trimethylolpropane triglycidyl ether, wherein the content of the cross-linking agent is at least 1 wt.% and not more than 30 wt.%.
  • the cross-linking agent includes: pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether and Y-glycidyl ether silylpropyl sesquioxane.
  • the cross-linking agent can serve as a cross-linking center, and form a unit structure by connecting to the cyclic ether monomer through ring opening, and then connect with the countless units formed to form a huge three-dimensional hybrid cross-linking network.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:10 to 10:1.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:5 to 5:1.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:2 to 2:1.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:1.
  • cyclic ether monomers are used to provide flexibility and interface compatibility.
  • the addition of an initiator allows the cyclic ether monomers to undergo in-situ ring-opening polymerization, thereby forming a linear polymer.
  • the addition of a cross-linking agent further allows the linear polymer to be cross-linked into a three-dimensional network polymer, thereby enhancing the structural stability.
  • the hybridization of silicon atoms in the cross-linking agent improves the thermal stability of the solid electrolyte, reduces the crystallinity of the polymer matrix, and thereby improves the ionic conductivity of the solid electrolyte, ultimately obtaining a solid polymer electrolyte with high ionic conductivity, low interface impedance and high stability.
  • Step S30 allowing the quasi-solid electrolyte precursor liquid to stand to obtain a cross-linked polymer solid electrolyte.
  • the quasi-solid electrolyte precursor liquid is allowed to stand and gradually solidify to obtain a cross-linked polymer solid electrolyte.
  • the standing temperature of the quasi-solid electrolyte precursor liquid is at least 15° C. and not more than 60° C., and the standing time is at least 0.5 h and not more than 72 h.
  • a liquid electrolyte is obtained by dissolving a lithium salt in an organic solvent; a cyclic ether monomer, an initiator and a cross-linking agent are then added to the liquid electrolyte and stirred until uniform, thereby obtaining a quasi-solid electrolyte precursor liquid; the quasi-solid electrolyte precursor liquid is then allowed to stand, so that the quasi-solid precursor liquid gradually solidifies, and a cross-linked polymer solid electrolyte with low impedance and high ionic conductivity is obtained;
  • the addition of the initiator causes the cyclic ether monomer to undergo in-situ ring-opening polymerization to form a linear polymer
  • the addition of the cross-linking agent further causes the linear polymer to cross-link into a three-dimensional network polymer, thereby enhancing the structural stability, and the hybridization of silicon atoms in the cross-linking agent improves the thermal stability of the solid electrolyte, reduces the crystallinity of the poly
  • the preparation method is simple and can utilize the existing liquid electrolyte production process without increasing equipment investment, so it has prospects for industrialization. It reduces hydrogen bonds through cross-linking, thereby increasing the activity of polymer chain segments, improving the ionic conductivity of the solid electrolyte, and significantly reduces the impedance of the electrolyte through the synergistic effect between the components, so that the solid electrolyte can be discharged at a high rate like a liquid electrolyte, and the solid electrolyte maintains good interface contact with the battery electrodes, thereby improving the safety and cycle stability of the battery.
  • a second aspect of the present application provides a cross-linked polymer solid electrolyte, wherein the cross-linked polymer solid electrolyte is prepared by the following method:
  • the quasi-solid electrolyte precursor liquid is allowed to stand to obtain a cross-linked polymer solid electrolyte.
  • the lithium salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium iodide, lithium bis(oxalatoborate) and lithium hexafluoroarsenate, wherein the concentration of the lithium salt is at least 0.1 mol/L and not more than 10 mol/L.
  • the organic solvent includes one or more of ethylene glycol dimethyl ether, tetrahydrofuran, N,N-dimethylformamide, 1,2-dimethoxypropane (DMP), toluene, N-methylpyrrolidone and 4-methyl-1,3-dioxolane.
  • the cyclic ether monomer includes one or more of 1,3-dioxolane, polyethylene glycol dimethyl ether, fluoroethylene carbonate and vinylene carbonate.
  • the initiator includes one or more of lithium hexafluorophosphate, tin fluoride, magnesium trifluoromethanesulfonate, 1-hydroxycyclohexyl phenyl ketone, Lewis acid and aluminum trifluoromethanesulfonate, wherein the concentration of the initiator is at least 0.1 mol/L and not more than 5 mol/L.
  • the cross-linking agent includes one or more of pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, Y-glycidyl ether silyl propyl sesquioxane and trimethylolpropane triglycidyl ether, wherein the content of the cross-linking agent is at least 1 wt.% and not more than 30 wt.%.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:10 to 10:1.
  • the standing temperature of the quasi-solid electrolyte precursor liquid is at least 15° C. and not more than 60° C.
  • the standing time is at least 0.5 h and not more than 72 h.
  • the third aspect of the embodiment of the present application provides an application of a cross-linked polymer solid electrolyte, and the application of the cross-linked polymer solid electrolyte in the preparation of a lithium metal battery; wherein the cross-linked polymer solid electrolyte is prepared by the following method:
  • the quasi-solid electrolyte precursor liquid is allowed to stand to obtain a cross-linked polymer solid electrolyte.
  • the lithium salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium iodide, lithium bis(oxalatoborate) and lithium hexafluoroarsenate, wherein the concentration of the lithium salt is at least 0.1 mol/L and not more than 10 mol/L.
  • the organic solvent includes one or more of ethylene glycol dimethyl ether, tetrahydrofuran, N,N-dimethylformamide, toluene, N-methylpyrrolidone and 4-methyl-1,3-dioxolane.
  • the cyclic ether monomer includes one or more of 1,3-dioxolane, polyethylene glycol dimethyl ether, fluoroethylene carbonate and vinylene carbonate.
