WO2023046091A1 - Solid electrolyte and use thereof - Google Patents

Solid electrolyte and use thereof Download PDF

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Publication number
WO2023046091A1
WO2023046091A1 PCT/CN2022/120961 CN2022120961W WO2023046091A1 WO 2023046091 A1 WO2023046091 A1 WO 2023046091A1 CN 2022120961 W CN2022120961 W CN 2022120961W WO 2023046091 A1 WO2023046091 A1 WO 2023046091A1
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Prior art keywords
solid electrolyte
substituted
unsubstituted
polymer
electrode sheet
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PCT/CN2022/120961
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French (fr)
Chinese (zh)
Inventor
唐伟超
夏定国
李素丽
赵伟
李俊义
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珠海冠宇电池股份有限公司
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Publication of WO2023046091A1 publication Critical patent/WO2023046091A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the application belongs to the field of lithium ion batteries, and relates to a solid electrolyte, in particular to a solid electrolyte and its application.
  • the all-solid-state battery is to replace the flammable electrolyte in the traditional lithium-ion battery with a non-flammable solid electrolyte, which fundamentally avoids the safety problems caused by the volatility and flammability of organic solvents, and thus eliminates to a certain extent Safety hazards due to flatulence or burning of lithium-ion batteries.
  • the present application provides a solid electrolyte, which is conducive to further improving the safety performance of lithium-ion batteries due to its special composition, especially in terms of high-temperature safety.
  • the present application also provides a lithium-ion battery, which includes the above-mentioned solid electrolyte, and therefore has excellent safety performance.
  • the present application also provides a positive electrode sheet, which includes the above-mentioned solid electrolyte, thus helping to improve the safety performance of the lithium-ion battery.
  • the present application also provides a negative electrode sheet, which includes the above-mentioned solid electrolyte, thus helping to improve the safety performance of the lithium-ion battery.
  • the present application also provides a lithium-ion battery, including the above-mentioned positive electrode sheet and/or negative electrode sheet, so the high-temperature safety performance of the lithium-ion battery is excellent.
  • the present application provides a solid electrolyte comprising a polymer comprising a first structural unit derived from a monoolefin compound containing substituted or unsubstituted ureido groups and a polyolefin crosslinking agent the second structural unit.
  • R 1 , R 3 , and R 4 are independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 1-12 alkoxy substituted or unsubstituted amino group;
  • R 2 is selected from carbonyl, substituted or unsubstituted (hetero) aryl, ester group, substituted or unsubstituted C 1 ⁇ 12 alkylene, carboxyl or chemical bond;
  • M 1 is selected from H, carbonyl, substituted or unsubstituted C 1 to 20 alkyl, substituted or unsubstituted C 1 to 20 alkoxy, hydroxyl, halogen, amino, nitro, trifluoromethyl, hydrocarbon thio, substituted or unsubstituted Substituted (hetero)aryl;
  • M 2 and M 3 are independently selected from hydrogen, substituted or unsubstituted C 4-60 (hetero)aryl
  • the solid electrolyte comprises: 40%-90% of polymer, 10%-40% of lithium salt, and 0%-20% of auxiliary agent in terms of mass percentage.
  • the present application provides a lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet, and any one of the solid electrolytes described above located between the positive electrode sheet and the negative electrode sheet.
  • the present application provides a positive electrode sheet, which includes the solid electrolyte described in any one of the above;
  • the positive electrode sheet includes a positive electrode active layer, and the interior and/or surface of the positive electrode active layer has the solid electrolyte.
  • the present application provides a negative electrode sheet, which includes the solid electrolyte described in any one of the above;
  • the negative electrode sheet includes a negative electrode matrix, and the interior and/or surface of the negative electrode matrix has the solid electrolyte.
  • the present application provides a lithium ion battery, comprising the above-mentioned positive electrode sheet, and/or the above-mentioned negative electrode sheet.
  • the present application provides a solid electrolyte, and the polymer in the solid electrolyte is obtained by copolymerizing monomers containing ureido groups and multiolefin crosslinking monomers.
  • the polymer has more excellent mechanical strength, so it has excellent performance in improving the high-temperature performance of lithium-ion batteries.
  • the lithium-ion battery of the present application includes the above-mentioned solid electrolyte, which can not only realize the conduction of lithium ions, but also significantly improve the safety performance of the lithium-ion battery. Therefore, the lithium-ion battery of the present application has excellent performance in high temperature performance.
  • the positive electrode sheet of the present application includes the above-mentioned solid electrolyte, which can significantly improve the safety performance of the positive electrode sheet, and can still maintain a normal working state under high temperature conditions.
  • the negative electrode sheet of the present application includes the above-mentioned solid electrolyte, which can significantly improve the safety performance of the negative electrode sheet, and can still maintain a normal working state under high temperature conditions.
  • the lithium-ion battery of the present application includes the positive electrode sheet and/or the negative electrode sheet, so it has excellent safety performance, especially in high temperature performance.
  • the first aspect of the present application provides a solid electrolyte, which includes a polymer, and the polymer includes a first structural unit derived from a monoolefin compound containing a substituted or unsubstituted ureido group and a polyene derived from a The second structural unit of the crosslinker.
  • the polymer in the solid electrolyte of the present application includes substituted or unsubstituted ureido groups, wherein the structure of the unsubstituted ureido groups is:
  • the substituted ureido group refers to a hydrogen in the ureido group or is substituted by a substituent R or both hydrogens are substituted by a substituent R, and the structural formula is as follows:
  • R can be acyl, carboxyl, substituted or unsubstituted C1-C36 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted Substituted C3-C30 heteroaryl, substituted or unsubstituted alkoxy, etc., when these groups have substituents, the substituents are independently selected from halogen, cyano, nitro, amino, C1-C10 One or more of alkyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 aryl, C3-C30 heteroaryl, etc.
  • the polymers of the present application in addition to the first structural unit derived from a monoolefin compound containing substituted or unsubstituted ureido groups, also comprise a second structural unit derived from a multiolefin crosslinking agent.
  • the present application is not limited to the specific structure of the multi-olefin crosslinking agent, as long as it can realize crosslinking and has at least two alkenyl groups.
  • the above-mentioned polymers are derived from the polymerization of monomers, and the monomers include at least two kinds, which are respectively monoolefin compounds containing substituted or unsubstituted ureido groups (hereinafter referred to as the first monomer) and polyolefin compounds.
  • Olefin crosslinking agent hereinafter referred to as the second monomer.
  • the first monomer can specifically be a monoolefin compound containing a substituted or unsubstituted ureido group, or it can be a plurality of compounds that are different from each other, but these multiple compounds that are different from each other Both are monoolefin compounds containing substituted or unsubstituted ureido groups; similarly, the second monomer can be seen as a multiolefin compound with crosslinking function, or it can be a plurality of compounds that are different from each other, However, these plural mutually different compounds are all polyene compounds and have a crosslinking function.
  • the solid-state electrolyte of the present application includes lithium salts and additives in addition to the above-mentioned polymers.
  • lithium salts commonly used in the art can be used, specifically lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), Lithium tetrafluoroborate (LiBF4), lithium bisoxalate borate (LiBOB), lithium difluoroborate oxalate (LiDFOB), lithium bisdifluorosulfonyl imide (LiFSI), lithium bistrifluoromethylsulfonyl imide (LiTFSI) , lithium trifluoromethanesulfonate (LiCF3SO3), bismalonate borate (LiBMB), lithium malonate oxalate borate (LiMOB), lithium hexafluoroantimonate (LiSbF6), lithium difluorophosphate (LiPF2O2),
  • the auxiliary agent is selected from at least one of oxide electrolytes, nano fillers and organic auxiliary agents.
  • the oxidation electrolyte can be selected from lithium phosphate, lithium titanate, lithium titanium phosphate, lithium titanium aluminum phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium germanium aluminum phosphate, lithium aluminosilicate, lithium silicon phosphate, titanic acid At least one of lanthanum lithium; nanofillers can be selected from at least one of alumina, magnesia, boehmite, barium sulfate, barium titanate, zinc oxide, calcium oxide, silicon dioxide, silicon carbide, nickel oxide ; Organic additives can be selected from nitrogen-containing organic small molecule compounds, which are used to improve the electrolyte processing window and avoid changes in electrolyte components during processing.
  • nitrogen-containing organic small molecule compounds can be selected from succinonitrile, N-methylacetamide, 3-cyano-7-azaindole, 7-azaindole-4-carbonitrile, 3,3' -Azotoluene, 5-methylbenzotriazole, 3,4,5-trifluorophenylacetonitrile, 3,4,5,6-tetrafluorophthalonitrile, 1,2-naphthalene dicarbonitrile, 2-Amino-4,5-imidazoledicarbonitrile, 5-methylbenzotriazole, methylurea, 1,3-diethylurea, ethylurea, fluoroether, 2-fluorophenetole, At least one of perfluorocyclic ether and acifluorfen.
  • the solid electrolyte comprises: 40%-90% of polymer, 10%-40% of lithium salt, and 0%-20% of auxiliary agent in terms of mass percentage.
  • the solid electrolyte comprising the above polymer of the present application can not only realize the conduction of lithium ions, complete the deintercalation of lithium ions in the positive and negative electrodes, but also effectively ensure the safety performance of lithium ion batteries, especially lithium ion batteries containing the solid electrolyte It can still maintain a safe state in a high temperature state, avoiding the occurrence of fire and explosion accidents caused by high temperature. Based on this phenomenon, the inventor analyzed the reason for the improvement of safety performance, and believed that it may be that the polymer containing the first structural unit and the second structural unit can provide a denser network structure for the solid electrolyte, thereby achieving Good mechanical properties of solid electrolytes.
