WO2022117082A1 - Gel-type polymer and lithium ion battery containing gel-type polymer - Google Patents

Gel-type polymer and lithium ion battery containing gel-type polymer Download PDF

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WO2022117082A1
WO2022117082A1 PCT/CN2021/135454 CN2021135454W WO2022117082A1 WO 2022117082 A1 WO2022117082 A1 WO 2022117082A1 CN 2021135454 W CN2021135454 W CN 2021135454W WO 2022117082 A1 WO2022117082 A1 WO 2022117082A1
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gel
formula
type polymer
polyether
electrolyte
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French (fr)
Chinese (zh)
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唐伟超
李素丽
赵伟
李俊义
徐延铭
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珠海冠宇电池股份有限公司
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Priority to US18/168,745 priority Critical patent/US20230265223A1/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
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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 invention relates to the technical field of lithium ion batteries, in particular to a gel polymer and a lithium ion battery containing the gel polymer.
  • Lithium-ion batteries have the advantages of high energy density, long cycle life, low self-discharge rate, and environmental protection. They have been widely used in consumer electronic products such as energy storage, power vehicles, notebook computers, mobile phones, and cameras. As the energy density of lithium-ion batteries increases, the safety issues of lithium-ion batteries are particularly important. As the next-generation lithium-ion battery closest to the application, solid-state battery is the key direction of lithium-ion battery development in the future.
  • the core material of solid-state batteries is solid-state electrolytes, which are currently mainly represented by oxide electrolytes, sulfide electrolytes and polymer electrolytes.
  • oxide electrolytes have problems such as low conductivity and poor interface contact
  • sulfide electrolytes have problems such as high processing requirements, poor oxidation resistance, and solid-solid interface
  • polyethylene oxide is a common polymer electrolyte, but it has low conductivity. , poor resistance to oxidation potential and other problems limit the application of polymer electrolytes.
  • the present invention provides a gel polymer and a lithium ion containing the gel polymer.
  • Battery The gel-type polymer can form a gel-type polymer electrolyte after being contacted with the electrolyte in the lithium-ion battery, and the gel-type polymer electrolyte has higher electrical conductivity and electrochemical stability, and can effectively reduce the battery Internal resistance, improve battery performance.
  • a gel-type polymer comprising repeating units derived from gelable monomers and repeating units as shown in Formula 1 below:
  • R 1 is selected from H or C 1-6 alkyl
  • R 2 is a linking group
  • R 3 is an end capping group
  • M is selected from a boronate chain segment, an aluminate ester chain segment or a phosphate chain segment
  • * indicates the connection end.
  • the repeating unit from the gelable monomer has the structure shown in the following formula 2 or formula 2':
  • R 4 is selected from H or C 1-6 alkyl;
  • R 5 is OH, C 1-6 alkoxy or a polyether segment; * represents a connecting end;
  • R 4 is selected from H or C 1-6 alkyl; * represents the connecting end.
  • the boronate ester segment has a structural unit represented by formula 3 or formula 4:
  • the aluminate segment has a structural unit shown in formula 5:
  • the phosphate chain segment has a structural unit shown in formula 6:
  • the number average molecular weight of M is 200-10000.
  • the monomer for preparing the repeating unit shown in formula 1 is selected from the compound shown in formula 7 below:
  • R 1 , R 2 , R 3 , and M are defined as described above.
  • the compound represented by formula 7 is selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate methyl ester At least one of base acrylate and polyether phosphate methacrylate.
  • R 4 is selected from H or C 1-3 alkyl; for example, R 4 is selected from H or methyl.
  • R 5 is selected from OH or C 1-3 alkoxy.
  • the polyether segment has a structural unit shown in formula 8:
  • the monomer for preparing the repeating unit shown in formula 2 is selected from the compound shown in formula 9 below:
  • the monomer for preparing the repeating unit represented by the formula 2' is selected from the compound represented by the following formula 9':
  • R 4 is as defined above.
  • the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2 in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50.
  • the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2' in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50.
  • the number-average molecular weight of the gel-type polymer is 1,000-500,000, preferably 5,000-300,000.
  • the electrical conductivity of the gel-type polymer is >4.5 mS/cm.
  • the present invention also provides a gel-type polymer electrolyte, the gel-type polymer electrolyte includes the above-mentioned gel-type polymer and an electrolyte.
  • the present invention also provides a lithium ion battery comprising the above-mentioned gel-type polymer electrolyte.
  • the present invention provides a gel-type polymer and a lithium ion battery containing the gel-type polymer.
  • a gel-type polymer electrolyte is prepared by selecting a type of gel-type polymer different from the prior art and contacting the gel-type polymer with the electrolyte in the lithium ion battery to form a gel-type polymer electrolyte.
  • the gel-type polymer electrolyte has high electrical conductivity, can replace the existing polyethylene oxide solid electrolyte, can effectively improve and enhance the transport performance of lithium ions, and reduce the internal resistance of lithium ion batteries.
  • the lithium-ion battery containing the gel-type polymer electrolyte has good resistance to oxidation potential, which greatly expands the application of the gel-type polymer in high-voltage systems, improves the electrochemical stability of the gel-type polymer, and effectively Improve the energy density of lithium-ion batteries and broaden their application fields.
  • the gel-type polymer of the present invention uses functional polymer monomers to replace polyethylene oxide.
  • the molecular weight of the functional polymer monomers is 100-10000, which can be efficiently dissolved in the solvent, so that the prepared slurry has a high solid content , low viscosity, easy to process; at the same time, the functional polymer monomer and the gelable monomer can be polymerized to obtain a gel polymer, which has a lower degree of crystallinity and a lower degree of crystallinity than polyethylene oxide.
  • the functional polymer monomer also has an acrylate group, which can well adsorb the carbonate small molecules in the electrolyte, form a continuous lithium conduction channel, and effectively improve the performance of lithium ion batteries;
  • Functional polymer monomers are liquid or semi-solid at room temperature, but can be prepared into compact and dense gel-type polymers after polymerization with gelable monomers, and further contact with electrolyte to form gel-type polymers electrolyte.
  • the polyethylene oxide electrolyte used in conventional solid-state batteries has poor high-voltage resistance performance, especially for voltages above 3.8V.
  • At least one of polyether-based borate, polyether-based aluminate and polyether-based phosphate is introduced into the gel polymer electrolyte of the present invention, which can effectively improve the high voltage resistance of the polymer electrolyte. performance, a significant improvement in high voltage performance compared to conventional polyethylene oxide electrolytes.
  • the gel-type polymer electrolyte of the present invention has higher lithium ion conductivity and higher lithium ion conductivity than conventional polyethylene oxide electrolytes. Compared with the polyethylene oxide electrolyte, the gel polymer electrolyte of the present invention has a lower crystallinity due to the branched structure of the polymer, and lithium ions have higher lithium ions in the gel polymer electrolyte.
  • the branched chain of the gel polymer is at least one of polyether borate, polyether aluminate and polyether phosphate, which can effectively promote gel polymerization
  • the dissociation of lithium salts in the polymer electrolyte can improve the conductivity of lithium ions and improve the electrochemical window of the gel polymer electrolyte.
  • the present invention provides a gel-type polymer comprising repeating units derived from gelatable monomers and repeating units as shown in Formula 1 below:
  • R 1 is selected from H or C 1-6 alkyl
  • R 2 is a linking group
  • R 3 is an end capping group
  • M is selected from a boronate chain segment, an aluminate ester chain segment or a phosphate chain segment
  • * indicates the connection end.
  • R 1 is selected from H or C 1-3 alkyl; for example, R 1 is selected from H or methyl.
  • R 3 is selected from H, OH or COOH.
  • the boronate ester segment has a structural unit represented by formula 3 or formula 4:
  • the aluminate segment has a structural unit represented by formula 5:
  • the phosphate ester segment has a structural unit shown in formula 6:
  • the number average molecular weight of M is 200-10000.
  • the monomer for preparing the repeating unit shown in formula 1 is selected from the compound shown in formula 7 below:
  • R 1 , R 2 , R 3 , and M are defined as described above.
  • the compound represented by formula 7 is selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate At least one of ester methacrylate and polyether phosphate methacrylate.
  • gelable monomer refers to a monomer capable of forming a gelable polymer, such as at least one of acrylonitrile and its modified derivatives, acrylates and its modified derivatives.
  • the repeating unit from the gelable monomer has the structure shown in the following formula 2 or formula 2':
  • R 4 is selected from H or C 1-6 alkyl;
  • R 5 is OH, C 1-6 alkoxy or a polyether segment; * represents a connecting end;
  • R 4 is selected from H or C 1-6 alkyl; * represents the connecting end.
  • R 4 is selected from H or C 1-3 alkyl; for example, R 4 is selected from H or methyl.
  • R 5 is selected from OH or C 1-3 alkoxy.
  • the polyether segment has a structural unit shown in formula 8:
  • the number average molecular weight of the polyether segment is 60-3000.
  • the monomer for preparing the repeating unit shown in formula 2 is selected from the compound shown in formula 9 below:
  • the monomer for preparing the repeating unit represented by the formula 2' is selected from the compound represented by the following formula 9':
  • R 4 is as defined above.
  • the gel-type polymer is selected from the group consisting of copolymers of polyether borate acrylate and acrylate monomers, copolymers of polyether aluminate acrylate and acrylate monomers, polyether borate acrylates and acrylate monomers.