  • the initiator includes one or more of lithium hexafluorophosphate, tin fluoride, magnesium trifluoromethanesulfonate, 1-hydroxycyclohexyl phenyl ketone, Lewis acid and aluminum trifluoromethanesulfonate, wherein the concentration of the initiator is at least 0.1 mol/L and not more than 5 mol/L.
  • the cross-linking agent includes one or more of pentaerythritol glycidyl ether, polyethylene glycol diglycidyl ether, Y-glycidyl ether silyl propyl sesquioxane and trimethylolpropane triglycidyl ether, wherein the content of the cross-linking agent is at least 1 wt.% and not more than 30 wt.%.
  • the volume ratio of the organic solvent to the cyclic ether monomer is 1:10 to 10:1.
  • the standing temperature of the quasi-solid electrolyte precursor liquid is at least 15° C. and not more than 60° C.
  • the standing time is at least 0.5 h and not more than 72 h.
  • DOL 1,3-dioxolane
  • LiPF6 lithium hexafluorophosphate
  • pentaerythritol glycidyl ether 1,3-dioxolane (DOL) with a volume ratio of 1:1 to DME, 2 mol/L lithium hexafluorophosphate (LiPF6) and 5 wt.% pentaerythritol glycidyl ether were added to the liquid electrolyte in batches and stirred until uniform to obtain a quasi-solid electrolyte precursor liquid;
  • LiPF6 lithium hexafluorophosphate
  • pentaerythritol glycidyl ether 5 wt.% pentaerythritol glycidyl ether
  • the quasi-solid electrolyte precursor solution was allowed to stand at 25 °C for 20 h to obtain a cross-linked polymer solid electrolyte.
  • the steps are the same as those in Example 1, except that the cross-linking agent added is polyethylene glycol diglycidyl ether.
  • the steps are the same as those in Example 1, except that the organic solvent added is 1,2-dimethoxypropane (DMP), and the cross-linking agent added is Y-glycidyl ether silyl propyl sesquioxane.
  • DMP 1,2-dimethoxypropane
  • Y-glycidyl ether silyl propyl sesquioxane is 1,2-dimethoxypropane
  • the prepared electrolyte was sandwiched between two stainless steel sheets and encapsulated in a CR2032 button cell.
  • steel sheet” battery was subjected to electrochemical impedance spectroscopy using a Shanghai Chenhua Electric CHI760e chemical workstation.
  • the electrolyte thickness was 50 ⁇ m, the amplitude was 5 mV, and the frequency range was 10-10 6 Hz.
  • Table 1 The results are shown in Figure 2 and Table 1:
  • the impedance of the solid electrolytes prepared in Examples 1-3 of the present application is about 2 ⁇ , which has a very small impedance; and the ionic conductivity is about 1.1 ⁇ 10-3 S ⁇ cm -1 .
  • the ionic conductivity is increased by one order of magnitude, and has a higher ionic conductivity.
  • the electrolyte prepared in Examples 1-3 was sandwiched between two stainless steel sheets and encapsulated in a CR2032 button cell.
  • steel sheet” battery was subjected to electrochemical impedance spectroscopy using Shanghai Chenhua Electric CHI760e chemical workstation.
  • the electrolyte thickness was 50 ⁇ m
  • the amplitude was 5 mV
  • the frequency range was 10-10 6 Hz
  • the experimental temperature was 25-80°C
  • the results are shown in Figures 3-5.
  • the ionic conductivity of the cross-linked polymeric solid electrolytes prepared in Examples 1-3 gradually increases with the increase of temperature, has a linear relationship with the temperature, and can maintain stable ionic conductivity at a relatively high temperature (80°C).
  • Battery assembly The solid electrolytes of Examples 1-3 and Comparative Example 1 are assembled into lithium batteries in the order of negative electrode shell, spring sheet, gasket, lithium metal, diaphragm, precursor liquid, lithium iron phosphate, lithium metal to positive electrode shell; after assembly, they are pressed and sealed, and the battery is left at room temperature for 24 hours to ensure the in-situ solidification of the precursor liquid; after standing, a 1C rate performance test is carried out, and the test results are shown in Figures 6-8, (a) is the voltage change curve of the cycle 0-800 h, and (b) is a local enlarged view of 795-800 h in (a).
  • the solid-state symmetrical batteries prepared in Examples 1-3 can be charged and discharged at extremely low overpotentials. After cycling to 800 h, the voltage polarization is still stable, showing very stable lithium deposition and dissolution behavior. Therefore, when the cross-linked polymer solid electrolyte prepared in this application is used in a battery, the battery exhibits excellent stability.
  • the solid-state symmetrical battery prepared in Comparative Example 1 has a larger overpotential, reaching about 420 mV at 800 h. The continuously increasing overpotential indicates that the uneven lithium plating/de-lithiation phenomenon is aggravated during the cycle.
  • Positive electrode preparation 0.4g lithium iron phosphate, 0.05g conductive carbon black, and 0.05g polyvinylidene fluoride were added to 1.5 mL N-methylpyrrolidone (NMP), mixed and stirred at room temperature for 24 h, and then coated on a 20-micron thick aluminum foil, and vacuum dried at 80 °C for 24 h.
  • NMP N-methylpyrrolidone
  • the electrode was cut into discs with a diameter of 14 mm, and the loading of active material lithium iron phosphate was 2.0 mg cm –2 .
  • Battery assembly The solid electrolytes prepared in Examples 1-3 were assembled into batteries in the order of negative electrode shell, spring sheet, gasket, lithium metal, diaphragm, precursor liquid, lithium iron phosphate, positive electrode, and positive electrode shell. After assembly, the batteries were pressed and sealed. The batteries were left standing at room temperature for 24 hours to ensure the in-situ solidification of the precursor liquid to obtain: lithium iron phosphate
  • the cross-linked polymer solid electrolyte batteries prepared in Examples 1-3 have excellent cycle performance. After 300 cycles, the capacities are 144.4 mAh/g, 144.9 mAh/g and 140.4 mAh/g, respectively; therefore, the cross-linked polymer electrolyte batteries prepared in this application have excellent cycle stability and high capacity.