  • the high-strength solid electrolyte can effectively slow down the growth and penetration process of lithium dendrites, thereby realizing the safety performance of lithium-ion batteries improvement.
  • the solid electrolyte can still maintain a normal state at high temperature, avoiding the occurrence of deformation caused by high temperature, reducing the contact probability of positive and negative electrodes, and suppressing thermal runaway.
  • the inventors have found that when the first structural unit in the polymer in the solid electrolyte comes from a monoolefin compound containing a substituted or unsubstituted ureido group shown in Formula 1, that is, the first monomer has the formula 1 When the structure is used, the improvement effect on the safety performance of the lithium-ion battery is more obvious.
  • R1, R3, and R4 are independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C1-12 alkoxy, substituted Or unsubstituted amino;
  • R2 is selected from carbonyl, substituted or unsubstituted (hetero) aryl, ester group, substituted or unsubstituted C1 ⁇ 12 alkylene, carboxyl or chemical bond;
  • M1 is selected from H, carbonyl, substituted or Unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 alkoxy, hydroxyl, halogen, amino, nitro, trifluoromethyl, hydrocarbon thio, substituted or unsubstituted (hetero)aryl;
  • M2 and M3 are independently selected from hydrogen, substituted or unsubstituted C4 ⁇ 60 (hetero)aryl, substituted or unsubstituted
  • the substituents can be selected from halogen, nitro, cyano, hydroxyl, trifluoromethyl, C1 ⁇ 12 hydrocarbon thio groups, etc.;
  • R2 is carbonyl RCO-* (R is a substituted or unsubstituted C1-12 alkanyl group, a substituted or unsubstituted C3-12 cycloalkyl group, a substituted or unsubstituted C1-12 alkoxy group, a substituted or Unsubstituted C4 ⁇ 60 (hetero)aryl, substituted or unsubstituted hydroxyl, the substituent is C4 ⁇ 60 (hetero)aryl, halogen, nitro, amino, cyano, etc.), substituted or unsubstituted (hetero) ) aryl group (the carbon atom (or heteroatom) on the (hetero) aryl group is directly bonded to the N atom in the ureido group, or the substituent on the (hetero) aryl group is directly bonded to the N atom in the urea group Connection, substituents are C1 ⁇ 12 alkyl, C1 ⁇ 12 alkoxy,
  • M1 is selected from H, substituted or unsubstituted C1-20 alkyl (substituents are C1-12 alkoxy, C4-30 hetero (aryl) group, halogen, amino, carboxyl, ester group, acyl group, etc.), Substituted or unsubstituted C1-20 alkoxy (substituents are C1-12 alkyl, C4-30 hetero (aryl) group, nitro, halogen, amino, carboxyl, ester, acyl, etc.), hydroxyl, Halogen, amino, nitro, trifluoromethyl, sulfenyl, substituted or unsubstituted (hetero)aryl (as defined in R2), carbonyl RCO-* (R defined as in R2), wherein, " -*" represents a chemical bond directly bonded to the N atom in the urea group;
  • M2 and M3 are independently selected from hydrogen, substituted or unsubstituted C4 ⁇ 60 (hetero)aryl (the definition is the same as in R2), substituted or unsubstituted C1 ⁇ 20 alkyl (the definition is the same as in M1), substituted Or unsubstituted C1 ⁇ 20 alkoxy (the definition is the same as in M1), carbonyl RCO-* (the definition of R is the same as in M1), substituted or unsubstituted C2 ⁇ 12 cycloalkyl containing heterocyclic atoms (the substituent is C1-12 alkoxy, C4-30 hetero (aryl) group, halogen, amino, carboxyl, ester, acyl, etc.), acyl RCO-* (R is a substituted or unsubstituted C1-12 alkyl or alkenyl group, halogen, amino, etc., substituents are C1-12 alkoxy, halogen, cyano, nitro, amino, etc.
  • the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 100-5000, preferably 150-2000.
  • the present application does not limit the preparation method of the compound represented by the above formula 1.
  • the compound represented by the above formula 1 is prepared by a method comprising the following process:
  • the solvent system comprising the first isocyanate compound and the first amine compound (primary amine or secondary amine) is reacted to obtain the monoolefin compound containing a substituted or unsubstituted ureido group, that is, the compound shown in formula 1 .
  • the first isocyanate satisfies the structure shown in formula 2a
  • the first amine compound satisfies the structure shown in formula 3a.
  • M1 is a hydrogen atom.
  • the first isocyanate compound satisfying the formula 2a may be selected from at least one of acryl isocyanate, acryl isocyanate, acryl isocyanate and derivatives thereof. Specifically, selected from methacryloyl isocyanate, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, isocyanate ethyl acrylate, isocyanoethyl methacrylate, vinyl isocyanate, 3- At least one of allyl isocyanate, 3-ethoxy-2-acryloyl isocyanate, and the like.
  • the first amine compound satisfying formula 3a can be selected from, for example, 2-aminopyrimidine-5-carboxylic acid, 2-amino-3-iodo-5-picoline, N-(4-pyridylmethyl)ethylamine, 3 -Methylthiophene-2-carboxamide, 2-bromo-3-amino-4-methylpyridine, 3-chloro-4-fluorobenzylamine, 2-amino-5,7-difluorobenzothiazole,, phenoline, 2,4-dichloroaniline, 3-aminophthalic anhydride, 2-amino-3-hydroxymethylpyridine, 3-amino-4-chloropyridine, tritylamine, 1,3-benzo Thiazol-5-amine, 2-amino-5-cyanopyridine, 4-aminoisoxazole, 2-aminoisonicotinic acid ethyl ester, 6-azauracil, 3,4-pyridine diimide, Dimethylpyridin
  • the compound represented by the above formula 1 can also be prepared according to the method comprising the following process:
  • M2 or M3 is a hydrogen atom.
  • the second amine compound satisfying formula 2b can be selected from, for example, olefinic compounds containing primary or secondary amine groups of pentenoic acids, olefinic compounds containing primary or secondary amine groups of glycines, carboxylic acid esters containing primary amines or at least one of olefinic compounds with secondary amine groups.
  • the second isocyanate compound satisfying formula 3b can be selected from, for example, p-4-methoxyphenylisocyanate, 3,4-dichlorophenylisocyanate, 4-methoxybenzylisocyanate, 2-phenylethylisocyanate, 4-bromo- 3-Tolyl isocyanate, 2-(methoxycarbonyl)phenyl isocyanate, 4-bromo-2-chlorophenyl isocyanate, 2,3,5-dimethylphenyl isocyanate, 2- Methoxy-4-nitrobenzene isocyanate, 4-chloro-3-nitrobenzene isocyanate, 2-chloro-5-(trifluoromethyl)phenyl isocyanate, 2-isocyanate , 5-difluorophenyl ester, 4-cyanobenzene isocyanate, 6-fluoro-1H-1,3-benzodiox (hetero)an-8-yl isocyanate, 4-isocyano-3
  • the reaction system also includes a solvent in addition to the isocyanate compound and the amine compound.
  • the solvent may be at least one of water, N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, toluene, and dimethyl sulfoxide.
  • the molar ratio of the isocyanate compound and the amine compound can be controlled to be 1:1.
  • the reaction can be completed at 30-60°C, and the reaction time is generally 2-30 hours.
  • the two raw materials can be fully mixed by controlling the stirring speed before reacting.
  • the mixing speed is 1200-2000r/min, and the mixing time is 30-400min. Do this under an inert atmosphere.
  • the application does not limit the type and structure of the second monomer, for example, it can be selected from divinylbenzene, 1,3-diisopropenylbenzene, o-vinylbutenylbenzene, p,p'-divinyl -1,2-diphenylethane, 9,10-divinyl anthracene, 1,3-divinylbenzene, 1,2,4-triethylcyclohexane or butadiene, polyethylene glycol diacrylic acid At least one of ester, polyethylene glycol dimethacrylate, dodecafluoro-1,9-decadiene or 1,4-divinylperfluorobutane.
  • the silicon-containing crosslinking agent is selected from divinyldimethylsilane, 1,3-divinyltetraethoxydisilane, 1,3-divinyl-1,3-dimethyl-1,3 -Dichlorodisilane, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisilane, tetramethyldivinyldisiloxane, 1,3 -Divinyltetraphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3-dimethyl Divinyl-1,3-diphenyldisiloxane, divinyltetramethyldisilane, 1,4-divinyl-1,1,4,4-tetramethyldis
  • a polyene crosslinking agent with a number average molecular weight of less than 2000 can be selected.
  • the molecular weight is greater than 2000, the activity of the active group in the crosslinking agent is low, and the degree of difficulty in the reaction is relatively large, which is not conducive to the preparation of polymers. .
  • the polymer in the solid electrolyte of the present application may also include other ureido groups that do not contain substituted or unsubstituted ureido groups and are not derived from polyene crosslinking agents.
  • Structural unit this application refers to this kind of structural unit as the third structural unit. It should be noted that the polymer may contain multiple different third structural units.
  • the third structural unit can be derived from acrylic acid, acrylate, polyethylene glycol methacrylate, methyl methacrylate, acrylonitrile, divinylbenzene, polyethylene glycol diacrylate, aminoacrylate, trihydroxy At least one of methyl propane trimethacrylate, terephthalic acid, and vinyl silicon.