  • Copolymers of ether phosphate acrylates and acrylate monomers copolymers of polyether borate methacrylates and acrylate monomers, copolymers of ether aluminate methacrylates and acrylate monomers compounds, copolymers of ether phosphate methacrylates and acrylate monomers, copolymers of polyether borate acrylates and acrylonitrile monomers, copolymers of polyether aluminate acrylates and acrylonitrile monomers Copolymers, copolymers of polyether phosphate acrylates and acrylonitrile monomers, copolymers of polyether borate methacrylates and acrylonitrile monomers, ether aluminate methacrylates and acrylonitriles At least one of copolymers of monomers, ether phosphate methacrylates, and acrylonitrile-based monomers.
  • the acrylate monomers include at least one of acrylic acid, polyethylene glycol methacrylate, polyethylene glycol acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate One; the acrylonitrile monomers include at least one of acrylonitrile and methacrylonitrile.
  • the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2 in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50.
  • the repeating unit shown in formula 1 is mainly used to improve the conductivity and the electrochemical window
  • the repeating unit shown in formula 2 is mainly used to improve the gelation of the polymer and the electrolyte.
  • the molar ratio of the repeating unit represented by formula 1 to the repeating unit represented by formula 2' in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50 .
  • the repeating unit shown in formula 1 is mainly used to improve the conductivity and the electrochemical window. liquid gelation.
  • the number-average molecular weight of the gel-type polymer is 1,000-500,000, preferably 5,000-300,000.
  • the electrical conductivity of the gel-type polymer is >10 -3 S/cm.
  • the present invention also provides a method for preparing the above-mentioned gel-type polymer, the method comprising the steps of:
  • the organic solvent, the polymer monomer shown in formula 7, the gelable monomer and the initiator are uniformly mixed and reacted to prepare the gel-type polymer.
  • the method comprises the steps:
  • the organic solvent, the polymer monomer represented by the formula 7, the polymer monomer represented by the formula 9 or the formula 9' and the initiator are uniformly mixed and reacted to prepare the gel-type polymer.
  • the added amount of the initiator is 0.05-1 wt % of the total mass of the polymer monomers.
  • the initiator is selected from azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide , one or more of 4-(N,N-dimethylamino) ethyl benzoate, methyl o-benzoyl benzoate, etc.
  • the organic solvent is selected from at least one of N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, and toluene.
  • the method specifically comprises the following steps:
  • the present invention also provides a gel-type polymer electrolyte
  • the gel-type polymer electrolyte includes the above-mentioned gel-type polymer and an electrolyte.
  • the electrolyte is derived from an electrolyte, and the electrolyte is an electrolyte commonly used in the art, for example, purchased through commercial channels, and is suitable for an electrolyte in a lithium-ion battery.
  • the present invention also provides a method for preparing the above-mentioned gel polymer electrolyte, the method comprising the following steps:
  • the gel polymer electrolyte is prepared by soaking the gel polymer in the electrolyte, and taking it out after standing for a period of time.
  • the standing time is not particularly limited, as long as the gel-type polymer is fully infiltrated.
  • the present invention also provides a lithium ion battery comprising the above-mentioned gel-type polymer electrolyte.
  • the structure of the polyether phosphate methacrylate used in the following examples is as shown in formula 7, wherein R 1 is CH 3 , R 2 is absent, R 3 is H, and M is shown in formula 6 .
  • a lithium ion battery cell is prepared by laminating the negative pole piece, gel-type polymer electrolyte film, and negative pole piece obtained above, and a lithium ion battery is obtained after welding, packaging, chemical formation, and sorting.
  • Example 1 The specific process refers to Example 1, the main difference is that in Comparative Example 1.1, polyethylene oxide of equal mass and molecular weight is used to replace the gel-type polymer in Example 1, and other conditions are consistent with Example 1.
  • Example 1 The specific process refers to Example 1, the main difference is that the monomer in the system of Comparative Example 1.2 is 0 g of polyether borate acrylate (the structure shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 H and M are shown in formula 3) and 100 g of methyl methacrylate (structure shown in formula 9, wherein R 4 is CH 3 and R 5 is OCH 3 ), and other conditions are the same as in Example 1.
  • Example 1 The specific process refers to Example 1, the main difference is that the monomer in the system of Comparative Example 1.3 is 100 g of polyether borate acrylate (structure shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 H and M are shown in formula 3) and 0 g of methyl methacrylate (structure shown in formula 9, wherein R 4 is CH 3 and R 5 is OCH 3 ), and other conditions are the same as in Example 1.
  • the specific process refers to Example 1, and the main differences are the process conditions, the amount of each component added, and the type of each component material. The specific details are shown in Table 1 and Table 2.
  • the gel-type polymer films prepared in the above examples and comparative examples were soaked in the electrolyte for 24 hours, and then the gel-type polymer electrolyte was subjected to electrochemical window test and electrical conductivity test.
  • Electrochemical window test using stainless steel/gel-type polymer electrolyte/lithium sheet structure, using Chenhua CHE660E electrochemical workstation to test the electrochemical stability of gel-type polymer electrolyte, the test range is 2-6V, the test frequency is 0.05 mV/S. The test results are shown in Table 2.
  • the electrochemical window of the gel-type polymer electrolyte prepared in Example 1 is about 4.45V
  • the electrochemical window of the polymer electrolyte prepared in Comparative Example 1.1 is about 3.80V
  • the electrochemical window of the gel-type polymer electrolyte prepared in Comparative Example 1.2 is about 3.80V.
  • the chemical window is about 4.40V
  • the electrochemical window of the gel-type polymer electrolyte prepared in Comparative Example 1.3 is about 4.50V. It shows that the gel-type polymer electrolyte of the present invention has good electrochemical stability, can be matched with high-voltage positive electrode materials, and has good application prospects.
  • the comprehensive electrochemical stability test and AC impedance test results show that the conductivity of the gel-type polymer electrolyte prepared in Example 1 is about 4.81 mS/cm, and the conductivity of the polymer electrolyte prepared in Comparative Example 1.1 is about 4.22 mS/cm.
  • the conductivity of the gel-type polymer electrolyte prepared in Comparative Example 1.2 is about 3.35 mS/cm, and the conductivity of the gel-type polymer electrolyte prepared in Comparative Example 1.3 is about 4.31 mS/cm.
  • the experimental results show that the specific structure of the polymer monomer shown in the embodiment of the present invention can effectively improve the lithium ion conductivity and electrochemical stability of the electrolyte.
  • the main reason is that the polymerized monomer of the present invention is polymerized from two monomers.
  • the gel-type polymer electrolyte of the present invention has a comb-like structure, and the branched chain has the structure of polyboron ether, polyaluminum ether, and polyphosphorus ether. It can conduct lithium conduction and has good electrochemical stability; at the same time, the gel-type polymer electrolyte of the present invention is formed by copolymerization of two monomers, has a lower degree of crystallization, has better affinity with the electrolyte, and has higher conductivity. Therefore, the gel-type polymer electrolyte prepared in Example 1 has better comprehensive performance.
  • Example 1 100% 97.8% 95.3% 94.5% Comparative Example 1.1 100% 94.3% 88.4% 85.2% Comparative Example 1.2 100% 95.6% 92.3% 90.7% Comparative Example 1.3 100% 96.4% 93.1% 91.3% Example 2 100% 97.1% 94.9% 93.3% Example 3 100% 98.3% 96.5% 95.1% Example 4 100% 96.7% 94.2% 92.4% Example 5 100% 97.2% 94.6% 93.9% Example 6 100% 98.0% 95.2% 94.7% Example 7 100% 97.5% 94.9% 93.7% Example 8 100% 98.5% 96.8% 95.3% Example 9 100% 98.2% 95.8% 94.9% Example 10 100% 97.0% 95.0% 93.6% Example 11 100% 97.5% 95.2% 93.9% Example 12 100% 97.4% 95.1% 94.1% Example 13 100% 97.5%
  • Example 1 Comparative Example 1.1, Comparative Example 1.2, Comparative Example 1.3, and the prepared lithium-ion batteries of Examples 2-13 were subjected to a rate test.
  • the test process was as follows: the lithium-ion battery was charged and discharged on a blue battery test cabinet for 3.0-4.45 V charge-discharge rate test, the test condition is 25 °C, using an uncycled battery, the battery is charged and discharged at a rate of 0.2C/0.2C, 0.5C/0.5C, 1.0C/1.0C, 1.5C/1.5C, Investigate the battery rate performance.
  • the test results are shown in Table 3.
  • the test results of the rate charge and discharge performance of Example 1, Comparative Example 1.1, Comparative Example 1.2 and Comparative Example 1.3 show that the lithium ion battery prepared in Example 1 of the present invention has better rate performance , especially at >0.5C magnification.
  • the main reason is the gel-type polymer electrolyte in the lithium-ion battery.
  • the gel-type polymer electrolyte prepared in Example 1 has good lithium ion conductivity. rate and electrochemical stability.

Abstract

The present invention relates to the technical field of lithium ion batteries, and particularly relates to a gel-type polymer and a lithium ion battery containing the gel-type polymer. In the present invention, by using a gel-type polymer which is different from the prior art and bringing the gel-type polymer into contact with an electrolyte solution in a lithium ion battery to form a gel-type polymer electrolyte, a lithium ion battery containing the gel-type polymer electrolyte is prepared. The gel-type polymer electrolyte has a high conductivity, and can be used to replace an existing polyoxyethylene solid electrolyte, such that the transmission performance of lithium ions can be effectively improved and promoted and the internal resistance of a lithium ion battery is reduced. In addition, the oxidation-resistant potential performance of the lithium ion battery containing the gel-type polymer electrolyte is good, whereby the application of the gel-type polymer in high-voltage systems is greatly broadened, the electrochemical stability of the gel-type polymer is improved, the energy density of the lithium ion battery is effectively increased, and the application field of the lithium ion battery is broadened.