  • the first-cycle charge and discharge test was carried out on the LFP
  • the first-cycle charge and discharge platform of the prepared polymer solid electrolyte battery is stable at a rate of 1C, and has a high first-cycle capacity of 165 mA/g (theoretical 170 mAh/g).
  • the cross-linked polymer solid electrolytes prepared in Examples 1-3 and Comparative Example 1 were tested for lithium ion migration numbers, and the test results are shown in Figures 13-16.
  • the lithium ion migration number of Comparative Example 1 is 0.34; referring to Figure 14, the lithium ion migration number of Example 1 is 0.81; referring to Figure 15, the lithium ion migration number of Example 2 is 0.55; referring to Figure 16, the lithium ion migration number of Example 3 is 0.88; therefore, the cross-linked polymer solid electrolyte prepared in the present application has the function of limiting anions, thereby reducing the polarization of battery charging and discharging, which is beneficial to the transfer of lithium ions.
  • the electrochemical stability window of the cross-linked polymer solid electrolytes prepared in Examples 1-3 was tested by linear sweep voltammetry (LSV), and the test results are shown in Figure 17. According to the content of Figure 17, the electrochemical stability window of Example 1 is 5.2 V, the electrochemical stability window of Example 2 is 5.2 V, and the electrochemical stability window of Example 3 is 5.3 V; therefore, the cross-linked polymer solid electrolyte prepared in this application has high voltage resistance stability.
  • Example 1 uses LiPF 6 as an initiator and pentaerythritol glycidyl ether as a cross-linking agent and a cross-linking center to design and synthesize a polymer network through in-situ ring-opening polymerization.
  • LiPF6 is added to DOL, and LiPF6 partially decomposes into lithium fluoride and phosphorus pentafluoride.
  • the above decomposition products enable it to proceed smoothly at room temperature; then phosphorus pentafluoride first combines with a small amount of water to form a complex, and then converts into an ion pair H + ( PF5OH ) - , becoming the initial active species of cationic polymerization, and triggering the DOL ring opening to become a monomer active species; then the DOL molecule continues to insert the ion pair to make the polymer chain grow; then pentaerythritol glycidyl ether (cross-linking agent) opens the ring so that its 4 epoxy groups are opened and connected to 8 DOL chains to form a unit structure, and then countless units are connected to form a huge three-dimensional hybrid cross-linked network, which provides rigidity and high cycle stability for the prepared cross-linked polymer solid electrolyte; and through the flexibility of the ether bond in pentaerythritol glycidyl ether, it
  • Example 2 Using LiPF6 as an initiator and polyethylene glycol diglycidyl ether as a cross-linking agent and cross-linking center, a polymer network was designed and synthesized through in-situ ring-opening polymerization. Referring to Figure 19, LiPF6 is added to DOL, and LiPF6 is partially decomposed into lithium fluoride and phosphorus pentafluoride.
  • the above decomposition products enable it to proceed smoothly at room temperature; then phosphorus pentafluoride first combines with a small amount of water to form a complex, and then converts into an ion pair H + ( PF5OH ) - , becoming the initial active species of cationic polymerization, and triggering the DOL ring opening to become a monomer active species; then the DOL molecule continues to insert the ion pair to make the polymer chain grow; then polyethylene glycol diglycidyl ether (cross-linking agent) opens the ring so that its two epoxy groups are opened and connected to four DOL chains to form a unit structure, and then countless units are connected to form a huge three-dimensional hybrid cross-linked network, which provides rigidity and high cycle stability for the prepared cross-linked polymer solid electrolyte; and through the flexibility of the ether bond in polyethylene glycol diglycidyl ether, it presents a very low glass transition temperature, which is conduc
  • Example 3 Using LiPF6 as an initiator and Y-glycidyl ether silyl propane as a cross-linking agent and cross-linking center, a polymer network was designed and synthesized through in-situ ring-opening polymerization. Referring to Figure 20, LiPF6 is added to DOL, and LiPF6 is partially decomposed into lithium fluoride and phosphorus pentafluoride.