  • the number average molecular weight of the polymer is 3,000-100,000.
  • the mass proportion of the first structural unit in the polymer is 10%-99.5%, and the mass proportion of the second structural unit in the polymer is 0.5%-90.0%.
  • the mass proportion of the first structural unit in the polymer is 10%-95%, and the mass proportion of the second structural unit in the polymer is 0.5%-85%.
  • the mass proportion of the three structural units in the polymer is 0.1%-20%.
  • the preparation method of the polymer of the present application has no other particularity with the polymer preparation method in this field, for example, the solvent system comprising monomer and initiator is heated to a certain temperature under the protection of inert gas to initiate polymerization reaction, and can be Real-time monitoring of the degree of polymerization of the reaction system to judge the progress of the reaction, which is beneficial to obtain a polymer that meets the target molecular weight.
  • the amount of the initiator added is 0.01-0.5% of the total mass of the polymer monomers.
  • the initiator can be an initiator commonly used in the art, including but not limited to azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tertiary benzoyl peroxide At least one of butyl ester, ethyl 4-(N,N-dimethylamino)benzoate, and methyl o-benzoylbenzoate.
  • the polymer, lithium salt, and additives can be mixed and dispersed in a solvent to prepare a slurry, and then the slurry is coated on the substrate, dried, After rolling, the solid electrolyte of the present application is obtained.
  • the second aspect of the present application provides a lithium-ion battery, which includes a positive electrode sheet, a negative electrode sheet, and the solid electrolyte of the first aspect arranged between the positive and negative electrode sheets.
  • the lithium ion battery of the present application has outstanding performance in terms of high temperature safety.
  • the present application does not limit the preparation method of the lithium-ion battery, for example, it can be prepared by stacking the positive electrode sheet, the solid electrolyte, and the negative electrode sheet sequentially and then encapsulating them.
  • the positive electrode sheet, separator, and negative electrode sheet can also be stacked in sequence to form a basic battery cell, and then the precursor liquid is injected into it, and after being fully soaked, the lithium ion battery of the present application can be obtained by baking.
  • the precursor solution is a dispersion system of polymer monomers, lithium salts, additives, and initiators in a solvent.
  • the positive electrode sheet and the negative electrode sheet in the lithium ion battery of the present application have no special requirements compared with the existing positive electrode sheet and negative electrode sheet in the art.
  • the third aspect of the present application provides a positive electrode sheet, the positive electrode sheet includes the solid electrolyte described in the first aspect; the positive electrode sheet includes a positive electrode active layer, and the interior and/or surface of the positive electrode active layer has the solid electrolyte.
  • the positive electrode slurry can be prepared by mixing and dispersing the positive electrode active material, solid electrolyte, conductive agent, and binder in a solvent, and then coating the positive electrode slurry Distributed on at least one functional surface of the positive electrode current collector, after drying and rolling, the positive electrode sheet containing the solid electrolyte in the application is obtained; further, a dispersion liquid containing the solid electrolyte can also be prepared, and the dispersion liquid can be coated on the On the surface of the above-mentioned positive electrode sheet, a positive electrode sheet including a solid electrolyte is obtained both inside and on the surface.
  • the positive electrode slurry is prepared by mixing and dispersing the positive electrode active material, the conductive agent, the binder, etc. in a solvent, and at the same time, a dispersion liquid including a solid electrolyte can also be prepared. Then apply the positive electrode slurry on at least one functional surface of the positive electrode current collector, and after drying, apply the dispersion liquid on the dried surface, and roll it after drying again to obtain the positive electrode sheet of the present application that includes a solid electrolyte on the surface .
  • the drying in the above preparation process includes treatment at 80-120° C. for 12-48 hours.
  • the positive electrode active material is selected from lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium nickel cobalt manganese oxide (LizNixCoyMn1-x-yO2 , where 0.95 ⁇ z ⁇ 1.05, x>0, y>0, 0 ⁇ x+y ⁇ 1), lithium manganate (LiMnO2), lithium nickel cobalt aluminate (LizNixCoyAl1-x-yO2, where 0.95 ⁇ z ⁇ 1.05 , x>0, y>0, 0.8 ⁇ x+y ⁇ 1), lithium nickel cobalt manganese aluminate (LizNixCoyMnwAl1-x-y-wO2, where 0.95 ⁇ z ⁇ 1.05, x>0, y>0, w>0, 0.8 ⁇ x+y+w ⁇ 1), nickel-cobalt-alum
  • the positive electrode sheet includes: 75-98.5% positive electrode active material, 0.5-5% solid electrolyte, 0.5-10% conductive agent and 0.5-10% binder according to mass percentage.
  • the positive electrode sheet of the present application includes the solid electrolyte of the first aspect, which is not only conducive to the conduction of lithium ions, but also conducive to improving the safety performance of the positive electrode sheet under high temperature conditions.
  • the fourth aspect of the present application provides a negative electrode sheet, the negative electrode sheet includes the solid electrolyte described in the first aspect; the negative electrode sheet includes a negative electrode matrix, and the interior and/or surface of the negative electrode matrix has the solid electrolyte.
  • the above-mentioned negative electrode substrate is different according to the composition of the negative electrode sheet.
  • the negative electrode sheet is a non-lithium metal negative electrode sheet
  • the negative electrode substrate refers to the current collector and the negative electrode active layer located on at least one functional surface of the current collector;
  • the negative electrode sheet is a lithium metal negative electrode sheet
  • the negative electrode matrix refers to lithium metal.
  • the present application does not limit the preparation method of the negative electrode sheet.
  • the negative electrode matrix includes a current collector and a negative active layer located on at least one functional surface of the current collector
  • it is also possible to prepare a dispersion liquid including a solid electrolyte and apply the dispersion liquid on the surface of the above-mentioned negative electrode sheet to obtain a negative electrode sheet including a solid electrolyte inside and on the surface.
  • the positive electrode slurry is prepared by mixing and dispersing the negative electrode active material, the conductive agent, the binder, etc. in a solvent, and at the same time, a dispersion liquid including a solid electrolyte can also be prepared. Then apply the negative electrode slurry on at least one functional surface of the negative electrode current collector, and after drying, apply the dispersion liquid on the dried surface, and roll it after drying again to obtain the negative electrode sheet of the application whose surface includes a solid electrolyte .
  • the negative electrode active material is selected from nano-silicon, SiOx (0 ⁇ x ⁇ 2), aluminum-silicon alloy, magnesium-silicon alloy, boron-silicon alloy, phosphorus-silicon alloy, lithium-silicon alloy, artificial graphite, natural graphite, hard carbon, soft carbon , mesophase microspheres, fullerene, graphene, lithium metal, boron and its derivatives (such as boron powder, boron oxide), aluminum and its derivatives (such as aluminum powder, lithium aluminum alloy), magnesium and its derivatives (such as magnesium, magnesium aluminum alloy), bismuth and its derivatives (such as bismuth, lithium bismuth alloy), nickel and its derivatives (such as nickel, lithium nickel alloy, lithium nickel nitride), silver and its derivatives (such as silver powder , lithium-silver alloy), zinc and its derivatives (such as zinc powder, zinc-lithium alloy, zinc nitride), titanium and its derivatives (such as titanium powder, lithium titanate, titanium dioxide, lithium-titanium
  • the negative electrode sheet includes: 75-98.5% negative electrode active material, 0.5-5% solid electrolyte, 0.5-10% conductive agent and 0.5-10% binder according to mass percentage.
  • the slurry dispersed with a solid electrolyte is directly coated on the surface of the metal negative electrode sheet and dried to obtain the lithium metal negative electrode sheet of the present application including a solid electrolyte on the surface.
  • the negative electrode sheet of the present application includes the solid electrolyte of the first aspect, which is not only beneficial to the conduction of lithium ions, but also conducive to improving the high-temperature safety performance of the negative electrode sheet.
  • a fifth aspect of the present application provides a lithium-ion battery, which includes the positive electrode sheet of the third aspect and/or the negative electrode sheet of the fourth aspect.
  • the lithium-ion battery of the present application can be a liquid lithium-ion battery (the electrolyte is an electrolyte) or a solid-state lithium-ion battery (the electrolyte is a solid electrolyte), and the safety performance of the lithium-ion battery can be improved through positive and negative plates.
  • the polymer, lithium salt, and additives are dispersed in acetonitrile to obtain a slurry, and the slurry is coated on the surface of the substrate, followed by drying and rolling to obtain a solid electrolyte.
  • Ni0.6Co0.2Mn0.2]O2 nickel-cobalt-manganese ternary material
  • 2g of conductive carbon black 1g of polyvinylidene fluoride (dissolved in 100g of NMP), 50g of NMP, 3g of PEO (molecular weight 500W, Dissolved in acetonitrile, with a solid content of 3%), 4g LITFSI, uniformly mixed, coated on the surface of the aluminum foil current collector, dried, rolled, and cut to obtain the positive electrode sheet;
  • the 50 micron copper-based composite lithium provided by Tianjin Zhongneng Lithium Industry Co., Ltd. is used as the negative electrode, in which the thickness of the copper foil is 10 microns, and the lithium layer is 20 microns;
  • the preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 1-9 respectively, the difference lies in the polymer in the step 1) of the example (the polymerized monomer does not contain the first monomer, and the polymerized monomer The quality of body is equal to the monomer total mass of embodiment) different.
  • the preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to Examples 1-9 respectively, and the difference lies in the polymer (the polymerized monomer only contains the first monomer in the step 1) of the example, and the first The quality of the monomer is equal to the sum of the monomer quality in the embodiment) different.