Description

一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池A gel-type polymer and a lithium-ion battery containing the gel-type polymer
本申请要求于2020年12月03日提交中国专利局、申请号为202011396209.6、申请名称为“一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires the priority of the Chinese patent application with the application number of 202011396209.6 and the application title of "a gel-type polymer and a lithium-ion battery containing the gel-type polymer" submitted to the China Patent Office on December 3, 2020 rights, the entire contents of which are incorporated herein by reference.
技术领域technical field
本发明涉及锂离子电池技术领域，尤其涉及一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池。The present invention relates to the technical field of lithium ion batteries, in particular to a gel polymer and a lithium ion battery containing the gel polymer.
背景技术Background technique
锂离子电池具有能量密度高，循环寿命长，自放电率小，绿色环保等优点，其已广泛用于储能领域、动力汽车、笔记本电脑、手机、摄影机等消费电子产品。随着锂离子电池能量密度的增加，锂离子电池的安全问题显得尤其重要。固态电池作为最接近应用的下一代锂离子电池，是锂离子电池未来发展重点方向。Lithium-ion batteries have the advantages of high energy density, long cycle life, low self-discharge rate, and environmental protection. They have been widely used in consumer electronic products such as energy storage, power vehicles, notebook computers, mobile phones, and cameras. As the energy density of lithium-ion batteries increases, the safety issues of lithium-ion batteries are particularly important. As the next-generation lithium-ion battery closest to the application, solid-state battery is the key direction of lithium-ion battery development in the future.
固态电池的核心材料是固态电解质，固态电解质目前主要代表有氧化物电解质、硫化物电解质和聚合物电解质。其中，氧化物电解质存在电导率低、界面接触差等问题；硫化物电解质存在加工要求高、耐氧化性差、固固界面等问题；聚氧化乙烯为常见的聚合物电解质，但是其存在电导率低、耐氧化电位性能差等问题，限制了聚合物电解质的应用。The core material of solid-state batteries is solid-state electrolytes, which are currently mainly represented by oxide electrolytes, sulfide electrolytes and polymer electrolytes. Among them, oxide electrolytes have problems such as low conductivity and poor interface contact; sulfide electrolytes have problems such as high processing requirements, poor oxidation resistance, and solid-solid interface; polyethylene oxide is a common polymer electrolyte, but it has low conductivity. , poor resistance to oxidation potential and other problems limit the application of polymer electrolytes.
发明内容SUMMARY OF THE INVENTION
为了改善现有技术中聚合物电解质，特别是聚氧化乙烯类聚合物电解质电导率低、耐氧化性差等不足，本发明提供一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池。所述凝胶型聚合物与锂离子电池中的电解液接触后可 以形成凝胶型聚合物电解质，所述凝胶型聚合物电解质具有更高的电导率和电化学稳定性，能够有效降低电池内阻，提升电池性能。In order to improve the shortcomings of polymer electrolytes in the prior art, especially polyethylene oxide polymer electrolytes with low electrical conductivity and poor oxidation resistance, the present invention provides a gel polymer and a lithium ion containing the gel polymer. Battery. The gel-type polymer can form a gel-type polymer electrolyte after being contacted with the electrolyte in the lithium-ion battery, and the gel-type polymer electrolyte has higher electrical conductivity and electrochemical stability, and can effectively reduce the battery Internal resistance, improve battery performance.
本发明目的是通过如下技术方案实现的：The object of the invention is to be achieved through the following technical solutions:
一种凝胶型聚合物，所述凝胶型聚合物包括来自可凝胶单体的重复单元和如下式1所示的重复单元：A gel-type polymer comprising repeating units derived from gelable monomers and repeating units as shown in Formula 1 below:
Figure PCTCN2021135454-appb-000001
Figure PCTCN2021135454-appb-000001
式1中，R 1选自H或C 1-6烷基；R 2为连接基团；R 3为封端基团；M选自硼酸酯链段、铝酸酯链段或磷酸酯链段；*表示连接端。 In formula 1, R 1 is selected from H or C 1-6 alkyl; R 2 is a linking group; R 3 is an end capping group; M is selected from a boronate chain segment, an aluminate ester chain segment or a phosphate chain segment; * indicates the connection end.
根据本发明，所述来自可凝胶单体的重复单元具有如下式2或式2’所示结构：According to the present invention, the repeating unit from the gelable monomer has the structure shown in the following formula 2 or formula 2':
Figure PCTCN2021135454-appb-000002
Figure PCTCN2021135454-appb-000002
式2中，R 4选自H或C 1-6烷基；R 5为OH、C 1-6烷氧基或聚醚链段；*表示连接端； In formula 2, R 4 is selected from H or C 1-6 alkyl; R 5 is OH, C 1-6 alkoxy or a polyether segment; * represents a connecting end;
式2’中，R 4选自H或C 1-6烷基；*表示连接端。 In formula 2', R 4 is selected from H or C 1-6 alkyl; * represents the connecting end.
根据本发明，所述硼酸酯链段具有式3或式4所示结构单元：According to the present invention, the boronate ester segment has a structural unit represented by formula 3 or formula 4:
Figure PCTCN2021135454-appb-000003
Figure PCTCN2021135454-appb-000003
式3和式4中，*表示连接端，n为聚合度。In Formula 3 and Formula 4, * represents the connection end, and n represents the degree of polymerization.
根据本发明，所述铝酸酯链段具有式5所示结构单元：According to the present invention, the aluminate segment has a structural unit shown in formula 5:
Figure PCTCN2021135454-appb-000004
Figure PCTCN2021135454-appb-000004
式5中，*表示连接端，m为聚合度。In formula 5, * represents the connection end, and m is the degree of polymerization.
根据本发明，所述磷酸酯链段具有式6所示结构单元：According to the present invention, the phosphate chain segment has a structural unit shown in formula 6:
Figure PCTCN2021135454-appb-000005
Figure PCTCN2021135454-appb-000005
式6中，*表示与R 3的连接端，**表示与R 2的连接端，q为聚合度。 In formula 6, * represents the connection end with R 3 , ** represents the connection end with R 2 , and q is the degree of polymerization.
根据本发明，所述M的数均分子量为200-10000。According to the present invention, the number average molecular weight of M is 200-10000.
根据本发明，制备式1所示重复单元的单体选自如下式7所示化合物：According to the present invention, the monomer for preparing the repeating unit shown in formula 1 is selected from the compound shown in formula 7 below:
Figure PCTCN2021135454-appb-000006
Figure PCTCN2021135454-appb-000006
式7中，R 1、R 2、R 3、M的定义如上所述。 In Formula 7, R 1 , R 2 , R 3 , and M are defined as described above.
根据本发明，式7所示化合物选自聚醚硼酸酯丙烯酸酯、聚醚铝酸酯丙烯酸酯、聚醚磷酸酯丙烯酸酯、聚醚硼酸酯甲基丙烯酸酯、聚醚铝酸酯甲基丙烯酸酯、聚醚磷酸酯甲基丙烯酸酯中的至少一种。According to the present invention, the compound represented by formula 7 is selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate methyl ester At least one of base acrylate and polyether phosphate methacrylate.
根据本发明，R 4选自H或C 1-3烷基；如R 4选自H或甲基。 According to the present invention, R 4 is selected from H or C 1-3 alkyl; for example, R 4 is selected from H or methyl.
根据本发明，R 5选自OH或C 1-3烷氧基。 According to the present invention, R 5 is selected from OH or C 1-3 alkoxy.
根据本发明，所述聚醚链段具有式8所示结构单元：According to the present invention, the polyether segment has a structural unit shown in formula 8:
Figure PCTCN2021135454-appb-000007
Figure PCTCN2021135454-appb-000007
式8中，*表示连接端，p为聚合度。In Formula 8, * represents the connection end, and p represents the degree of polymerization.
根据本发明，制备式2所示重复单元的单体选自如下式9所示化合物：According to the present invention, the monomer for preparing the repeating unit shown in formula 2 is selected from the compound shown in formula 9 below:
Figure PCTCN2021135454-appb-000008
Figure PCTCN2021135454-appb-000008
式9中，R 4、R 5的定义如上所述。 In Formula 9, the definitions of R 4 and R 5 are as described above.
根据本发明，制备式2’所示重复单元的单体选自如下式9’所示化合物：According to the present invention, the monomer for preparing the repeating unit represented by the formula 2' is selected from the compound represented by the following formula 9':
Figure PCTCN2021135454-appb-000009
Figure PCTCN2021135454-appb-000009
式9’中，R 4的定义如上所述。 In formula 9', R 4 is as defined above.
根据本发明，所述凝胶型聚合物中式1所示的重复单元与式2所示的重复单元的摩尔比为30-99:1-70，优选为50-99:1-50。According to the present invention, the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2 in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50.
根据本发明，所述凝胶型聚合物中式1所示的重复单元与式2’所示的重复 单元的摩尔比为30-99:1-70，优选为50-99:1-50。According to the present invention, the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2' in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50.
根据本发明，所述凝胶型聚合物的数均分子量为1000-500000，优选为5000-300000。According to the present invention, the number-average molecular weight of the gel-type polymer is 1,000-500,000, preferably 5,000-300,000.