  • the above decomposition products enable it to proceed smoothly at room temperature; then phosphorus pentafluoride first combines with a small amount of water to form a complex, and then converts into an ion pair H + ( PF5OH ) - , becoming the initial active species of cationic polymerization, and triggering the DOL ring opening to become a monomer active species; then the DOL molecule continues to insert the ion pair to make the polymer chain grow; then Y-glycidyl ether silylene (cross-linking agent) opens the ring so that its 8 vertices are connected to 16 DOL chains to form a unit structure, and then countless units are connected to form a huge three-dimensional hybrid cross-linked network, which provides rigidity and high cycle stability for the prepared cross-linked polymer solid electrolyte; and through the flexibility of the Si-O-Si bond in Y-glycidyl ether silylene, it presents a very

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Abstract

本申请公开了一种交联聚合物固态电解质及其制备方法和应用，属于新能源材料技术领域。所述交联聚合物固态电解质的制备方法包括：将锂盐溶解于有机溶剂，得到液态电解液；将环醚类单体、引发剂和交联剂加入所述液态电解液中，均匀搅拌，得到准固态电解质前驱体；静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。

Description

交联聚合物固态电解质及其制备方法和应用
本申请要求于2023年5月10日提交中国专利局、申请号为202310519392.1、发明名称为“交联聚合物固态电解质及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在申请中。
技术领域
本申请涉及新能源材料技术领域，尤其涉及一种交联聚合物固态电解质及其制备方法和应用。
 背景技术
目前，锂离子电池在电子设备、新能源电动汽车、大规模储能等领域应用广泛。常规的锂离子电池使用易燃的液态电解质，具有潜在的安全隐患，尤其是在穿刺、撞击、高温等突发情况下，可能会出现电解液泄漏，进而引起安全事故；因此，不易燃的固态电解质开始取代液态电解质的使用。
但常规的固态电解质的阻抗较大，离子电导率低，进而在应用于电池时导致电池在循环后期，由于正、负极不断膨胀和收缩，产生大量的内部微裂纹，导致电池快速失效，循环稳定性能差。
上述内容仅用于辅助理解本申请的技术方案，并不代表承认上述内容是现有技术。
 技术问题
本申请的主要目的在于提供一种交联聚合物固态电解质及其制备方法和应用，旨在解决常规的固态电解质的阻抗较大，离子电导率较低的技术问题。
 技术解决方案
为实现上述目的，本申请提供一种交联聚合物固态电解质的制备方法，所述交联聚合物固态电解质的制备方法包括以下步骤：
将锂盐溶解于有机溶剂，得到液态电解液；
将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，得到准固态电解质前驱体液；
静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。
可选地，所述锂盐包括：二（三氟甲磺酰）亚胺锂（LiTFSI）、双(氟磺酰)亚胺锂（LiFSI）、碘化锂（LiI）、二草酸硼酸锂（LiBOB）和六氟砷酸锂（LiAsF6）中的一种或多种，其中，所述锂盐的浓度至少为0.1 mol/L且不超过10 mol/L。
可选地，所述有机溶剂包括：乙二醇二甲醚（DME）、四氢呋喃（THF）、N,N-二甲基甲酰胺（DMF）、甲苯、N-甲基吡咯烷酮和4-甲基-1,3-二氧环戊中的一种或多种。
可选地，所述环醚类单体包括：1,3-二氧戊环（DOL）、聚乙二醇二甲醚（NHD）、氟代碳酸乙烯酯（FEC）和碳酸亚乙烯酯（VC）中的一种或多种。
可选地，所述引发剂包括：六氟磷酸锂（LiPF6）、氟化锡(SnF4)、三氟甲磺酸镁（Mg(OTf)2）、1-羟基环己基苯基酮、路易斯酸和三氟甲磺酸铝（Al(OTf)3）中的一种或多种，其中，所述引发剂的浓度至少为0.1 mol/L且不超过5 mol/L。
可选地，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚、Y-缩水甘油醚氧硅丙基倍半氧烷和三羟甲基丙烷三缩水甘油醚中的一种或多种，其中，所述交联剂的含量至少为1 wt.%且不超过30 wt.%。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:10至10:1。
可选地，所述准固态电解质前驱体液的静置温度至少为15 ℃且不超过60 ℃，静置时间至少为0.5 h且不超过72 h。
本申请还提供一种交联聚合物固态电解质，所述交联聚合物固态电解质通过上述交联聚合物固态电解质制备方法制得。
本申请还提供一种交联聚合物固态电解质的应用，所述交联聚合物固态电解质通过上述交联聚合物固态电解质的制备方法制得，所述交联聚合物固态电解质在制备锂金属电池中的应用。