  • the preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to Examples 1-9, the difference is that the polymer in the examples is replaced by polyethylene oxide PEO of equal mass.
  • Example 1 Polymer 1/84 LiTFSI: LiBOB (mass ratio 3:1)/30 N-Methylacetamide/5 100 Comparative Example 1a Polymer 1a/84 LiTFSI: LiBOB (mass ratio 3:1)/30 N-Methylacetamide/5 100 Comparative Example 1b Polymer 1b/84 LiTFSI: LiBOB (mass ratio 3:1)/30 N-Methylacetamide/5 100 Comparative example 1c PEO/84 LiTFSI: LiBOB (mass ratio 3:1)/30 N-Methylacetamide/5 100 Example 2 Polymer 2/90 LiTFSI/15 3,3'-Azotoluene/1 150 Comparative Example 2a Polymer 2a/90 LiTFSI/15 3,3'-Azotoluene/1 150 Comparative example 2b Polymer 2b/90 LiTFSI/15 3,3'-Azotoluene/1 150 Comparative example 2b Polymer 2b/90 LiTFSI/15 3,3'-Azotolu
  • the preparation method of polymer 1 in embodiment 1 comprises the following steps:
  • the preparation method of polymer 1a in comparative example 1a comprises the following steps:
  • the preparation method of polymer 1b in comparative example 1b comprises the following steps:
  • the preparation steps of the polymers in other examples and comparative examples are roughly similar to the preparation steps of polymer 1, polymer 1a and polymer 1b, except that the raw materials for the preparation of the first monomer, the second monomer and the trigger
  • the selection of the agent and the polymerization process are different, see Table 2 and Table 3 for details.
  • the preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 10-11, the difference is that the first monomer is not contained in the step 1).
  • the specific parameters are shown in Table 5.
  • the preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 10-11, the difference is that the second monomer is not contained in the step 1).
  • the specific parameters are shown in Table 5.
  • the 50 micron copper-based composite lithium provided by Tianjin Zhongneng Lithium Industry Co., Ltd. is used as the negative electrode, in which the thickness of the copper foil is 10 microns, and the lithium layer is 20 microns;
  • the number-average molecular weight detection of the polymer of the embodiment the polymer is dissolved in a solvent to form a uniform liquid system, which is filtered through an organic membrane, and the sample is taken into a Shimadzu GPC-20A gel chromatograph Perform detection and collect molecular weight information;
  • the test method for the ionic conductivity of the solid electrolyte is: use the AC impedance method to test the ionic conductivity of the solid electrolyte, and the instrument used is the CHI660E electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd. In an argon glove box, assemble a button battery in the order of the positive electrode case, stainless steel gasket, solid polymer electrolyte, stainless steel gasket, shrapnel, and negative electrode case.
  • the AC impedance test frequency is 100mHz-1000KHz, and the amplitude voltage is 5mV, The test temperature is 30°C.
  • R is the bulk impedance of the solid polymer electrolyte ( ⁇ ); L is the thickness of the solid electrolyte (cm); S is the effective contact area of the button battery (cm2).
  • the samples of Examples 13 and 14 are the same, and both have the composition: a mixture of 3g of Polymer 1, 4g of LITFSI, and 5g of methylurea.
  • Furnace temperature test at 150°C adopt the thermal abuse test method specified in IEC 62133:2002, put the fully charged battery into a constant temperature and humidity chamber with natural or circulating air convection after it is stabilized at room temperature, and the temperature of the test chamber is 5°C Raise the temperature at a rate of /min ⁇ 2°C/min to about 150 ⁇ 2°C, keep the temperature for 30 minutes, and observe whether the battery has thermal runaway.
  • the specific results are shown in Table 7.
  • the battery cycle performance test method of lithium-ion battery is: put the lithium-ion battery on the blue battery charge-discharge test cabinet for charge-discharge cycle test. 3.0-4.55V, record the number of cycles experienced when the capacity decays to 80% of the first discharge capacity. The specific results are shown in Table 7.
  • the solid electrolyte of the present application not only satisfies the high-efficiency transmission of lithium ions, but also has excellent safety strength, especially at high temperatures, which can ensure normal working conditions and avoid thermal runaway.

Abstract

The present application provides a solid electrolyte and the use thereof. The solid electrolyte comprises a polymer, which comprises a first structural unit derived from a monoolefin compound containing a substituted or unsubstituted ureido group and a second structural unit derived from a polyolefin cross-linking agent. The solid electrolyte is beneficial for further improving the safety performance of a lithium-ion battery, and is especially good in terms of high-temperature safety.

Description

一种固态电解质及其应用A kind of solid electrolyte and its application
本申请要求于2021年09月26日提交中国专利局、申请号为202111130484.8、申请名称为“一种固态电解质及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202111130484.8 and the application title "A Solid Electrolyte and Its Application" submitted to the China Patent Office on September 26, 2021, the entire contents of which are incorporated in this application by reference .
技术领域technical field
本申请属于锂离子电池领域，涉及一种固态电解质，尤其涉及一种固态电解质及其应用。The application belongs to the field of lithium ion batteries, and relates to a solid electrolyte, in particular to a solid electrolyte and its application.
背景技术Background technique
全固态电池就是用不可燃的固体电解质取代传统锂离子电池中的易燃的电解液，从根本上避免了有机溶剂的易挥发性和易燃性导致的安全问题，进而在一定程度上消除了由于锂离子电池胀气或燃烧而引发的安全隐患。The all-solid-state battery is to replace the flammable electrolyte in the traditional lithium-ion battery with a non-flammable solid electrolyte, which fundamentally avoids the safety problems caused by the volatility and flammability of organic solvents, and thus eliminates to a certain extent Safety hazards due to flatulence or burning of lithium-ion batteries.
但是，随着全固态电池应用环境的不断扩大，对全固态电池的安全性能也提出了更高的要求，例如锂离子电池高温安全性能。However, with the continuous expansion of the application environment of all-solid-state batteries, higher requirements are placed on the safety performance of all-solid-state batteries, such as the high-temperature safety performance of lithium-ion batteries.
发明内容Contents of the invention
本申请提供一种固态电解质，该固态电解质由于具有特殊的组成，因此有利于进一步提升锂离子电池的安全性能，尤其高温安全方面表现优异。The present application provides a solid electrolyte, which is conducive to further improving the safety performance of lithium-ion batteries due to its special composition, especially in terms of high-temperature safety.
本申请还提供一种锂离子电池，该锂离子电池包括上述固态电解质，因此安全性能优异。The present application also provides a lithium-ion battery, which includes the above-mentioned solid electrolyte, and therefore has excellent safety performance.
本申请还提供一种正极片，该正极片包括上述固态电解质，因此有助于提升锂离子电池的安全性能。The present application also provides a positive electrode sheet, which includes the above-mentioned solid electrolyte, thus helping to improve the safety performance of the lithium-ion battery.
本申请还提供一种负极片，该负极片包括上述固态电解质，因此有助于提升锂离子电池的安全性能。The present application also provides a negative electrode sheet, which includes the above-mentioned solid electrolyte, thus helping to improve the safety performance of the lithium-ion battery.
本申请还提供一种锂离子电池，包括上述正极片和/或负极片，因此锂离子电池的高温安全性能表现优异。The present application also provides a lithium-ion battery, including the above-mentioned positive electrode sheet and/or negative electrode sheet, so the high-temperature safety performance of the lithium-ion battery is excellent.
本申请提供一种固态电解质，所述固态电解质包括聚合物，所述聚合物包括来自于含有取代或未取代的脲基基团的单烯烃化合物的第一结构单元和来自于多烯烃交联剂的第二结构单元。The present application provides a solid electrolyte comprising a polymer comprising a first structural unit derived from a monoolefin compound containing substituted or unsubstituted ureido groups and a polyolefin crosslinking agent the second structural unit.
如上所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物 具有式1所示的结构，The solid electrolyte as described above, wherein the monoolefin compound containing a substituted or unsubstituted ureido group has a structure shown in formula 1,
Figure PCTCN2022120961-appb-000001
Figure PCTCN2022120961-appb-000001
其中，R 1、R 3、R 4分别独立地选自H、卤素、硝基、氰基、取代或未取代的C 1～12的烷基、取代或未取代的C 1～12的烷氧基、取代或未取代的氨基；R 2选自羰基、取代或未取代的(杂)芳基、酯基、取代或未取代的C 1～12亚烷基、羧基或者化学键；M 1选自H、羰基、取代或未取代的C 1～20烷基、取代或未取代的C 1～20烷氧基、羟基、卤素、氨基、硝基、三氟甲基、烃硫基、取代或未取代的(杂)芳基；M 2、M 3分别独立地选自氢、取代或未取代的C 4～60(杂)芳基、取代或未取代的C 1～20烷基、取代或未取代的C 1～20烷氧基、羰基、取代或未取代含有杂环原子的C 2～12环烷基、酰基、羧基、酯基、或者M 2、M 3键结成环。 Wherein, R 1 , R 3 , and R 4 are independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 1-12 alkoxy substituted or unsubstituted amino group; R 2 is selected from carbonyl, substituted or unsubstituted (hetero) aryl, ester group, substituted or unsubstituted C 1～12 alkylene, carboxyl or chemical bond; M 1 is selected from H, carbonyl, substituted or unsubstituted C 1 to 20 alkyl, substituted or unsubstituted C 1 to 20 alkoxy, hydroxyl, halogen, amino, nitro, trifluoromethyl, hydrocarbon thio, substituted or unsubstituted Substituted (hetero)aryl; M 2 and M 3 are independently selected from hydrogen, substituted or unsubstituted C 4-60 (hetero)aryl, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted A substituted C 1-20 alkoxy group, carbonyl group, substituted or unsubstituted C 2-12 cycloalkyl group containing a heterocyclic atom, an acyl group, a carboxyl group, an ester group, or M 2 and M 3 are bonded to form a ring.