根据本发明，所述凝胶型聚合物的电导率为>4.5mS/cm。According to the present invention, the electrical conductivity of the gel-type polymer is >4.5 mS/cm.
本发明还提供一种凝胶型聚合物电解质，所述凝胶型聚合物电解质包括上述的凝胶型聚合物和电解质。The present invention also provides a gel-type polymer electrolyte, the gel-type polymer electrolyte includes the above-mentioned gel-type polymer and an electrolyte.
本发明还提供一种锂离子电池，其包括上述的凝胶型聚合物电解质。The present invention also provides a lithium ion battery comprising the above-mentioned gel-type polymer electrolyte.
本发明的有益效果：Beneficial effects of the present invention:
本发明提供了一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池。本发明通过选用一类与现有技术不同的凝胶型聚合物并将该凝胶型聚合物与锂离子电池中的电解液接触后形成凝胶型聚合物电解质，制备得到含有该凝胶型聚合物电解质的锂离子电池。所述凝胶型聚合物电解质具有高电导率，可以替代现有的聚氧化乙烯固态电解质，能够有效改善并提升锂离子的传输性能，降低锂离子电池的内阻。同时，含有该凝胶型聚合物电解质的锂离子电池的耐氧化电位性能好，这大大拓展了凝胶型聚合物在高电压体系的应用，改善凝胶型聚合物的电化学稳定性，有效提升锂离子电池的能量密度，扩宽了其应用领域。The present invention provides a gel-type polymer and a lithium ion battery containing the gel-type polymer. In the present invention, a gel-type polymer electrolyte is prepared by selecting a type of gel-type polymer different from the prior art and contacting the gel-type polymer with the electrolyte in the lithium ion battery to form a gel-type polymer electrolyte. Lithium-ion batteries with polymer electrolytes. The gel-type polymer electrolyte has high electrical conductivity, can replace the existing polyethylene oxide solid electrolyte, can effectively improve and enhance the transport performance of lithium ions, and reduce the internal resistance of lithium ion batteries. At the same time, the lithium-ion battery containing the gel-type polymer electrolyte has good resistance to oxidation potential, which greatly expands the application of the gel-type polymer in high-voltage systems, improves the electrochemical stability of the gel-type polymer, and effectively Improve the energy density of lithium-ion batteries and broaden their application fields.
本发明的凝胶型聚合物采用功能聚合物单体替代聚氧化乙烯，该功能聚合物单体的分子量为100-10000，其能够高效溶解于溶剂中，使得制备得到的浆料的固含量高、粘度低，易于加工；同时该功能聚合物单体与可凝胶单体可以进行聚合制备得到凝胶型聚合物，该凝胶型聚合物与聚氧化乙烯相比具有更低的结晶程度和更好的电导率；该功能聚合物单体还具有丙烯酸酯基团，能够很好地吸附电解液中的碳酸酯类小分子，形成连续的导锂通道，有效提升锂离子电池的性能；该功能聚合物单体在常温下为液态或半固态，但与可凝胶单体进行聚合反应后可以制备成紧实致密的凝胶型聚合物，进一步与电 解液接触后形成凝胶型聚合物电解质。The gel-type polymer of the present invention uses functional polymer monomers to replace polyethylene oxide. The molecular weight of the functional polymer monomers is 100-10000, which can be efficiently dissolved in the solvent, so that the prepared slurry has a high solid content , low viscosity, easy to process; at the same time, the functional polymer monomer and the gelable monomer can be polymerized to obtain a gel polymer, which has a lower degree of crystallinity and a lower degree of crystallinity than polyethylene oxide. Better electrical conductivity; the functional polymer monomer also has an acrylate group, which can well adsorb the carbonate small molecules in the electrolyte, form a continuous lithium conduction channel, and effectively improve the performance of lithium ion batteries; Functional polymer monomers are liquid or semi-solid at room temperature, but can be prepared into compact and dense gel-type polymers after polymerization with gelable monomers, and further contact with electrolyte to form gel-type polymers electrolyte.
常规固态电池中采用的聚氧化乙烯电解质耐高电压性能较差，尤其是>3.8V以上电压。本发明的凝胶型聚合物电解质中引入了聚醚类的硼酸酯、聚醚类的铝酸酯和聚醚类的磷酸酯中的至少一种，能够有效改善聚合物电解质的耐高电压性能，与常规聚氧化乙烯电解质相比，在高电压性能方面显著提升。The polyethylene oxide electrolyte used in conventional solid-state batteries has poor high-voltage resistance performance, especially for voltages above 3.8V. At least one of polyether-based borate, polyether-based aluminate and polyether-based phosphate is introduced into the gel polymer electrolyte of the present invention, which can effectively improve the high voltage resistance of the polymer electrolyte. performance, a significant improvement in high voltage performance compared to conventional polyethylene oxide electrolytes.
本发明的凝胶型聚合物电解质与常规聚氧化乙烯电解质相比具有更高的锂离子电导率和更高的锂离子导通性。本发明的凝胶型聚合物电解质与聚氧化乙烯电解质相比，所述聚合物由于具有支链结构，故其结晶程度更低，锂离子在凝胶型聚合物电解质中具有更高的锂离子电导率；与此同时，所述凝胶型聚合物的支链为聚醚类硼酸酯、聚醚类铝酸酯和聚醚类磷酸酯中的至少一种，能够有效促进凝胶型聚合物电解质中锂盐的解离，提高锂离子的导通性，同时改善凝胶型聚合物电解质的电化学窗口。The gel-type polymer electrolyte of the present invention has higher lithium ion conductivity and higher lithium ion conductivity than conventional polyethylene oxide electrolytes. Compared with the polyethylene oxide electrolyte, the gel polymer electrolyte of the present invention has a lower crystallinity due to the branched structure of the polymer, and lithium ions have higher lithium ions in the gel polymer electrolyte. electrical conductivity; at the same time, the branched chain of the gel polymer is at least one of polyether borate, polyether aluminate and polyether phosphate, which can effectively promote gel polymerization The dissociation of lithium salts in the polymer electrolyte can improve the conductivity of lithium ions and improve the electrochemical window of the gel polymer electrolyte.
附图说明Description of drawings
图1实施例1制备的凝胶型聚合物电解质的LSV曲线测试结果。Fig. 1 Test results of the LSV curve of the gel polymer electrolyte prepared in Example 1.
图2对比例1.1制备的凝胶型聚合物电解质的LSV曲线测试结果。Figure 2. The LSV curve test results of the gel-type polymer electrolyte prepared in Comparative Example 1.1.
图3对比例1.2制备的凝胶型聚合物电解质的LSV曲线测试结果。Figure 3. The LSV curve test results of the gel-type polymer electrolyte prepared in Comparative Example 1.2.
图4对比例1.3制备的凝胶型聚合物电解质的LSV曲线测试结果。Figure 4. The LSV curve test results of the gel-type polymer electrolyte prepared in Comparative Example 1.3.
具体实施方式Detailed ways
<凝胶型聚合物><Gel type polymer>
如前所述，本发明提供一种凝胶型聚合物，所述凝胶型聚合物包括来自可凝胶单体的重复单元和如下式1所示的重复单元：As mentioned above, the present invention provides a gel-type polymer comprising repeating units derived from gelatable monomers and repeating units as shown in Formula 1 below:
Figure PCTCN2021135454-appb-000010
Figure PCTCN2021135454-appb-000010
式1中，R 1选自H或C 1-6烷基；R 2为连接基团；R 3为封端基团；M选自硼酸酯链段、铝酸酯链段或磷酸酯链段；*表示连接端。 In formula 1, R 1 is selected from H or C 1-6 alkyl; R 2 is a linking group; R 3 is an end capping group; M is selected from a boronate chain segment, an aluminate ester chain segment or a phosphate chain segment; * indicates the connection end.
在一个优选方案中，R 1选自H或C 1-3烷基；如R 1选自H或甲基。 In a preferred embodiment, R 1 is selected from H or C 1-3 alkyl; for example, R 1 is selected from H or methyl.
在一个优选方案中，R 3选自H、OH或COOH。 In a preferred embodiment, R 3 is selected from H, OH or COOH.
在一个优选方案中，所述硼酸酯链段具有式3或式4所示结构单元：In a preferred embodiment, the boronate ester segment has a structural unit represented by formula 3 or formula 4:
Figure PCTCN2021135454-appb-000011
Figure PCTCN2021135454-appb-000011
式3和式4中，*表示连接端，n为聚合度。In Formula 3 and Formula 4, * represents the connection end, and n represents the degree of polymerization.
在一个优选方案中，所述铝酸酯链段具有式5所示结构单元：In a preferred embodiment, the aluminate segment has a structural unit represented by formula 5:
Figure PCTCN2021135454-appb-000012
Figure PCTCN2021135454-appb-000012
式5中，*表示连接端，m为聚合度。In formula 5, * represents the connection end, and m is the degree of polymerization.
在一个优选方案中，所述磷酸酯链段具有式6所示结构单元：In a preferred embodiment, the phosphate ester segment has a structural unit shown in formula 6:
Figure PCTCN2021135454-appb-000013
Figure PCTCN2021135454-appb-000013
式6中，*表示与R 3的连接端，**表示与R 2的连接端，q为聚合度。 In formula 6, * represents the connection end with R 3 , ** represents the connection end with R 2 , and q is the degree of polymerization.