本申请公开了一种交联聚合物固态电解质及其制备方法和应用，通过将锂盐溶解于有机溶剂，得到液态电解液；进而将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，从而得到准固态电解质前驱体液；进而静置所述准固态电解质前驱体液，使得准固态的前驱体液逐渐凝固，得到低阻抗、高离子电导率的交联聚合物固态电解质；本申请中，引发剂的加入使环醚类单体进行原位开环聚合从而形成线性聚合物，而加入的交联剂通过开环与环醚类单体连接，进一步使得线性聚合物交联形成巨大的三维杂化交联网络，增强了结构稳定性；并且通过杂化提高了固态电解质的热稳定性，降低了聚合物基质的结晶度，进而提高了固态电解质的离子电导率，最终得到具有高离子电导率、低界面阻抗和高稳定性的固态聚合物电解质。而该制备方法工艺简单，可利用现有的液态电解质生产工艺，而无需增加设备投入，具有产业化的前景；通过交联减少氢键，进而增加聚合物链段的活动性，提高固态电解质的离子电导率，并通过各组分之间的协同作用显著降低了电解质的阻抗，使固态电解质能够像液态电解液一样进行大倍率放电，使固态电解质与电池电极保持良好的界面接触，提升电池的安全性和循环稳定性。
 附图说明
图1为本申请实施例方案涉及的交联聚合物固态电解质的制备方法的流程示意图；
图2为本申请实施例和对比例的交流阻抗测试图；
图3为本申请实施例1的离子电导率与温度关系测试图；
图4为本申请实施例2的离子电导率与温度关系测试图；
图5为本申请实施例3的离子电导率与温度关系测试图；
图6为本申请实施例1和对比例1所制备对称电池的稳定性能测试图；
图7为本申请实施例2和对比例1所制备对称电池的稳定性能测试图；
图8为本申请实施例3和对比例1所制备对称电池的稳定性能测试图；
图9为本申请实施例1所制备电池的循环性能测试图；
图10为本申请实施例2所制备电池的循环性能测试图；
图11为本申请实施例3所制备电池的循环性能测试图；
图12为本申请实施例1所制备电池的首圈充放电测试图；
图13为本申请对比例1的锂离子迁移数曲线图；
图14为本申请实施例1的锂离子迁移数曲线图；
图15为本申请实施例2的锂离子迁移数曲线图；
图16为本申请实施例3的锂离子迁移数曲线图；
图17为本申请实施例1-3的线性扫描伏安图；
图18为本申请实施例1的聚合物网络结构示意图；
图19为本申请实施例2的聚合物网络结构示意图；
图20为本申请实施例3的聚合物网络结构示意图。
本申请目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
 本发明的最佳实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
另外，全文中出现的“和/或”的含义，包括三个并列的方案，以“A和/或B”为例，包括A方案、或B方案、或A和B同时满足的方案。此外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本申请要求的保护范围之内。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
锂离子电池应用于人们生活的方方面面，例如手机、电脑、电动汽车以及各种电动工具等，但锂离子电池的安全风险和续航能力问题，促使人们一直寻求高安全与高比能的新型电池。常规的锂离子电池多使用电解液，利用有机醚类或者有机酯类电解液将锂盐溶解，并通过添加成膜保护剂等实现锂离子电池的安全长循环。在众多的液态有机电解液中，碳酸脂类是一类具有较高介电常数和宽电化学窗口的有机溶剂，是目前使用最广泛的锂离子电池溶剂之一。常用的有机溶剂包括：碳酸二乙酯、碳酸乙烯酯、碳酸二甲酯、碳酸甲乙酯等。但是这一类的有机溶剂容易挥发、易燃，存在着较大的安全隐患；同时有机电解液的加入，增加了电池中非活性物质的总体占比，导致锂离子电池的总体比能量降低，而大量的有机酯类或者有机醚类电解液在电池内部容易发生短路，从而极易引发起火，造成严重的安全事故。
为了进一步的提升电池的比能量，同时解决电池整体的安全风险，不易燃的固态电解质开始取代液态电解质的使用。但常规的固态电解质的阻抗较大，离子电导率低（约为10-7S cm-1），进而在应用于电池时导致电池在循环后期，由于正、负极不断膨胀和收缩，产生大量的内部微裂纹，导致电池快速失效，循环稳定性能差。
鉴于此，本申请提出一种交联聚合物固态电解质及其制备方法和应用，通过将锂盐溶解于有机溶剂，得到液态电解液；进而将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀；引发剂的加入使得单体进行原位开环聚合形成线性聚合物，而交联剂的加入进一步使得线性聚合物交联为三维网络聚合物，从而得到准固态电解质前驱体液；进而静置所述准固态电解质前驱体液，使得准固态的前驱体液逐渐凝固，得到交联聚合物固态电解质；该制备方法工艺简单，可利用现有的液态电解质生产工艺，而无需增加设备投入，具有产业化前景；通过交联减少氢键，进而增加聚合物链段活动性，从而提高固态电解质的离子电导率，并通过各组分之间的协同作用显著降低了电解质的阻抗，使固态电解质能够像液态电解液一样进行大倍率放电，使固态电解质与电池电极保持良好的界面接触，提升电池的安全性和循环稳定性。
本申请实施例第一方面提供一种交联聚合物固态电解质的制备方法，所述制备方法包括以下步骤：
步骤S10，将锂盐溶解于有机溶剂，得到液态电解液；
将锂盐加入有机溶剂中进行搅拌直至锂盐全部溶解，以得到液态电解液。
在一可行实施方式中，所述锂盐包括：二（三氟甲磺酰）亚胺锂（LiTFSI）、双(氟磺酰)亚胺锂（LiFSI）、碘化锂（LiI）、二草酸硼酸锂（LiBOB）和六氟砷酸锂（LiAsF 6）中的一种或多种，其中，所述锂盐的浓度至少为0.1 mol/L且不超过10 mol/L。
示例性的，若应用于其他金属电池，可以适应性修改金属盐，将锂盐替换为对应金属电池的金属盐，钠离子电池，锂盐替换为钠盐等。
在另一可行实施方式中，所述有机溶剂包括：乙二醇二甲醚（DME）、四氢呋喃（THF）、N,N-二甲基甲酰胺（DMF）、1,2-二甲氧基丙烷（DMP）、甲苯、N-甲基吡咯烷酮和4-甲基-1,3-二氧环戊中的一种或多种。
可选地，所有机溶剂包括：乙二醇二甲醚（DME）和1,2-二甲氧基丙烷（DMP）中的一种或多种。
步骤S20，将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，得到准固态电解质前驱体液；