如上所述的固态电解质，其中，所述多烯烃交联剂的数均分子量小于2000。The above solid electrolyte, wherein the number average molecular weight of the polyene crosslinking agent is less than 2000.
如上所述的固态电解质，其中，所述聚合物的数均分子量为3000-100000。The above-mentioned solid electrolyte, wherein the number average molecular weight of the polymer is 3,000-100,000.
如上所述的固态电解质，其中，所述第一结构单元在所述聚合物中的质量占比为10-99.5％，所述第二结构单元在所述聚合物中的质量占比为0.5-90％。The above-mentioned solid electrolyte, wherein, the mass proportion of the first structural unit in the polymer is 10-99.5%, and the mass proportion of the second structural unit in the polymer is 0.5-99.5%. 90%.
如上所述的固态电解质，其中，所述聚合物还包括第三结构单元，所述第三结构单元来自于丙烯酸、丙烯酸酯、聚乙二醇甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯腈、氨基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、乙烯基硅材料中的至少一种。The solid electrolyte as described above, wherein the polymer further includes a third structural unit, and the third structural unit is derived from acrylic acid, acrylate, polyethylene glycol methacrylate, methyl methacrylate, acrylonitrile , amino acrylate, trimethylolpropane trimethacrylate, vinyl silicon material at least one.
如上所述的固态电解质，其中，所述第一结构单元在所述聚合物中的质量占比为10％-95％，所述第二结构单元在所述聚合物中的质量占比为0.5％-85％，所述第三结构单元在所述聚合物中的质量占比为0.1％-20％。The above-mentioned solid electrolyte, wherein, the mass proportion of the first structural unit in the polymer is 10%-95%, and the mass proportion of the second structural unit in the polymer is 0.5% %-85%, the mass proportion of the third structural unit in the polymer is 0.1%-20%.
如上所述的固态电解质，其中，所述固态电解质按照质量百分含量包括：聚合物40％～90％、锂盐10％～40％、助剂0％～20％。The above-mentioned solid electrolyte, wherein, the solid electrolyte comprises: 40%-90% of polymer, 10%-40% of lithium salt, and 0%-20% of auxiliary agent in terms of mass percentage.
如上所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物的分子量为100-5000。The above-mentioned solid electrolyte, wherein the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 100-5000.
如上所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物的分子量为150-2000。The above-mentioned solid electrolyte, wherein the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 150-2000.
如上所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物按照包括以下过程的方法制备得到：The above-mentioned solid electrolyte, wherein the monoolefin compound containing a substituted or unsubstituted ureido group is prepared according to a method comprising the following process:
使包含第一异氰酸酯类化合物和第一胺类化合物的溶剂体系，或者包含第二异氰酸酯类化合物和第二胺类化合物的溶剂体系反应，得到所述含有取代或未取代的脲基基团的单烯烃化合物；其中，所述第一异氰酸酯类化合物满足式2a所示的结构，所述第一胺类化合物满足式3a所示的结构，所述第一胺类化合物满足式2b所示的结构，所述第二异氰酸酯类化合物满足式3b所示的结构，式3b中，M x为M 2或者M 3， reacting a solvent system comprising a first isocyanate compound and a first amine compound, or a solvent system comprising a second isocyanate compound and a second amine compound, to obtain the mono-containing substituted or unsubstituted ureido group An olefin compound; wherein, the first isocyanate compound satisfies the structure shown in formula 2a, the first amine compound satisfies the structure shown in formula 3a, and the first amine compound satisfies the structure shown in formula 2b, The second isocyanate compound satisfies the structure shown in formula 3b, in formula 3b, M x is M 2 or M 3 ,
Figure PCTCN2022120961-appb-000002
Figure PCTCN2022120961-appb-000002
本申请提供一种锂离子电池，包括正极片、负极片以及位于所述正极片和负极片之间的上述任一项所述的固态电解质。The present application provides a lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet, and any one of the solid electrolytes described above located between the positive electrode sheet and the negative electrode sheet.
本申请提供一种正极片，所述正极片包括上述任一项所述的固态电解质；The present application provides a positive electrode sheet, which includes the solid electrolyte described in any one of the above;
所述正极片包括正极活性层，所述正极活性层的内部和/或表面具有所述固态电解质。The positive electrode sheet includes a positive electrode active layer, and the interior and/or surface of the positive electrode active layer has the solid electrolyte.
本申请提供一种负极片，所述负极片包括上述任一项所述的固态电解质；The present application provides a negative electrode sheet, which includes the solid electrolyte described in any one of the above;
所述负极片包括负极基体，所述负极基体的内部和/或表面具有所述固态电解质。The negative electrode sheet includes a negative electrode matrix, and the interior and/or surface of the negative electrode matrix has the solid electrolyte.
本申请提供一种锂离子电池，包括上述所述的正极片，和/或上述所述的负极片。The present application provides a lithium ion battery, comprising the above-mentioned positive electrode sheet, and/or the above-mentioned negative electrode sheet.
本申请提供一种固态电解质，该固态电解质中的聚合物通过含有脲基基团的单体和多烯烃交联单体的共聚得到。该聚合物具有更为优异的力学强度，因此在改善锂离子电池高温性能方面具有优异的表现。The present application provides a solid electrolyte, and the polymer in the solid electrolyte is obtained by copolymerizing monomers containing ureido groups and multiolefin crosslinking monomers. The polymer has more excellent mechanical strength, so it has excellent performance in improving the high-temperature performance of lithium-ion batteries.
本申请的锂离子电池，包括上述固态电解质，该固态电解质不仅能够实现锂离子的导通，更能够显著提升锂离子电池的安全性能，因此本申请的锂离子电池在高温性能方面表现优异。The lithium-ion battery of the present application includes the above-mentioned solid electrolyte, which can not only realize the conduction of lithium ions, but also significantly improve the safety performance of the lithium-ion battery. Therefore, the lithium-ion battery of the present application has excellent performance in high temperature performance.
本申请的正极片，包括上述固态电解质，该固态电解质能够显著提升正极片的安全性能，在高温条件下依旧能够维持正常的工作形态。The positive electrode sheet of the present application includes the above-mentioned solid electrolyte, which can significantly improve the safety performance of the positive electrode sheet, and can still maintain a normal working state under high temperature conditions.
本申请的负极片，包括上述固态电解质，该固态电解质能够显著提升负极片的安全性能，在高温条件下依旧能够维持正常的工作形态。The negative electrode sheet of the present application includes the above-mentioned solid electrolyte, which can significantly improve the safety performance of the negative electrode sheet, and can still maintain a normal working state under high temperature conditions.
本申请的锂离子电池，包括上述正极片和/或负极片，因此安全性能优异，尤其在高温性能方面表现优异。The lithium-ion battery of the present application includes the positive electrode sheet and/or the negative electrode sheet, so it has excellent safety performance, especially in high temperature performance.
具体实施方式Detailed ways
下文将结合具体实施例对本申请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申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。The present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present application, and should not be construed as limiting the protection scope of the present application. All technologies implemented based on the above contents of the application are covered within the scope of protection intended by the application.
本申请第一方面提供一种固态电解质，所述固态电解质包括聚合物，所述聚合物包 括来自于含有取代或未取代的脲基基团的单烯烃化合物的第一结构单元和来自于多烯烃交联剂的第二结构单元。The first aspect of the present application provides a solid electrolyte, which includes a polymer, and the polymer includes a first structural unit derived from a monoolefin compound containing a substituted or unsubstituted ureido group and a polyene derived from a The second structural unit of the crosslinker.
本申请的固态电解质中的聚合物包括取代或未取代的脲基基团，其中，未被取代基取代的脲基基团的结构为：The polymer in the solid electrolyte of the present application includes substituted or unsubstituted ureido groups, wherein the structure of the unsubstituted ureido groups is:
Figure PCTCN2022120961-appb-000003
Figure PCTCN2022120961-appb-000003
被取代的脲基基团是指脲基基团中的一个氢或被取代基R取代或两个氢均被取代基R取代，结构式如下：The substituted ureido group refers to a hydrogen in the ureido group or is substituted by a substituent R or both hydrogens are substituted by a substituent R, and the structural formula is as follows:
Figure PCTCN2022120961-appb-000004
Figure PCTCN2022120961-appb-000004
本申请不限脲基基团的取代基，例如可以是，R可以是酰基、羧基、取代或未取代的C1-C36的烷基、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基、取代或未取代的烷氧基等，当这些基团存在取代基时，取代基分别独立地选自卤素、氰基、硝基、氨基、C1-C10的烷基、C2-C6的烯基、C1-C6的烷氧基或硫代烷氧基、C6-C30的芳基、C3-C30的杂芳基等中的一种或多种。The application is not limited to the substituent of the ureido group, for example, R can be acyl, carboxyl, substituted or unsubstituted C1-C36 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted Substituted C3-C30 heteroaryl, substituted or unsubstituted alkoxy, etc., when these groups have substituents, the substituents are independently selected from halogen, cyano, nitro, amino, C1-C10 One or more of alkyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 aryl, C3-C30 heteroaryl, etc.