在一个优选方案中，所述M的数均分子量为200-10000。In a preferred embodiment, the number average molecular weight of M is 200-10000.
在一个优选方案中，制备式1所示重复单元的单体选自如下式7所示化合物：In a preferred embodiment, the monomer for preparing the repeating unit shown in formula 1 is selected from the compound shown in formula 7 below:
Figure PCTCN2021135454-appb-000014
Figure PCTCN2021135454-appb-000014
式7中，R 1、R 2、R 3、M的定义如上所述。 In Formula 7, R 1 , R 2 , R 3 , and M are defined as described above.
在一个优选方案中，式7所示化合物选自聚醚硼酸酯丙烯酸酯、聚醚铝酸酯丙烯酸酯、聚醚磷酸酯丙烯酸酯、聚醚硼酸酯甲基丙烯酸酯、聚醚铝酸酯甲基丙烯酸酯、聚醚磷酸酯甲基丙烯酸酯中的至少一种。In a preferred solution, the compound represented by formula 7 is selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate At least one of ester methacrylate and polyether phosphate methacrylate.
本发明中，“可凝胶单体”是指能形成可凝胶化聚合物的单体，例如丙烯腈类及其改性衍生物、丙烯酸酯类及其改性衍生物中至少一个。In the present invention, "gelable monomer" refers to a monomer capable of forming a gelable polymer, such as at least one of acrylonitrile and its modified derivatives, acrylates and its modified derivatives.
在一个优选方案中，所述来自可凝胶单体的重复单元具有如下式2或式2’所示结构：In a preferred embodiment, the repeating unit from the gelable monomer has the structure shown in the following formula 2 or formula 2':
Figure PCTCN2021135454-appb-000015
Figure PCTCN2021135454-appb-000015
式2中，R 4选自H或C 1-6烷基；R 5为OH、C 1-6烷氧基或聚醚链段；*表示连接端； In formula 2, R 4 is selected from H or C 1-6 alkyl; R 5 is OH, C 1-6 alkoxy or a polyether segment; * represents a connecting end;
式2’中，R 4选自H或C 1-6烷基；*表示连接端。 In formula 2', R 4 is selected from H or C 1-6 alkyl; * represents the connecting end.
在一个优选方案中，R 4选自H或C 1-3烷基；如R 4选自H或甲基。 In a preferred embodiment, R 4 is selected from H or C 1-3 alkyl; for example, R 4 is selected from H or methyl.
在一个优选方案中，R 5选自OH或C 1-3烷氧基。 In a preferred embodiment, R 5 is selected from OH or C 1-3 alkoxy.
在一个优选方案中，所述聚醚链段具有式8所示结构单元：In a preferred embodiment, the polyether segment has a structural unit shown in formula 8:
Figure PCTCN2021135454-appb-000016
Figure PCTCN2021135454-appb-000016
式8中，*表示连接端，p为聚合度。In Formula 8, * represents the connection end, and p represents the degree of polymerization.
在一个优选方案中，所述聚醚链段的数均分子量为60-3000。In a preferred embodiment, the number average molecular weight of the polyether segment is 60-3000.
在一个优选方案中，制备式2所示重复单元的单体选自如下式9所示化合物：In a preferred embodiment, the monomer for preparing the repeating unit shown in formula 2 is selected from the compound shown in formula 9 below:
Figure PCTCN2021135454-appb-000017
Figure PCTCN2021135454-appb-000017
式9中，R 4、R 5的定义如上所述。 In Formula 9, the definitions of R 4 and R 5 are as described above.
在一个优选方案中，制备式2’所示重复单元的单体选自如下式9’所示化合物：In a preferred embodiment, the monomer for preparing the repeating unit represented by the formula 2' is selected from the compound represented by the following formula 9':
Figure PCTCN2021135454-appb-000018
Figure PCTCN2021135454-appb-000018
式9’中，R 4的定义如上所述。 In formula 9', R 4 is as defined above.
在一个优选方案中，所述凝胶型聚合物选自聚醚硼酸酯丙烯酸酯和丙烯酸酯类单体的共聚物、聚醚铝酸酯丙烯酸酯和丙烯酸酯类单体的共聚物、聚醚磷酸酯丙烯酸酯和丙烯酸酯类单体的共聚物、聚醚硼酸酯甲基丙烯酸酯和丙烯酸酯类单体的共聚物、醚铝酸酯甲基丙烯酸酯和丙烯酸酯类单体的共聚物、醚磷酸酯甲基丙烯酸酯和丙烯酸酯类单体的共聚物、聚醚硼酸酯丙烯酸酯和丙烯腈类单体的共聚物、聚醚铝酸酯丙烯酸酯和丙烯腈类单体的共聚物、聚醚磷酸酯丙烯酸酯和丙烯腈类单体的共聚物、聚醚硼酸酯甲基丙烯酸酯和丙烯腈类单体的共聚物、醚铝酸酯甲基丙烯酸酯和丙烯腈类单体的共聚物、醚磷酸酯甲基丙烯酸酯和丙烯腈类单体的共聚物中的至少一种。其中，所述丙烯酸酯类单体包括丙烯酸、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯和甲基丙烯酸乙酯中的至少一种；所述丙烯腈类单体包括丙烯腈、甲基丙烯腈中的至少一种。In a preferred embodiment, the gel-type polymer is selected from the group consisting of copolymers of polyether borate acrylate and acrylate monomers, copolymers of polyether aluminate acrylate and acrylate monomers, polyether borate acrylates and acrylate monomers. Copolymers of ether phosphate acrylates and acrylate monomers, copolymers of polyether borate methacrylates and acrylate monomers, copolymers of ether aluminate methacrylates and acrylate monomers compounds, copolymers of ether phosphate methacrylates and acrylate monomers, copolymers of polyether borate acrylates and acrylonitrile monomers, copolymers of polyether aluminate acrylates and acrylonitrile monomers Copolymers, copolymers of polyether phosphate acrylates and acrylonitrile monomers, copolymers of polyether borate methacrylates and acrylonitrile monomers, ether aluminate methacrylates and acrylonitriles At least one of copolymers of monomers, ether phosphate methacrylates, and acrylonitrile-based monomers. Wherein, the acrylate monomers include at least one of acrylic acid, polyethylene glycol methacrylate, polyethylene glycol acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate One; the acrylonitrile monomers include at least one of acrylonitrile and methacrylonitrile.
在一个优选方案中，所述凝胶型聚合物中式1所示的重复单元与式2所示的重复单元的摩尔比为30-99:1-70，优选为50-99:1-50。式1所示的重复单元主要用于提升电导率、提高电化学窗口等作用，式2所示的重复单元主要用于改善聚合物与电解液的凝胶化。In a preferred embodiment, the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2 in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50. The repeating unit shown in formula 1 is mainly used to improve the conductivity and the electrochemical window, and the repeating unit shown in formula 2 is mainly used to improve the gelation of the polymer and the electrolyte.
在一个优选方案中，所述凝胶型聚合物中式1所示的重复单元与式2’所示的重复单元的摩尔比为30-99:1-70，优选为50-99:1-50。式1所示的重复单元主要用于提升电导率、提高电化学窗口等作用，式2’所示的重复单元主要用于降低凝胶型聚合物的结晶程度，改善凝胶型聚合物与电解液的凝胶化。In a preferred solution, the molar ratio of the repeating unit represented by formula 1 to the repeating unit represented by formula 2' in the gel-type polymer is 30-99:1-70, preferably 50-99:1-50 . The repeating unit shown in formula 1 is mainly used to improve the conductivity and the electrochemical window. liquid gelation.
在一个优选方案中，所述凝胶型聚合物的数均分子量为1000-500000，优选为5000-300000。In a preferred embodiment, the number-average molecular weight of the gel-type polymer is 1,000-500,000, preferably 5,000-300,000.
在一个优选方案中，所述凝胶型聚合物的电导率为>10 -3S/cm。 In a preferred embodiment, the electrical conductivity of the gel-type polymer is >10 -3 S/cm.
<凝胶型聚合物的制备方法><Method for producing gel-type polymer>
本发明还提供上述凝胶型聚合物的制备方法，所述方法包括如下步骤：The present invention also provides a method for preparing the above-mentioned gel-type polymer, the method comprising the steps of:
将有机溶剂、式7所示的聚合物单体、可凝胶单体和引发剂均匀混合，反应，制备得到所述凝胶型聚合物。The organic solvent, the polymer monomer shown in formula 7, the gelable monomer and the initiator are uniformly mixed and reacted to prepare the gel-type polymer.
在一个优选方案中，所述方法包括如下步骤：In a preferred version, the method comprises the steps:
将有机溶剂、式7所示的聚合物单体、式9或式9’所示的聚合物单体和引发剂均匀混合，反应，制备得到所述凝胶型聚合物。The organic solvent, the polymer monomer represented by the formula 7, the polymer monomer represented by the formula 9 or the formula 9' and the initiator are uniformly mixed and reacted to prepare the gel-type polymer.
在一个优选方案中，所述引发剂的加入量为聚合物单体总质量的0.05-1wt％。In a preferred embodiment, the added amount of the initiator is 0.05-1 wt % of the total mass of the polymer monomers.
在一个优选方案中，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯、过氧化苯甲酰、过氧化苯甲酰叔丁酯、4-(N,N-二甲氨基)苯甲酸乙酯、邻苯甲酰苯甲酸甲酯等中的一种或几种。In a preferred embodiment, the initiator is selected from azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide , one or more of 4-(N,N-dimethylamino) ethyl benzoate, methyl o-benzoyl benzoate, etc.