将环醚类单体、引发剂和交联剂加入液态电解液中搅拌至均匀，得到准固态电解质前驱体液。
在一可行实施方式中，所述环醚类单体包括：1,3-二氧戊环（DOL）、聚乙二醇二甲醚（NHD）、氟代碳酸乙烯酯（FEC）和碳酸亚乙烯酯（VC）中的一种或多种。
可选地，所述环醚类单体包括：1,3-二氧戊环（DOL）。
在另一可行实施方式中，所述引发剂包括：六氟磷酸锂（LiPF 6）、氟化锡(SnF 4)、三氟甲磺酸镁（Mg(OTf) 2）、1-羟基环己基苯基酮、路易斯酸和三氟甲磺酸铝（Al(OTf) 3）中的一种或多种，其中，所述引发剂的浓度至少为0.1 mol/L且不超过5 mol/L。
可选地，所述引发剂包括：六氟磷酸锂（LiPF 6）。
在又一可行实施方式中，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚、Y-缩水甘油醚氧硅丙基倍半氧烷和三羟甲基丙烷三缩水甘油醚中的一种或多种，其中，所述交联剂的含量至少为1 wt.%且不超过30 wt.%。
可选地，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚和Y-缩水甘油醚氧硅丙基倍半氧烷。
在本实施例中，交联剂可以作为交联中心，通过开环连接至环醚类单体中形成一个单位结构，进而和所形成的的无数单位连接形成一个巨大的三维杂化交联网络。
在又一可行实施方式中，所述有机溶剂与所述环醚类单体的体积比为1:10至10:1。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:5至5:1。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:2至2:1。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:1。
在本实施例中，以环醚类单体提供柔韧性和界面相容性，通过引发剂的加入使得环醚类单体进行原位开环聚合，从而形成了线性聚合物，进而通过交联剂的加入进一步使得线性聚合物交联为三维网络聚合物，增强了结构稳定性，并且交联剂中硅原子杂化提高了固态电解质的热稳定性，降低了聚合物基质的结晶度，进而提高了固态电解质的离子电导率，最终得到具有高离子电导率、低界面阻抗和高稳定性的固态聚合物电解质。
步骤S30，静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。
静置准固态电解质前驱体液，待准固态电解质前驱体液逐渐凝固，以获得交联聚合物固态电解质。
在一可行实施方式中，所述准固态电解质前驱体液的静置温度至少为15 ℃且不超过60 ℃，静置时间至少为0.5 h且不超过72 h。
在本实施例中，通过将锂盐溶解于有机溶剂，得到液态电解液；进而将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，从而得到准固态电解质前驱体液；进而静置所述准固态电解质前驱体液，使得准固态的前驱体液逐渐凝固，得到低阻抗、高离子电导率的交联聚合物固态电解质；本申请中，引发剂的加入使环醚类单体进行原位开环聚合从而形成线性聚合物，而交联剂的加入进一步使得线性聚合物交联为三维网络聚合物，增强了结构稳定性，并且交联剂中硅原子杂化提高了固态电解质的热稳定性，降低了聚合物基质的结晶度，进而提高了固态电解质的离子电导率，最终得到具有高离子电导率、低界面阻抗和高稳定性的固态聚合物电解质。而该制备方法工艺简单，可利用现有的液态电解质生产工艺，而无需增加设备投入，具有产业化的前景；通过交联减少氢键，进而增加聚合物链段的活动性，提高固态电解质的离子电导率，并通过各组分之间的协同作用显著降低了电解质的阻抗，使固态电解质能够像液态电解液一样进行大倍率放电，使固态电解质与电池电极保持良好的界面接触，提升电池的安全性和循环稳定性。
本申请实施例第二方面提供一种交联聚合物固态电解质，所述交联聚合物固态电解质通过以下方法制得：
将锂盐溶解于有机溶剂，得到液态电解液；
将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，得到准固态电解质前驱体液；
静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。
可选地，所述锂盐包括：二（三氟甲磺酰）亚胺锂、双(氟磺酰)亚胺锂、碘化锂、二草酸硼酸锂和六氟砷酸锂中的一种或多种，其中，所述锂盐的浓度至少为0.1 mol/L且不超过10 mol/L。
可选地，所述有机溶剂包括：乙二醇二甲醚、四氢呋喃、N,N-二甲基甲酰胺、1,2-二甲氧基丙烷（DMP）、甲苯、N-甲基吡咯烷酮和4-甲基-1,3-二氧环戊中的一种或多种。
可选地，所述环醚类单体包括：1,3-二氧戊环、聚乙二醇二甲醚、氟代碳酸乙烯酯和碳酸亚乙烯酯中的一种或多种。
可选地，所述引发剂包括：六氟磷酸锂、氟化锡、三氟甲磺酸镁、1-羟基环己基苯基酮、路易斯酸和三氟甲磺酸铝中的一种或多种，其中，所述引发剂的浓度至少为0.1 mol/L且不超过5 mol/L。
可选地，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚、Y-缩水甘油醚氧硅丙基倍半氧烷和三羟甲基丙烷三缩水甘油醚中的一种或多种，其中，所述交联剂的含量至少为1 wt.%且不超过30 wt.%。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:10至10:1。
可选地，所述准固态电解质前驱体液的静置温度至少为15 ℃且不超过60 ℃，静置时间至少为0.5 h且不超过72 h。
本申请实施例第三方面提供一种交联聚合物固态电解质的应用，所述交联聚合物固态电解质在制备锂金属电池中的应用；其中，所述交联聚合物固态电解质通过以下方法制得：
将锂盐溶解于有机溶剂，得到液态电解液；
将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，得到准固态电解质前驱体液；
静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。
可选地，所述锂盐包括：二（三氟甲磺酰）亚胺锂、双(氟磺酰)亚胺锂、碘化锂、二草酸硼酸锂和六氟砷酸锂中的一种或多种，其中，所述锂盐的浓度至少为0.1 mol/L且不超过10 mol/L。