本申请的聚合物，除了包括来自于含有取代或未取代的脲基基团的单烯烃化合物的第一结构单元之外，还包括来自于多烯烃交联剂的第二结构单元。本申请不限多烯烃的交联剂的具体结构，只要能够实现交联且具有至少两个烯基即可。The polymers of the present application, in addition to the first structural unit derived from a monoolefin compound containing substituted or unsubstituted ureido groups, also comprise a second structural unit derived from a multiolefin crosslinking agent. The present application is not limited to the specific structure of the multi-olefin crosslinking agent, as long as it can realize crosslinking and has at least two alkenyl groups.
具体的，上述聚合物来自于单体之间聚合，且单体至少包括两种，分别为包括含有取代或未取代的脲基基团的单烯烃化合物(以下称为第一单体)以及多烯烃交联剂(以下称为第二单体)。需要指出的是，第一单体可以具体为一个含有取代或未取代的脲基基团的单烯烃化合物，也可以为多个彼此互不相同的化合物，但是这多个彼此互不相同的化合物均为含有取代或未取代的脲基基团的单烯烃化合物；同样的，第二单体可以看具体为一个具有交联功能的多烯烃化合物，也可以为多个彼此互不相同的化合物，但是这多个彼此互不相同的化合物均为多烯烃化合物且具有交联功能。Specifically, the above-mentioned polymers are derived from the polymerization of monomers, and the monomers include at least two kinds, which are respectively monoolefin compounds containing substituted or unsubstituted ureido groups (hereinafter referred to as the first monomer) and polyolefin compounds. Olefin crosslinking agent (hereinafter referred to as the second monomer). It should be noted that the first monomer can specifically be a monoolefin compound containing a substituted or unsubstituted ureido group, or it can be a plurality of compounds that are different from each other, but these multiple compounds that are different from each other Both are monoolefin compounds containing substituted or unsubstituted ureido groups; similarly, the second monomer can be seen as a multiolefin compound with crosslinking function, or it can be a plurality of compounds that are different from each other, However, these plural mutually different compounds are all polyene compounds and have a crosslinking function.
本申请的固态电解质，除了包括上述聚合物外，还包括锂盐、助剂。The solid-state electrolyte of the present application includes lithium salts and additives in addition to the above-mentioned polymers.
本申请对固态电解质中的锂盐不作特别的限定，均可以使用本领域常用的锂盐，具体可选自高氯酸锂(LiClO4)、六氟磷酸锂(LiPF6)、六氟砷酸锂(LiAsF6)、四氟硼酸锂(LiBF4)、双草酸硼酸锂(LiBOB)、草酸二氟硼酸锂(LiDFOB)、双二氟磺酰亚胺锂(LiFSI)、双三氟甲基磺酰亚胺锂(LiTFSI)、三氟甲基磺酸锂(LiCF3SO3)、双丙二酸硼酸(LiBMB)、丙二酸草酸硼酸锂(LiMOB)、六氟锑酸锂(LiSbF6)、二氟磷酸锂(LiPF2O2)、4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)、二(三氟甲基磺酰)亚胺锂(LiN(SO2CF3)2)、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2的至少一种。The present application does not specifically limit the lithium salt in the solid electrolyte, and lithium salts commonly used in the art can be used, specifically lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), Lithium tetrafluoroborate (LiBF4), lithium bisoxalate borate (LiBOB), lithium difluoroborate oxalate (LiDFOB), lithium bisdifluorosulfonyl imide (LiFSI), lithium bistrifluoromethylsulfonyl imide (LiTFSI) , lithium trifluoromethanesulfonate (LiCF3SO3), bismalonate borate (LiBMB), lithium malonate oxalate borate (LiMOB), lithium hexafluoroantimonate (LiSbF6), lithium difluorophosphate (LiPF2O2), 4, 5-dicyano-2-trifluoromethylimidazolium lithium (LiDTI), lithium bis(trifluoromethylsulfonyl)imide (LiN(SO2CF3)2), LiN(SO2C2F5)2, LiC(SO2CF3)3, At least one of LiN(SO2F)2.
此外，助剂选自氧化物电解质、纳米填料和有机助剂中的至少一种。具体的，氧化 电解质可选自磷酸锂、钛酸锂、磷酸钛锂、磷酸钛铝锂、钛酸镧锂、钽酸镧锂、磷酸锗铝锂、硅铝酸锂、磷酸硅锂、钛酸镧锂中的至少一种；纳米填料可选自氧化铝、氧化镁、勃姆石、硫酸钡、钛酸钡、氧化锌、氧化钙、二氧化硅、碳化硅、氧化镍中的至少一种；有机助剂可选自含氮有机小分子化合物，用于改善电解质加工窗口，避免加工过程中电解质组分变化。其中，含氮有机小分子化合物可选自丁二腈、N-甲基乙酰胺、3-氰基-7-氮杂吲哚、7-氮杂吲哚-4-甲腈、3,3'-偶氮甲苯、5-甲基苯并三氮唑、3,4,5-三氟苯乙腈、3,4,5,6-四氟邻苯二腈、1,2-萘二甲腈、2-氨基-4,5-咪唑二腈、5-甲基苯并三氮唑、甲基脲、1,3-二乙基脲、乙基脲、氟代醚、2-氟代苯***、全氟环醚、乙羧氟草醚中的至少一种。In addition, the auxiliary agent is selected from at least one of oxide electrolytes, nano fillers and organic auxiliary agents. Specifically, the oxidation electrolyte can be selected from lithium phosphate, lithium titanate, lithium titanium phosphate, lithium titanium aluminum phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium germanium aluminum phosphate, lithium aluminosilicate, lithium silicon phosphate, titanic acid At least one of lanthanum lithium; nanofillers can be selected from at least one of alumina, magnesia, boehmite, barium sulfate, barium titanate, zinc oxide, calcium oxide, silicon dioxide, silicon carbide, nickel oxide ; Organic additives can be selected from nitrogen-containing organic small molecule compounds, which are used to improve the electrolyte processing window and avoid changes in electrolyte components during processing. Among them, nitrogen-containing organic small molecule compounds can be selected from succinonitrile, N-methylacetamide, 3-cyano-7-azaindole, 7-azaindole-4-carbonitrile, 3,3' -Azotoluene, 5-methylbenzotriazole, 3,4,5-trifluorophenylacetonitrile, 3,4,5,6-tetrafluorophthalonitrile, 1,2-naphthalene dicarbonitrile, 2-Amino-4,5-imidazoledicarbonitrile, 5-methylbenzotriazole, methylurea, 1,3-diethylurea, ethylurea, fluoroether, 2-fluorophenetole, At least one of perfluorocyclic ether and acifluorfen.
在一种实施方式中，固态电解质按照质量百分含量包括：聚合物40％～90％、锂盐10％～40％、助剂0％～20％。In one embodiment, the solid electrolyte comprises: 40%-90% of polymer, 10%-40% of lithium salt, and 0%-20% of auxiliary agent in terms of mass percentage.
本申请的包括上述聚合物的固态电解质不仅能够实现锂离子的传导，完成锂离子在正负极片的脱嵌，更能够有效保证锂离子电池的安全性能，尤其含有该固态电解质的锂离子电池在高温状态下依旧能够保持安全的状态，避免了由于高温导致的失火***的事故发生。发明人基于此现象对安全性能改善的原因进行了分析，认为可能是：含有第一结构单元和第二结构单元的聚合物能够为固态电解质提供更加致密的网状结构，从而实现了高温情况下固态电解质良好的力学性能。一方面，当含有该固态电解质的锂离子电池在应用过程中，即便伴随着负极表面锂金属的析出，高强度固态电解质能够有效减缓锂枝晶生长穿透过程，从而实现了锂离子电池安全性能的改善。另一方面，固态电解质在高温下依旧能够维持正常状态，避免高温导致的变形现象的发生，降低了正负极接触概率，抑制了热失控。The solid electrolyte comprising the above polymer of the present application can not only realize the conduction of lithium ions, complete the deintercalation of lithium ions in the positive and negative electrodes, but also effectively ensure the safety performance of lithium ion batteries, especially lithium ion batteries containing the solid electrolyte It can still maintain a safe state in a high temperature state, avoiding the occurrence of fire and explosion accidents caused by high temperature. Based on this phenomenon, the inventor analyzed the reason for the improvement of safety performance, and believed that it may be that the polymer containing the first structural unit and the second structural unit can provide a denser network structure for the solid electrolyte, thereby achieving Good mechanical properties of solid electrolytes. On the one hand, when the lithium-ion battery containing the solid electrolyte is in the application process, even with the precipitation of lithium metal on the surface of the negative electrode, the high-strength solid electrolyte can effectively slow down the growth and penetration process of lithium dendrites, thereby realizing the safety performance of lithium-ion batteries improvement. On the other hand, the solid electrolyte can still maintain a normal state at high temperature, avoiding the occurrence of deformation caused by high temperature, reducing the contact probability of positive and negative electrodes, and suppressing thermal runaway.
发明人发现，当固态电解质中的聚合物中的第一结构单元来自于式1所示的含有取代或未取代的脲基基团的单烯烃化合物时，即第一单体具有式1所示的结构时，对锂离子电池的安全性能的改善作用更为明显。The inventors have found that when the first structural unit in the polymer in the solid electrolyte comes from a monoolefin compound containing a substituted or unsubstituted ureido group shown in Formula 1, that is, the first monomer has the formula 1 When the structure is used, the improvement effect on the safety performance of the lithium-ion battery is more obvious.