在一个优选方案中，所述有机溶剂选自N-甲基吡咯烷酮、乙腈、氢氟醚、丙酮、四氢呋喃、二氯甲烷、吡啶等、二甲苯、甲苯中的至少一种。In a preferred embodiment, the organic solvent is selected from at least one of N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, and toluene.
在一个优选方案中，所述方法具体包括如下步骤：In a preferred version, the method specifically comprises the following steps:
将60-100g式7所示的聚合物单体、0.5-50g式9或式9’所示的聚合物单体、100-600g溶剂，在氩气气体氛围下，以200-2000r/min的转速搅拌120-600min，然后加入0.01-0.5g引发剂，然后50-95℃条件下反应3-50h，得到所述凝胶型聚合物。Mix 60-100g of the polymer monomer represented by formula 7, 0.5-50g of the polymer monomer represented by formula 9 or formula 9', and 100-600g of solvent, under an argon gas atmosphere, at a rate of 200-2000r/min. Stir at a rotational speed for 120-600 min, then add 0.01-0.5 g of an initiator, and then react at 50-95° C. for 3-50 h to obtain the gel-type polymer.
<凝胶型聚合物电解质及其制备><Gel type polymer electrolyte and its preparation>
如上所述，本发明还提供一种凝胶型聚合物电解质，所述凝胶型聚合物电解质包括上述的凝胶型聚合物和电解质。As described above, the present invention also provides a gel-type polymer electrolyte, the gel-type polymer electrolyte includes the above-mentioned gel-type polymer and an electrolyte.
在一个优选方案中，所述电解质来源于电解液，所述电解液为本领域常规使用的电解液，例如是通过商业途径购买的，适用于锂离子电池中的电解液。In a preferred solution, the electrolyte is derived from an electrolyte, and the electrolyte is an electrolyte commonly used in the art, for example, purchased through commercial channels, and is suitable for an electrolyte in a lithium-ion battery.
本发明还提供上述凝胶型聚合物电解质的制备方法，所述方法包括如下步骤：The present invention also provides a method for preparing the above-mentioned gel polymer electrolyte, the method comprising the following steps:
将凝胶型聚合物浸泡在电解液中，静置一段时间后取出，制备得到所述凝胶型聚合物电解质。The gel polymer electrolyte is prepared by soaking the gel polymer in the electrolyte, and taking it out after standing for a period of time.
在一个优选方案中，所述静置的时间没有特别的限定，待凝胶型聚合物充分浸润即可。In a preferred solution, the standing time is not particularly limited, as long as the gel-type polymer is fully infiltrated.
<锂离子电池><Lithium-ion battery>
如上所述，本发明还提供一种锂离子电池，其包括上述的凝胶型聚合物电解质。As described above, the present invention also provides a lithium ion battery comprising the above-mentioned gel-type polymer electrolyte.
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
下述实施例中所使用的聚醚硼酸酯丙烯酸酯的结构为如式7所示，其中，R 1为H、R 2为不存在、R 3为H、M为式3所示； The structure of the polyether borate acrylate used in the following examples is as shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 is H, and M is shown in formula 3;
下述实施例中所使用的聚醚硼酸酯甲基丙烯酸酯的结构为如式7所示，其中，R 1为CH 3、R 2为不存在、R 3为H、M为式3所示； The structure of the polyether borate methacrylate used in the following examples is as shown in formula 7, wherein R 1 is CH 3 , R 2 is absent, R 3 is H, and M is represented by formula 3 Show;
下述实施例中所使用的聚醚铝酸酯丙烯酸酯的结构为如式7所示，其中，R 1为H、R 2为不存在、R 3为H、M为式5所示； The structure of the polyether aluminate acrylate used in the following examples is as shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 is H, and M is shown in formula 5;
下述实施例中所使用的聚醚铝酸酯甲基丙烯酸酯的结构为如式7所示，其中，R 1为CH 3、R 2为不存在、R 3为H、M为式5所示； The structure of the polyether aluminate methacrylate used in the following examples is as shown in formula 7, wherein R 1 is CH 3 , R 2 is absent, R 3 is H, and M is represented by formula 5 Show;
下述实施例中所使用的聚醚磷酸酯丙烯酸酯的结构为如式7所示，其中，R 1为H、R 2为不存在、R 3为H、M为式6所示； The structure of the polyether phosphate acrylate used in the following examples is as shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 is H, and M is shown in formula 6;
下述实施例中所使用的聚醚磷酸酯甲基丙烯酸酯的结构为如式7所示，其中，R 1为CH 3、R 2为不存在、R 3为H、M为式6所示。 The structure of the polyether phosphate methacrylate used in the following examples is as shown in formula 7, wherein R 1 is CH 3 , R 2 is absent, R 3 is H, and M is shown in formula 6 .
实施例1Example 1
1)正极极片的制备：1) Preparation of positive pole piece:
将95.5g正极活性物质钴酸锂、1.5g粘结剂聚偏氟乙烯(PVDF)、2.5g导电剂导电炭黑、0.5g导电剂碳纳米管进行混合，加入400gN-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌，直至混合体系成均一流动性的正极浆料；将正极浆料均匀涂覆于厚度为10μm的铝箔上；经过烘干80℃处理36小时后，抽真空处理后得到极片，并将该极片进行辊压后，裁切得到正极极片；Mix 95.5g positive electrode active material lithium cobaltate, 1.5g binder polyvinylidene fluoride (PVDF), 2.5g conductive agent conductive carbon black, 0.5g conductive agent carbon nanotubes, and add 400g N-methylpyrrolidone (NMP) , stir under the action of a vacuum mixer until the mixed system becomes a uniform fluid positive electrode slurry; the positive electrode slurry is evenly coated on an aluminum foil with a thickness of 10 μm; after drying at 80 °C for 36 hours, vacuuming to obtain pole piece, and after rolling the pole piece, cutting to obtain a positive pole piece;
2)负极极片制备：2) Preparation of negative pole piece:
将20g氧化亚硅、71g石墨、5g导电剂碳纳米管、2.5g丁苯粘结剂、1.5g羧甲基纤维素钠，溶解在300g水中，均匀混合后，涂覆于负极集流体铜箔的表面，经烘干(温度：80℃，时间：20h)、辊压和模切得到负极极片；Dissolve 20g of silicon oxide, 71g of graphite, 5g of conductive agent carbon nanotubes, 2.5g of styrene-butadiene binder, and 1.5g of sodium carboxymethyl cellulose in 300g of water, mix them evenly, and coat them on the negative current collector copper foil After drying (temperature: 80°C, time: 20h), rolling and die-cutting, the negative pole piece was obtained;
3)凝胶型聚合物薄膜电解质的制备：3) Preparation of gel-type polymer film electrolyte:
将80g聚醚硼酸酯丙烯酸酯(式7所示的结构，其中，R 1为H、R 2为不存在、R 3为H、M为式3所示)、20g甲基丙烯酸甲酯(式9所示的结构，其中，R 4为CH 3、R 5为OCH 3)、500g二甲苯，在氩气气体氛围下，以1000r/min的转速搅拌300min，然后加入0.05g偶氮二异丁腈，然后75℃条件下反应20h，提纯处理后采用流延法制备得到凝胶型聚合物薄膜，将该凝胶型聚合物薄膜浸泡在电解液(商用锂离子电池用电解液)中24h后得到凝胶型聚合物电解质薄膜； 80g polyether borate acrylate (structure shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 is H, and M is shown in formula 3), 20 g methyl methacrylate ( The structure shown in formula 9, wherein, R 4 is CH 3 , R 5 is OCH 3 ), 500 g of xylene, under an argon gas atmosphere, stirred at a rotational speed of 1000 r/min for 300 min, and then added 0.05 g of azodiiso Butyronitrile, then reacted at 75°C for 20h, after purification treatment, a gel-type polymer film was prepared by casting method, and the gel-type polymer film was immersed in electrolyte (electrolyte for commercial lithium-ion battery) for 24h Then a gel-type polymer electrolyte film is obtained;
4)锂离子电池的制备4) Preparation of lithium-ion batteries
将上述得到的负极极片、凝胶型聚合物电解质薄膜、负极极片通过叠片方式制备锂离子电池电芯，经过焊接、封装、化成、分选后得到锂离子电池。A lithium ion battery cell is prepared by laminating the negative pole piece, gel-type polymer electrolyte film, and negative pole piece obtained above, and a lithium ion battery is obtained after welding, packaging, chemical formation, and sorting.
对比例1.1Comparative Example 1.1
具体工艺参考实施例1，主要区别对比例1.1中采用等质量等分子量量的聚氧化乙烯替代实施例1中凝胶型聚合物，其他条件与实施例1一致。The specific process refers to Example 1, the main difference is that in Comparative Example 1.1, polyethylene oxide of equal mass and molecular weight is used to replace the gel-type polymer in Example 1, and other conditions are consistent with Example 1.
对比例1.2Comparative Example 1.2
具体工艺参考实施例1，主要区别对比例1.2的体系中的单体为0g聚醚硼酸酯丙烯酸酯(式7所示的结构，其中，R 1为H、R 2为不存在、R 3为H、M为式3所示)和100g甲基丙烯酸甲酯(式9所示的结构，其中，R 4为CH 3、R 5为OCH 3)，其他条件与实施例1一致。 The specific process refers to Example 1, the main difference is that the monomer in the system of Comparative Example 1.2 is 0 g of polyether borate acrylate (the structure shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 H and M are shown in formula 3) and 100 g of methyl methacrylate (structure shown in formula 9, wherein R 4 is CH 3 and R 5 is OCH 3 ), and other conditions are the same as in Example 1.