可选地，所述有机溶剂包括：乙二醇二甲醚、四氢呋喃、N,N-二甲基甲酰胺、甲苯、N-甲基吡咯烷酮和4-甲基-1,3-二氧环戊中的一种或多种。
可选地，所述环醚类单体包括：1,3-二氧戊环、聚乙二醇二甲醚、氟代碳酸乙烯酯和碳酸亚乙烯酯中的一种或多种。
可选地，所述引发剂包括：六氟磷酸锂、氟化锡、三氟甲磺酸镁、1-羟基环己基苯基酮、路易斯酸和三氟甲磺酸铝中的一种或多种，其中，所述引发剂的浓度至少为0.1 mol/L且不超过5 mol/L。
可选地，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚、Y-缩水甘油醚氧硅丙基倍半氧烷和三羟甲基丙烷三缩水甘油醚中的一种或多种，其中，所述交联剂的含量至少为1 wt.%且不超过30 wt.%。
可选地，所述有机溶剂与所述环醚类单体的体积比为1:10至10:1。
可选地，所述准固态电解质前驱体液的静置温度至少为15 ℃且不超过60 ℃，静置时间至少为0.5 h且不超过72 h。
为使本申请上述实施例细节和操作能清楚地被本领域技术人员理解，以及本申请实施例交联聚合物固态电解质及其制备方法和应用的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。
实施例1
将1 mol/L的二（三氟甲磺酰）亚胺锂溶解于乙二醇二甲醚（DME）中，得到液态电解液；
将与DME体积比为1:1的1，3-二氧戊环（DOL）、2 mol/L六氟磷酸锂（LiPF6）和5 wt.%的季戊四醇缩水甘油醚分次加入液态电解液中，搅拌至均匀得到准固态电解质前驱体液；
在25 ℃下静置准固态电解质前驱体液20 h，得到交联聚合物固态电解质。
实施例2
步骤与实施例1相同，不同之处在于：所加入的交联剂为聚乙二醇二缩水甘油醚。
实施例3
步骤与实施例1相同，不同之处在于：所加入的有机溶剂为1,2-二甲氧基丙烷（DMP），所加入的交联剂为Y-缩水甘油醚氧硅丙基倍半氧烷。
对比例1
步骤与实施例1相同，不同之处在于：未添加交联剂。
进一步的，为了验证本申请实施例的进步性，对各实施例和对比例进行了如下性能测试：
1、离子电导率与阻抗测试：
将制备的电解质夹在两片不锈钢片之间，并封装在CR2032扣式电池中，使用上海辰华电CHI760e化学工作站对组装的“钢片|电解质|钢片”电池进行电化学阻抗测试，其中，电解质厚度为50μm，振幅为5 mV，频率范围为10-10 6Hz。结果如图2和表1所示：
表1
根据图2中的交流阻抗图以及表1中的阻抗数据可知，本申请实施例1-3所制备的固态电解质的阻抗在2Ω左右，具有极小的阻抗；而离子电导率在1.1×10 -3S·cm -1左右，相较于对比例1中所制备的固态电解质，离子电导率提高了一个数量级，具有较高的离子电导率。
2、离子电导率与温度关系测试：
对实施例1-3中所制备的电解质夹在两片不锈钢片之间，并封装在CR2032扣式电池中，使用上海辰华电CHI760e化学工作站对组装的“钢片|电解质|钢片”电池进行电化学阻抗测试，其中，电解质厚度为50μm，振幅为5 mV，频率范围为10-10 6Hz，实验温度25-80℃，结果如图3-5所示。
根据图3-5内容可知，实施例1-3所制备的交联聚合固态电解质的离子电导率均随着温度的升高而逐渐升增加，与温度之间成线性关系，并且能够在较高的温度（80℃）下均保持稳定的离子电导率。
3、所制备对称电池的稳定性能测试：
电池的组装：将实施例1-3与对比例1的固态电解质，分别按照负极壳、弹片、垫片、锂金属、隔膜、前驱体液、磷酸铁锂、锂金属到正极壳的顺序组装成锂电池；组装后进行压制密封，常温静置电池24h以确保前驱体液的原位固态化；静置完毕后进行1C倍率性能测试，测试结果如图6-8所示，（a）为循环0-800 h的电压变化曲线，（b）为（a）中795-800 h的局部放大图。
根据图6-8可知，在1 mA/cm 2电流密度下，实施例1-3所制备的固态对称电池能够在极低的过电位下进行充放电，在循环至800 h后，电压极化依旧平稳，表现出非常稳定的锂的沉积与溶解行为，因此，本申请所制备的交联聚合固态电解质应用于电池中时，使电池表现出优良的稳定性能。而对比例1所制备的固态对称电池，过电位较大，在800 h时达到420 mV左右，持续增加的过电位表明循环过程中不均匀的镀锂/脱锂现象的加剧。
4、所制备电池的循环性能测试：
正极制备：将0.4g磷酸铁锂、0.05g导电炭黑、0.05g聚偏氟乙烯加入到1.5 mL的 N-甲基吡咯烷酮（NMP）中，在常温下混合搅拌24 h后涂覆在20微米厚的铝箔上，在80 ℃下真空干燥24 h。将电极裁成直径14 mm的圆片，活性物质磷酸铁锂的载量为2.0mg·cm –2。
电池的组装：将实施例1-3所制备的固态电解质，分别按照负极壳、弹片、垫片、锂金属、隔膜、前驱体液、磷酸铁锂、正极、正极壳的顺序组装电池，组装后进行压制密封，常温静置电池24h以确保前驱体液的原位固态化制得：磷酸铁锂 | 聚合物固态电解质 | 锂（LFP | SPE | Li）电池，静置完毕后进行1C倍率性能测试，测试结果如图9-11所示。
在1C倍率下，参照图9-11，实施例1-3所制备的交联聚合物固态电解质电池具有优良的循环性能，在循环了300圈后，容量分别为144.4 mAh/g、144.9 mAh/g和140.4 mAh/g；故本申请所制备的交联聚合物电解质电池的循环稳定性优异，且容量高。
5、所制备电池的首圈充放电测试：
使用根据实施例1的交联聚合物固态电解质所制备的LFP | SPE | Li电池进行首圈充放电测试，结果参照图12；根据图12可知，所制备的聚合物固态电解质电池在1C倍率下的首圈充放电平台稳定，具有较高的首圈容量，首圈容量为165 mA/g（理论为170 mAh/g）。
6、锂离子迁移数测试：
对实施例1-3和对比例1中制备的交联聚合物固态电解质进行锂离子迁移数测试，测试结果如图13-16所示。参照图13，对比例1的锂离子迁移数为0.34；参照图14，实施例1的锂离子迁移数为0.81；参照图15，实施例2的锂离子迁移数为0.55；参照图16，实施例3的锂离子迁移数为0.88；因此，本申请所制备的交联聚合物固态电解质具有限制阴离子的作用，进而减少电池充放电的极化，有利于锂离子的传递。
7、电化学稳定窗口测试：