Figure PCTCN2022120961-appb-000005
Figure PCTCN2022120961-appb-000005
式1中，R1、R3、R4分别独立地选自H、卤素、硝基、氰基、取代或未取代的C1～12的烷基、取代或未取代的C1～12的烷氧基、取代或未取代的氨基；R2选自羰基、取代或未取代的(杂)芳基、酯基、取代或未取代的C1～12亚烷基、羧基或者化学键；M1选自H、羰基、取代或未取代的C1～20烷基、取代或未取代的C1～20烷氧基、羟基、卤素、氨基、硝基、三氟甲基、烃硫基、取代或未取代的(杂)芳基；M2、M3分别独立地选自氢、取代或未取代的C4～60(杂)芳基、取代或未取代的C1～20烷基、取代或未取代的C1～20烷氧基、羰基、取代或未取代含有杂环原子的C2～12环烷基、酰基、羧基、酯基、或者M2、M3键结成环。In Formula 1, R1, R3, and R4 are independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C1-12 alkoxy, substituted Or unsubstituted amino; R2 is selected from carbonyl, substituted or unsubstituted (hetero) aryl, ester group, substituted or unsubstituted C1～12 alkylene, carboxyl or chemical bond; M1 is selected from H, carbonyl, substituted or Unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 alkoxy, hydroxyl, halogen, amino, nitro, trifluoromethyl, hydrocarbon thio, substituted or unsubstituted (hetero)aryl; M2 and M3 are independently selected from hydrogen, substituted or unsubstituted C4~60 (hetero)aryl, substituted or unsubstituted C1~20 alkyl, substituted or unsubstituted C1~20 alkoxy, carbonyl, substituted Or an unsubstituted C2-12 cycloalkyl group containing a heterocyclic atom, an acyl group, a carboxyl group, an ester group, or M2, M3 are bonded to form a ring.
具体地，当R1、R3、R4具有取代基时，取代基可以选自卤素、硝基、氰基、羟基、 三氟甲基、C 1～12烃硫基等；Specifically, when R1, R3, and R4 have substituents, the substituents can be selected from halogen, nitro, cyano, hydroxyl, trifluoromethyl, C1～12 hydrocarbon thio groups, etc.;
R2为羰基RCO-*(R为取代或未取代的C1～12的链烷基、取代或未取代的C3～12的环烷基、取代或未取代的C1～12的烷氧基、取代或未取代的C4～60(杂)芳基、取代或未取代的羟基，取代基为C4～60(杂)芳基、卤素、硝基、氨基、氰基等)、取代或未取代的(杂)芳基((杂)芳基上的碳原子(或杂原子)和脲基中的N原子直接键结连接，或者(杂)芳基上的取代基和脲基中的N原子直接键结连接，取代基为C1～12的烷基、C1～12的烷氧基、硝基、卤素、氨基、羧基、酯基、酰基等)、酯基-COOR-*(R为取代或未取代的C1～12的链烷基、取代或未取代的C3～12的环烷基，取代基为氰基、硝基、氨基、卤素等)、化学键(即双键碳原子和脲基中的氮原子直接键结)、取代或未取代的C1～12亚烷基(取代基为氰基、硝基、氨基、卤素等)、羧基RCOOH(R为取代或未取代的C1～12烷基或烯基且同时与脲基中的N原子和双键碳原子直接键结，取代基为C1～12的烷氧基、卤素、氰基、硝基、氨基、卤素等)。其中，“-*”表示与脲基中的N原子直接键结的化学键，“-”表示与双键碳原子直接键结的化学键；R2 is carbonyl RCO-* (R is a substituted or unsubstituted C1-12 alkanyl group, a substituted or unsubstituted C3-12 cycloalkyl group, a substituted or unsubstituted C1-12 alkoxy group, a substituted or Unsubstituted C4~60 (hetero)aryl, substituted or unsubstituted hydroxyl, the substituent is C4~60 (hetero)aryl, halogen, nitro, amino, cyano, etc.), substituted or unsubstituted (hetero) ) aryl group (the carbon atom (or heteroatom) on the (hetero) aryl group is directly bonded to the N atom in the ureido group, or the substituent on the (hetero) aryl group is directly bonded to the N atom in the urea group Connection, substituents are C1~12 alkyl, C1~12 alkoxy, nitro, halogen, amino, carboxyl, ester, acyl, etc.), ester -COOR-* (R is substituted or unsubstituted C1-12 chain alkyl, substituted or unsubstituted C3-12 cycloalkyl, substituents are cyano, nitro, amino, halogen, etc.), chemical bonds (ie double bond carbon atom and nitrogen atom in urea group direct bond), substituted or unsubstituted C1~12 alkylene (substituents are cyano, nitro, amino, halogen, etc.), carboxyl RCOOH (R is substituted or unsubstituted C1~12 alkyl or alkenyl And at the same time, it is directly bonded to the N atom and the double-bonded carbon atom in the ureido group, and the substituents are C1-12 alkoxy, halogen, cyano, nitro, amino, halogen, etc.). Among them, "-*" represents the chemical bond directly bonded to the N atom in the urea group, and "-" represents the chemical bond directly bonded to the double-bonded carbon atom;
M1选自H、取代或未取代的C1～20烷基(取代基为C1～12的烷氧基、C4～30的杂(芳)基、卤素、氨基、羧基、酯基、酰基等)、取代或未取代的C1～20烷氧基(取代基为C1～12的烷基、C4～30的杂(芳)基、硝基、卤素、氨基、羧基、酯基、酰基等)、羟基、卤素、氨基、硝基、三氟甲基、烃硫基、取代或未取代的(杂)芳基(定义与R2中相同)、羰基RCO-*(R定义与R2中相同)，其中，“-*”表示与脲基中的N原子直接键结的化学键；M1 is selected from H, substituted or unsubstituted C1-20 alkyl (substituents are C1-12 alkoxy, C4-30 hetero (aryl) group, halogen, amino, carboxyl, ester group, acyl group, etc.), Substituted or unsubstituted C1-20 alkoxy (substituents are C1-12 alkyl, C4-30 hetero (aryl) group, nitro, halogen, amino, carboxyl, ester, acyl, etc.), hydroxyl, Halogen, amino, nitro, trifluoromethyl, sulfenyl, substituted or unsubstituted (hetero)aryl (as defined in R2), carbonyl RCO-* (R defined as in R2), wherein, " -*" represents a chemical bond directly bonded to the N atom in the urea group;
M2、M3分别独立地选自氢、取代或未取代的C4～60(杂)芳基(定义与R2中相同)、取代或未取代的C1～20烷基(定义与M1中相同)、取代或未取代的C1～20烷氧基(定义与M1中相同)、羰基RCO-*(R定义与M1中相同)、取代或未取代含有杂环原子的C2～12环烷基(取代基为C1～12的烷氧基、C4～30的杂(芳)基、卤素、氨基、羧基、酯基、酰基等)、酰基RCO-*(R为取代或未取代的C1～12烷基或烯基、卤素、氨基等，取代基为C1～12的烷氧基、卤素、氰基、硝基、氨基等)、羧基RCOOH(R为取代或未取代的C1～12烷基或烯基且与脲基中的N原子直接键结，取代基为C1～12的烷氧基、卤素、氰基、硝基、氨基、卤素等)、酯基RCOOR-*(R为取代或未取代的C1～12烷基或烯基，取代基为C1～12的烷氧基、卤素、氰基、硝基、氨基、卤素等)、酯基*-RCOOR-(R为取代或未取代的C1～12烷基或烯基，取代基为C1～12的烷氧基、卤素、氰基、硝基、氨基、卤素等)或者M2、M3键结成环(例如取代或未取代的C4～30环烷基、取代或未取代的C4～30环烯基、取代或未取代的C4～30芳基等，进一步地，成环原子还包括杂原子，取代基为C1～12的烷基、C1～12的烷氧基、硝基、卤素、三氟甲基、氨基、羟基、甲硫基、羧基、酯基、酰基、羰基等)，其中，“*-”和“-*”均表示与脲基中的N原子直接键结的化学键。M2 and M3 are independently selected from hydrogen, substituted or unsubstituted C4~60 (hetero)aryl (the definition is the same as in R2), substituted or unsubstituted C1~20 alkyl (the definition is the same as in M1), substituted Or unsubstituted C1～20 alkoxy (the definition is the same as in M1), carbonyl RCO-* (the definition of R is the same as in M1), substituted or unsubstituted C2～12 cycloalkyl containing heterocyclic atoms (the substituent is C1-12 alkoxy, C4-30 hetero (aryl) group, halogen, amino, carboxyl, ester, acyl, etc.), acyl RCO-* (R is a substituted or unsubstituted C1-12 alkyl or alkenyl group, halogen, amino, etc., substituents are C1-12 alkoxy, halogen, cyano, nitro, amino, etc.), carboxyl RCOOH (R is a substituted or unsubstituted C1-12 alkyl or alkenyl and The N atom in the urea group is directly bonded, and the substituent is C1~12 alkoxy, halogen, cyano, nitro, amino, halogen, etc.), ester group RCOOR-* (R is a substituted or unsubstituted C1~ 12 Alkyl or alkenyl, the substituent is C1-12 alkoxy, halogen, cyano, nitro, amino, halogen, etc.), ester group *-RCOOR- (R is a substituted or unsubstituted C1-12 alkane group or alkenyl, the substituent is C1-12 alkoxy, halogen, cyano, nitro, amino, halogen, etc.) or M2, M3 bonded to form a ring (such as substituted or unsubstituted C4-30 cycloalkyl , substituted or unsubstituted C4~30 cycloalkenyl, substituted or unsubstituted C4~30 aryl, etc., further, the ring atoms also include heteroatoms, and the substituents are C1~12 alkyl, C1~12 alkoxy, nitro, halogen, trifluoromethyl, amino, hydroxyl, methylthio, carboxyl, ester, acyl, carbonyl, etc.), where "*-" and "-*" both represent A chemical bond in which the N atoms are directly bonded.