对比例1.3Comparative Example 1.3
具体工艺参考实施例1，主要区别对比例1.3的体系中的单体为100g聚醚硼酸酯丙烯酸酯(式7所示的结构，其中，R 1为H、R 2为不存在、R 3为H、M为式3所示)和0g甲基丙烯酸甲酯(式9所示的结构，其中，R 4为CH 3、R 5为OCH 3)，其他条件与实施例1一致。 The specific process refers to Example 1, the main difference is that the monomer in the system of Comparative Example 1.3 is 100 g of polyether borate acrylate (structure shown in formula 7, wherein R 1 is H, R 2 is absent, R 3 H and M are shown in formula 3) and 0 g of methyl methacrylate (structure shown in formula 9, wherein R 4 is CH 3 and R 5 is OCH 3 ), and other conditions are the same as in Example 1.
实施例2-13Examples 2-13
具体流程参考实施例1，主要区别是工艺条件、各组分加入量、各组分物料种类，具体详情见表1和表2。The specific process refers to Example 1, and the main differences are the process conditions, the amount of each component added, and the type of each component material. The specific details are shown in Table 1 and Table 2.
表1实施例和对比例的凝胶型聚合物的组分含量及制备条件Table 1 Component content and preparation conditions of the gel-type polymers of the examples and comparative examples
Figure PCTCN2021135454-appb-000019
Figure PCTCN2021135454-appb-000019
Figure PCTCN2021135454-appb-000020
Figure PCTCN2021135454-appb-000020
测试例1Test Example 1
对上述实施例和对比例的制备的凝胶型聚合物薄膜，浸泡在电解液24h后，对凝胶型聚合物电解质进行电化学窗口测试和电导率测试。The gel-type polymer films prepared in the above examples and comparative examples were soaked in the electrolyte for 24 hours, and then the gel-type polymer electrolyte was subjected to electrochemical window test and electrical conductivity test.
电化学窗口测试：采用不锈钢/凝胶型聚合物电解质/锂片结构，采用辰华CHE660E型电化学工作站对凝胶型聚合物电解质进行电化学稳定性测试，测试区间2-6V，测试频率0.05mV/S。测试结果如表2所示。Electrochemical window test: using stainless steel/gel-type polymer electrolyte/lithium sheet structure, using Chenhua CHE660E electrochemical workstation to test the electrochemical stability of gel-type polymer electrolyte, the test range is 2-6V, the test frequency is 0.05 mV/S. The test results are shown in Table 2.
电导率测试：采用不锈钢/凝胶型聚合物电解质/不锈钢结构，采用辰华CHE660E型电化学工作站对凝胶型聚合物电解质进行交流阻抗测试，通过测试阻抗和凝胶型聚合物电解质厚度，计算出电导率。测试结果如表2所示。Conductivity test: using stainless steel/gel-type polymer electrolyte/stainless steel structure, using Chenhua CHE660E electrochemical workstation to conduct AC impedance test on gel-type polymer electrolyte, by testing impedance and gel-type polymer electrolyte thickness, calculate out the conductivity. The test results are shown in Table 2.
表2实施例和对比例的凝胶型聚合物电解质的电化学窗口和电导率测试结果Table 2 Electrochemical window and conductivity test results of gel-type polymer electrolytes of Examples and Comparative Examples
Figure PCTCN2021135454-appb-000021
Figure PCTCN2021135454-appb-000021
Figure PCTCN2021135454-appb-000022
Figure PCTCN2021135454-appb-000022
对实施例1、对比例1.1、对比例1.2、对比例1.3的聚合物电解质的电化学稳定性测试结果进行分析，结果如图1-图4所示，其中图中，横坐标为电压(单位，V)，纵坐标为电流(单位，A)。The electrochemical stability test results of the polymer electrolytes of Example 1, Comparative Example 1.1, Comparative Example 1.2, and Comparative Example 1.3 were analyzed. The results are shown in Figures 1 to 4, in which the abscissa is the voltage (unit , V), and the ordinate is the current (unit, A).
结果表明：实施例1制备的凝胶型聚合物电解质电化学窗口为4.45V左右，对比例1.1制备的聚合物电解质电化学窗口为3.80V左右，对比例1.2制备的凝胶型聚合物电解质电化学窗口为4.40V左右，对比例1.3制备的凝胶型聚合物电解质电化学窗口为4.50V左右。说明本发明的凝胶型聚合物电解质具有良好的电化学稳定性，可匹配高电压正极材料，具有良好的应用前景。The results show that the electrochemical window of the gel-type polymer electrolyte prepared in Example 1 is about 4.45V, the electrochemical window of the polymer electrolyte prepared in Comparative Example 1.1 is about 3.80V, and the electrochemical window of the gel-type polymer electrolyte prepared in Comparative Example 1.2 is about 3.80V. The chemical window is about 4.40V, and the electrochemical window of the gel-type polymer electrolyte prepared in Comparative Example 1.3 is about 4.50V. It shows that the gel-type polymer electrolyte of the present invention has good electrochemical stability, can be matched with high-voltage positive electrode materials, and has good application prospects.
综合电化学稳定性测试和交流阻抗测试结果表明，实施例1制备的凝胶型聚合物电解质电导率为4.81mS/cm左右，对比例1.1制备的聚合物电解质电导率为4.22mS/cm左右，对比例1.2制备的凝胶型聚合物电解质电导率为3.35mS/cm左右，对比例1.3制备的凝胶型聚合物电解质电导率为4.31mS/cm左右。该实验结果表明本发明实施例所示的特定结构的聚合物单体能够有效的提升电解质的锂离子电导率和电化学稳定性。主要原因是本发明的聚合单体由两种单体聚合而成，本发明凝胶型聚合物电解质具有梳状结构，支链具有聚硼醚、聚铝醚、聚磷醚结构，该类结构既可以进行导锂，有具有良好的电化学稳定性；同时本发明凝胶型聚合物电解质有两种单体共聚而成，具有较低的结晶程度，与电解液亲和性更好，具有更高的电导率。所以实施例1制备的凝胶型聚合物电解质综合性能较优。The comprehensive electrochemical stability test and AC impedance test results show that the conductivity of the gel-type polymer electrolyte prepared in Example 1 is about 4.81 mS/cm, and the conductivity of the polymer electrolyte prepared in Comparative Example 1.1 is about 4.22 mS/cm. The conductivity of the gel-type polymer electrolyte prepared in Comparative Example 1.2 is about 3.35 mS/cm, and the conductivity of the gel-type polymer electrolyte prepared in Comparative Example 1.3 is about 4.31 mS/cm. The experimental results show that the specific structure of the polymer monomer shown in the embodiment of the present invention can effectively improve the lithium ion conductivity and electrochemical stability of the electrolyte. The main reason is that the polymerized monomer of the present invention is polymerized from two monomers. The gel-type polymer electrolyte of the present invention has a comb-like structure, and the branched chain has the structure of polyboron ether, polyaluminum ether, and polyphosphorus ether. It can conduct lithium conduction and has good electrochemical stability; at the same time, the gel-type polymer electrolyte of the present invention is formed by copolymerization of two monomers, has a lower degree of crystallization, has better affinity with the electrolyte, and has higher conductivity. Therefore, the gel-type polymer electrolyte prepared in Example 1 has better comprehensive performance.
表3实施例和对比例的电池倍率性能测试结果Table 3 The battery rate performance test results of the embodiment and the comparative example
容量保持率capacity retention 0.2C/0.2C0.2C/0.2C 0.5C/0.5C0.5C/0.5C 1.0C/1.0C1.0C/1.0C 1.5C/1.5C1.5C/1.5C
实施例1Example 1 100％100% 97.8％97.8% 95.3％95.3% 94.5％94.5%
对比例1.1Comparative Example 1.1 100％100% 94.3％94.3% 88.4％88.4% 85.2％85.2%
对比例1.2Comparative Example 1.2 100％100% 95.6％95.6% 92.3％92.3% 90.7％90.7%
对比例1.3Comparative Example 1.3 100％100% 96.4％96.4% 93.1％93.1% 91.3％91.3%
实施例2Example 2 100％100% 97.1％97.1% 94.9％94.9% 93.3％93.3%
实施例3Example 3 100％100% 98.3％98.3% 96.5％96.5% 95.1％95.1%
实施例4Example 4 100％100% 96.7％96.7% 94.2％94.2% 92.4％92.4%
实施例5Example 5 100％100% 97.2％97.2% 94.6％94.6% 93.9％93.9%
实施例6Example 6 100％100% 98.0％98.0% 95.2％95.2% 94.7％94.7%
实施例7Example 7 100％100% 97.5％97.5% 94.9％94.9% 93.7％93.7%
实施例8Example 8 100％100% 98.5％98.5% 96.8％96.8% 95.3％95.3%
实施例9Example 9 100％100% 98.2％98.2% 95.8％95.8% 94.9％94.9%
实施例10Example 10 100％100% 97.0％97.0% 95.0％95.0% 93.6％93.6%
实施例11Example 11 100％100% 97.5％97.5% 95.2％95.2% 93.9％93.9%
实施例12Example 12 100％100% 97.4％97.4% 95.1％95.1% 94.1％94.1%
实施例13Example 13 100％100% 97.5％97.5% 95.0％95.0% 93.5％93.5%
测试例2 Test case 2
实施例1、对比例1.1、对比例1.2、对比例1.3、实施例2-13的制备的锂离子电池进行倍率测试，测试过程为：锂离子电池在蓝电电池充放电测试柜上进行3.0-4.45V充放电倍率测试，测试条件为25℃，采用未循环电池，对电池以0.2C/0.2C、0.5C/0.5C、1.0C/1.0C、1.5C/1.5C倍率，进行倍率充放电，考察电池倍率性能。测试结果如表3所示。Example 1, Comparative Example 1.1, Comparative Example 1.2, Comparative Example 1.3, and the prepared lithium-ion batteries of Examples 2-13 were subjected to a rate test. The test process was as follows: the lithium-ion battery was charged and discharged on a blue battery test cabinet for 3.0-4.45 V charge-discharge rate test, the test condition is 25 ℃, using an uncycled battery, the battery is charged and discharged at a rate of 0.2C/0.2C, 0.5C/0.5C, 1.0C/1.0C, 1.5C/1.5C, Investigate the battery rate performance. The test results are shown in Table 3.