采用线性扫描伏安法（LSV）对实施例1-3中制备的交联聚合物固态电解质进行电化学稳定性窗口测试，测试结果如图17所示。根据图17内容可知，实施例1的电化学稳定窗口为5.2 V，实施例2的电化学稳定窗口为5.2 V，实施例3的电化学稳定窗口为5.3 V；因此，本申请所制备的交联聚合物固态电解质具有耐高压的稳定性。
在本申请中，实施例1以LiPF 6为引发剂，季戊四醇缩水甘油醚为交联剂与交联中心，通过原位开环聚合设计并合成了聚合物网络。参照图18，将LiPF 6添加至DOL中，LiPF 6部分分解为氟化锂和五氟化磷，作为一种强路易斯酸和聚合的关键引发剂，上述分解产物使其能够在室温下顺利进行；进而五氟化磷首先与少量水结合形成复合物，然后转化为离子对H +（PF 5OH） -，成为阳离子聚合的初始活性物种，并引发DOL开环成为单体活性物种；进而DOL分子继续插入离子对，使聚合物链生长；进而季戊四醇缩水甘油醚（交联剂）通过开环，使其4个环氧基开环连接到8个DOL链形成一个单位结构，进而无数单位之间连接形成一个巨大的三维杂化交联网络，以为所制备的交联聚合物固态电解质提供了刚性和高度循环稳定性；并且通过季戊四醇缩水甘油醚中醚键的灵活性，使其呈现出非常低的玻璃化转变温度，有利于聚合物链段运动，进而使得交联聚合物固态电解质表现为具有高离子电导率的非晶态电解质材料。
实施例2以LiPF 6为引发剂，聚乙二醇二缩水甘油醚为交联剂与交联中心，通过原位开环聚合设计并合成了聚合物网络。参照图19，将LiPF 6添加至DOL中，LiPF 6部分分解为氟化锂和五氟化磷，作为一种强路易斯酸和聚合的关键引发剂，上述分解产物使其能够在室温下顺利进行；进而五氟化磷首先与少量水结合形成复合物，然后转化为离子对H +（PF 5OH） -，成为阳离子聚合的初始活性物种，并引发DOL开环成为单体活性物种；进而DOL分子继续插入离子对，使聚合物链生长；进而聚乙二醇二缩水甘油醚（交联剂）通过开环，使其2个环氧基开环连接到4个DOL链形成一个单位结构，进而无数单位之间连接形成一个巨大的三维杂化交联网络，以为所制备的交联聚合物固态电解质提供了刚性和高度循环稳定性；并且通过聚乙二醇二缩水甘油醚中醚键的灵活性，使其呈现出非常低的玻璃化转变温度，有利于聚合物链段运动，进而使得交联聚合物固态电解质表现为具有高离子电导率的非晶态电解质材料。
实施例3以LiPF 6为引发剂，Y-缩水甘油醚氧硅丙为交联剂与交联中心，通过原位开环聚合设计并合成了聚合物网络。参照图20，将LiPF 6添加至DOL中，LiPF 6部分分解为氟化锂和五氟化磷，作为一种强路易斯酸和聚合的关键引发剂，上述分解产物使其能够在室温下顺利进行；进而五氟化磷首先与少量水结合形成复合物，然后转化为离子对H +（PF 5OH） -，成为阳离子聚合的初始活性物种，并引发DOL开环成为单体活性物种；进而DOL分子继续插入离子对，使聚合物链生长；进而Y-缩水甘油醚氧硅丙（交联剂）通过开环，使其8个顶点连接到16个DOL链形成一个单位结构，进而无数单位之间连接形成一个巨大的三维杂化交联网络，以为所制备的交联聚合物固态电解质提供了刚性和高度循环稳定性；并且通过Y-缩水甘油醚氧硅丙中Si-O-Si键的灵活性，使其呈现出非常低的玻璃化转变温度，有利于聚合物链段运动，进而使得交联聚合物固态电解质表现为具有高离子电导率的非晶态电解质材料。
以上仅为本申请的优选实施例，并非因此限制本申请的专利范围，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包括在本申请的专利保护范围。

Claims (10)

  1. 一种交联聚合物固态电解质的制备方法，其中，所述制备方法包括以下步骤：
    将锂盐溶解于有机溶剂，得到液态电解液；
    将环醚类单体、引发剂和交联剂加入所述液态电解液中搅拌至均匀，得到准固态电解质前驱体液；
    静置所述准固态电解质前驱体液，得到交联聚合物固态电解质。
  2. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述锂盐包括：二（三氟甲磺酰）亚胺锂、双(氟磺酰)亚胺锂、碘化锂、二草酸硼酸锂和六氟砷酸锂中的一种或多种，其中，所述锂盐的浓度至少为0.1 mol/L且不超过10 mol/L。
  3. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述有机溶剂包括：乙二醇二甲醚、四氢呋喃、N,N-二甲基甲酰胺、甲苯、N-甲基吡咯烷酮和4-甲基-1,3-二氧环戊中的一种或多种。
  4. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述环醚类单体包括：1,3-二氧戊环、聚乙二醇二甲醚、氟代碳酸乙烯酯和碳酸亚乙烯酯中的一种或多种。
  5. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述引发剂包括：六氟磷酸锂、氟化锡、三氟甲磺酸镁、1-羟基环己基苯基酮、路易斯酸和三氟甲磺酸铝中的一种或多种，其中，所述引发剂的浓度至少为0.1 mol/L且不超过5 mol/L。
  6. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述交联剂包括：季戊四醇缩水甘油醚、聚乙二醇二缩水甘油醚、Y-缩水甘油醚氧硅丙基倍半氧烷和三羟甲基丙烷三缩水甘油醚中的一种或多种，其中，所述交联剂的含量至少为1 wt.%且不超过30 wt.%。
  7. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述有机溶剂与所述环醚类单体的体积比为1:10至10:1。
  8. 如权利要求1所述的交联聚合物固态电解质的制备方法，其中，所述准固态电解质前驱体液的静置温度至少为15 ℃且不超过60 ℃，静置时间至少为0.5 h且不超过72 h。
  9. 一种交联聚合物固态电解质，其中，所述交联聚合物固态电解质通过如权利要求1-6任一项所述方法制得。
  10. 一种交联聚合物固态电解质的应用，其中，所述交联聚合物固态电解质通过如权利要求1-6任一项所述方法制得，所述交联聚合物固态电解质在制备锂金属电池中的应用。
PCT/CN2023/114795 2023-05-10 2023-08-24 交联聚合物固态电解质及其制备方法和应用 Ceased WO2024230010A1 (zh)

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