本发明专利制备的锂离子电池，其中实施例1、对比例1.1、对比例1.2和对比例1.3的倍率充放电性能测试结果表明：本发明实施例1制备的锂离子电池具有更好的倍率性能，尤其是是在＞0.5C倍率以上。主要原因是锂离子电池中的凝胶型聚合物电解质，实施例1与对比例1.1、对比例1.2、对比例1.3相比，实施例1制备的凝胶型聚合物电解质具有良好的锂离子电导率和电化学稳定性。For the lithium ion battery prepared by the patent of the present invention, the test results of the rate charge and discharge performance of Example 1, Comparative Example 1.1, Comparative Example 1.2 and Comparative Example 1.3 show that the lithium ion battery prepared in Example 1 of the present invention has better rate performance , especially at >0.5C magnification. The main reason is the gel-type polymer electrolyte in the lithium-ion battery. Compared with Comparative Example 1.1, Comparative Example 1.2, and Comparative Example 1.3, the gel-type polymer electrolyte prepared in Example 1 has good lithium ion conductivity. rate and electrochemical stability.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实 施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种凝胶型聚合物，所述凝胶型聚合物包括来自可凝胶单体的重复单元和如下式1所示的重复单元：A gel-type polymer comprising repeating units derived from gelable monomers and repeating units as shown in Formula 1 below:
    Figure PCTCN2021135454-appb-100001
    Figure PCTCN2021135454-appb-100001
    式1中，R 1选自H或C 1-6烷基；R 2为连接基团；R 3为封端基团；M选自硼酸酯链段、铝酸酯链段或磷酸酯链段；*表示连接端。 In formula 1, R 1 is selected from H or C 1-6 alkyl; R 2 is a linking group; R 3 is an end capping group; M is selected from a boronate chain segment, an aluminate ester chain segment or a phosphate chain segment; * indicates the connection end.
  2. 根据权利要求1所述的凝胶型聚合物，其中，所述来自可凝胶单体的重复单元具有如下式2或式2’所示结构：The gel-type polymer according to claim 1, wherein the repeating unit derived from the gelable monomer has a structure represented by the following formula 2 or formula 2':
    Figure PCTCN2021135454-appb-100002
    Figure PCTCN2021135454-appb-100002
    式2中，R 4选自H或C 1-6烷基；R 5为OH、C 1-6烷氧基或聚醚链段；*表示连接端； In formula 2, R 4 is selected from H or C 1-6 alkyl; R 5 is OH, C 1-6 alkoxy or a polyether segment; * represents a connecting end;
    式2’中，R 4选自H或C 1-6烷基；*表示连接端。 In formula 2', R 4 is selected from H or C 1-6 alkyl; * represents the connecting end.
  3. 根据权利要求1或2所述的凝胶型聚合物，其中，所述硼酸酯链段具有式3或式4所示结构单元：The gel-type polymer according to claim 1 or 2, wherein the boronate ester segment has a structural unit represented by formula 3 or formula 4:
    Figure PCTCN2021135454-appb-100003
    Figure PCTCN2021135454-appb-100003
    式3和式4中，*表示连接端，n为聚合度。In Formula 3 and Formula 4, * represents the connection end, and n represents the degree of polymerization.
    优选地，所述铝酸酯链段具有式5所示结构单元：Preferably, the aluminate segment has a structural unit represented by formula 5:
    Figure PCTCN2021135454-appb-100004
    Figure PCTCN2021135454-appb-100004
    式5中，*表示连接端，m为聚合度；In formula 5, * represents the connection end, and m is the degree of polymerization;
    优选地，所述磷酸酯链段具有式6所示结构单元：Preferably, the phosphate segment has a structural unit shown in formula 6:
    Figure PCTCN2021135454-appb-100005
    Figure PCTCN2021135454-appb-100005
    式6中，*表示与R 3的连接端，**表示与R 2的连接端，q为聚合度。 In formula 6, * represents the connection end with R 3 , ** represents the connection end with R 2 , and q is the degree of polymerization.
  4. 根据权利要求1-3任一项所述的凝胶型聚合物，其中，制备式1所示重复单元的单体选自如下式7所示化合物：The gel-type polymer according to any one of claims 1-3, wherein the monomer for preparing the repeating unit represented by the formula 1 is selected from the compound represented by the following formula 7:
    Figure PCTCN2021135454-appb-100006
    Figure PCTCN2021135454-appb-100006
    式7中，R 1、R 2、R 3、M的定义如上所述； In formula 7, the definitions of R 1 , R 2 , R 3 , and M are as described above;
    优选地，式7所示化合物选自聚醚硼酸酯丙烯酸酯、聚醚铝酸酯丙烯酸酯、聚醚磷酸酯丙烯酸酯、聚醚硼酸酯甲基丙烯酸酯、聚醚铝酸酯甲基丙烯酸酯、聚醚磷酸酯甲基丙烯酸酯中的至少一种。Preferably, the compound represented by formula 7 is selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate methyl acrylate At least one of acrylate and polyether phosphate methacrylate.
  5. 根据权利要求2-4任一项所述的凝胶型聚合物，其中，R 4选自H或C 1-3烷基；和/或， The gel-type polymer according to any one of claims 2-4, wherein R 4 is selected from H or C 1-3 alkyl; and/or,
    R 5选自OH或C 1-3烷氧基；和/或， R 5 is selected from OH or C 1-3 alkoxy; and/or,
    所述聚醚链段具有式8所示结构单元：The polyether segment has a structural unit shown in formula 8:
    Figure PCTCN2021135454-appb-100007
    Figure PCTCN2021135454-appb-100007
    式8中，*表示连接端，p为聚合度。In Formula 8, * represents the connection end, and p represents the degree of polymerization.
  6. 根据权利要求2-5任一项所述的凝胶型聚合物，其中，制备式2所示重复单元的单体选自如下式9所示化合物：The gel-type polymer according to any one of claims 2-5, wherein the monomer for preparing the repeating unit represented by formula 2 is selected from the compound represented by the following formula 9:
    Figure PCTCN2021135454-appb-100008
    Figure PCTCN2021135454-appb-100008
    式9中，R 4、R 5的定义如上所述；和/或， In formula 9, R 4 and R 5 are as defined above; and/or,
    制备式2’所示重复单元的单体选自如下式9’所示化合物：The monomer for preparing the repeating unit represented by the formula 2' is selected from the compound represented by the following formula 9':
    Figure PCTCN2021135454-appb-100009
    Figure PCTCN2021135454-appb-100009
    式9’中，R 4的定义如上所述。 In formula 9', R 4 is as defined above.
  7. 根据权利要求1-6任一项所述的凝胶型聚合物，其中，所述凝胶型聚合 物中式1所示的重复单元与式2所示的重复单元的摩尔比为30-99:1-70；和/或，The gel-type polymer according to any one of claims 1-6, wherein the molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2 in the gel-type polymer is 30-99: 1-70; and/or,
    所述凝胶型聚合物中式1所示的重复单元与式2’所示的重复单元的摩尔比为30-99:1-70。The molar ratio of the repeating unit shown in formula 1 to the repeating unit shown in formula 2' in the gel-type polymer is 30-99:1-70.
  8. 根据权利要求1-7任一项所述的凝胶型聚合物，其中，所述凝胶型聚合物的数均分子量为1000-500000；和/或，The gel-type polymer according to any one of claims 1-7, wherein the number-average molecular weight of the gel-type polymer is 1,000-500,000; and/or,
    所述凝胶型聚合物的电导率为>4.5mS/cm。The conductivity of the gel-type polymer is >4.5 mS/cm.
  9. 一种凝胶型聚合物电解质，所述凝胶型聚合物电解质包括权利要求1-8任一项所述的凝胶型聚合物和电解质。A gel-type polymer electrolyte, the gel-type polymer electrolyte comprising the gel-type polymer according to any one of claims 1-8 and an electrolyte.
  10. 一种锂离子电池，其包括权利要求1-8任一项所述的凝胶型聚合物，或其包括权利要求9所述的凝胶型聚合物电解质。A lithium ion battery comprising the gel-type polymer of any one of claims 1-8, or comprising the gel-type polymer electrolyte of claim 9.
PCT/CN2021/135454 2020-09-15 2021-12-03 Gel-type polymer and lithium ion battery containing gel-type polymer WO2022117082A1 (en)

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