进一步地，含有取代或未取代的脲基基团的单烯烃化合物的分子量为100-5000，优选为150-2000。Further, the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 100-5000, preferably 150-2000.
本申请不限定上述式1所示的化合物的制备方法。The present application does not limit the preparation method of the compound represented by the above formula 1.
在一种实施方式中，上述式1所示的化合物按照包括以下过程的方法制备得到：In one embodiment, the compound represented by the above formula 1 is prepared by a method comprising the following process:
使包含第一异氰酸酯类化合物和第一胺类化合物(伯胺或者仲胺)的溶剂体系反应，得到所述含有取代或未取代的脲基基团的单烯烃化合物，即式1所示的化合物。其中，所述第一异氰酸酯满足式2a所示的结构，所述第一胺类化合物满足式3a所示的结构。式2a和式3a所示结构中的基团，可参考前述。The solvent system comprising the first isocyanate compound and the first amine compound (primary amine or secondary amine) is reacted to obtain the monoolefin compound containing a substituted or unsubstituted ureido group, that is, the compound shown in formula 1 . Wherein, the first isocyanate satisfies the structure shown in formula 2a, and the first amine compound satisfies the structure shown in formula 3a. For the groups in the structures shown in Formula 2a and Formula 3a, reference may be made to the foregoing.
Figure PCTCN2022120961-appb-000006
Figure PCTCN2022120961-appb-000006
通过该制备方法制备得到式1所示的化合物中，M1为氢原子。In the compound shown in Formula 1 prepared by this preparation method, M1 is a hydrogen atom.
满足式2a的第一异氰酸酯类化合物例如可以选自丙烯基异氰酸酯、丙烯酸基异氰酸酯与丙烯酰基异氰酸酯及其衍生物中的至少一种。具体地，选自甲基丙烯酰异氰酸酯、3-异丙烯基-α,α-二甲基苄基异氰酸酯、异氰酸酯丙烯酸乙酯、甲基丙烯酸异氰基乙酯、异氰酸乙烯酯、3-异氰酸丙烯、3-乙氧基-2-丙烯酰基异氰酸酯等的至少一种。The first isocyanate compound satisfying the formula 2a, for example, may be selected from at least one of acryl isocyanate, acryl isocyanate, acryl isocyanate and derivatives thereof. Specifically, selected from methacryloyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, isocyanate ethyl acrylate, isocyanoethyl methacrylate, vinyl isocyanate, 3- At least one of allyl isocyanate, 3-ethoxy-2-acryloyl isocyanate, and the like.
满足式3a的第一胺类化合物例如可以选自2-氨基嘧啶-5-羧酸、2-氨基-3-碘-5-甲基吡啶、N-(4-吡啶甲基)乙胺、3-甲基噻吩-2-羧酰胺、2-溴-3-氨基-4-甲基吡啶、3-氯-4-氟苄胺、2-氨基-5,7-二氟苯并噻唑、、吗啉、2,4-二氯苯胺、3-氨基邻苯二甲酸酐、2-氨基-3-羟甲基吡啶、3-氨基-4-氯吡啶、三苯甲胺、1,3-苯并噻唑-5-胺、2-氨基-5-氰基吡啶、4-胺基异噁唑、2-氨基异烟酸乙酯、6-氮杂脲嘧啶、3,4-吡啶二酰亚胺、二甲基吡啶胺、1,2-二甲基哌嗪、L-脯氨酰胺、丙硫氧嘧啶、5-氟-2-(3H)-苯并噻唑酮、5-溴嘧啶-4-酮、N-乙酰-D-丙氨酸、(S)-4-异丙基-2-唑烷酮、1-(2-哌嗪-1-基乙酰)吡咯烷、2-甲基-4-乙酰氨基吡啶、2-氯甲基-6-甲基-噻吩并[2,3-D]嘧啶-4-(3H)-酮、2-羟基-4-甲基吡啶、三聚硫氰酸、2-甲硫基-4,6-二羟基嘧啶、4-羟基-6-三氟甲基嘧啶、(1,4,7,10-四氮杂-环十二-1-基)-烯丙基乙酸酯、(S)-(-)-2-氨基-4-戊烯酸、Fmoc-L-烯丙基甘氨酸、Fmoc-D-烯丙基甘氨酸、DL-2-氨基-4-戊烯酸、D-2-氨基-4-溴戊烯酸、L-瓜氨酸、N,N-二乙基乙二胺、环戊胺、5-(二乙基氨基)戊胺、(2-吗啉-4-乙基)-肼、正丁胺、L-叔亮氨酸、异丁胺中的至少一种。The first amine compound satisfying formula 3a can be selected from, for example, 2-aminopyrimidine-5-carboxylic acid, 2-amino-3-iodo-5-picoline, N-(4-pyridylmethyl)ethylamine, 3 -Methylthiophene-2-carboxamide, 2-bromo-3-amino-4-methylpyridine, 3-chloro-4-fluorobenzylamine, 2-amino-5,7-difluorobenzothiazole,, phenoline, 2,4-dichloroaniline, 3-aminophthalic anhydride, 2-amino-3-hydroxymethylpyridine, 3-amino-4-chloropyridine, tritylamine, 1,3-benzo Thiazol-5-amine, 2-amino-5-cyanopyridine, 4-aminoisoxazole, 2-aminoisonicotinic acid ethyl ester, 6-azauracil, 3,4-pyridine diimide, Dimethylpyridinamine, 1,2-Dimethylpiperazine, L-Prolinamide, Propylthiouracil, 5-Fluoro-2-(3H)-Benzothiazolone, 5-Bromopyrimidin-4-one , N-acetyl-D-alanine, (S)-4-isopropyl-2-oxazolidinone, 1-(2-piperazin-1-ylacetyl)pyrrolidine, 2-methyl-4- Acetylaminopyridine, 2-chloromethyl-6-methyl-thieno[2,3-D]pyrimidin-4-(3H)-one, 2-hydroxy-4-methylpyridine, thiocyanic acid, 2-methylthio-4,6-dihydroxypyrimidine, 4-hydroxy-6-trifluoromethylpyrimidine, (1,4,7,10-tetraaza-cyclododec-1-yl)-allyl Acetyl acetate, (S)-(-)-2-amino-4-pentenoic acid, Fmoc-L-allylglycine, Fmoc-D-allylglycine, DL-2-amino-4-pentenoic acid enoic acid, D-2-amino-4-bromopentenoic acid, L-citrulline, N,N-diethylethylenediamine, cyclopentylamine, 5-(diethylamino)pentylamine, (2 At least one of -morpholine-4-ethyl)-hydrazine, n-butylamine, L-tert-leucine, and isobutylamine.
在另一种实施方式中，上述式1所示的化合物还可以按照包括以下过程的方法制备得到：In another embodiment, the compound represented by the above formula 1 can also be prepared according to the method comprising the following process:
使包含第二异氰酸酯类化合物和第二胺类化合物的溶剂体系反应，得到所述含有取代或未取代的脲基基团的单烯烃化合物；其中，所述第二胺类化合物满足式2b所示的结构，所述第二异氰酸酯类化合物满足式3b所示的结构，式3b中，Mx为M2或者M3。式2b和式3b所示结构中的基团，可参考前述。reacting a solvent system comprising a second isocyanate compound and a second amine compound to obtain the monoolefin compound containing a substituted or unsubstituted ureido group; wherein, the second amine compound satisfies the formula 2b The structure of the second isocyanate compound satisfies the structure shown in formula 3b, in formula 3b, Mx is M2 or M3. For the groups in the structures shown in Formula 2b and Formula 3b, reference may be made to the foregoing.
Figure PCTCN2022120961-appb-000007
Figure PCTCN2022120961-appb-000007
通过该制备方法制备得到式1所示的化合物中，M2或M3为氢原子。In the compound shown in Formula 1 prepared by this preparation method, M2 or M3 is a hydrogen atom.
满足式2b的第二胺类化合物例如可以选自戊烯酸类含伯胺或仲胺基团的烯烃化合物、甘氨酸类含伯胺或仲胺基团的烯烃化合物、羧酸酯类含伯胺或仲胺基团的烯烃化合物中的至少一种。具体地，选自(1,4,7,10-四氮杂-环十二-1-基)-烯丙基乙酸酯、(S)-(-)-2-氨基-4-戊烯酸、Fmoc-L-烯丙基甘氨酸、Fmoc-D-烯丙基甘氨酸、DL-2-氨基-4-戊烯酸、D-2-氨基-4-溴戊烯酸等中的至少一种。The second amine compound satisfying formula 2b can be selected from, for example, olefinic compounds containing primary or secondary amine groups of pentenoic acids, olefinic compounds containing primary or secondary amine groups of glycines, carboxylic acid esters containing primary amines or at least one of olefinic compounds with secondary amine groups. Specifically, selected from (1,4,7,10-tetraaza-cyclododec-1-yl)-allyl acetate, (S)-(-)-2-amino-4-pentene At least one of acid, Fmoc-L-allylglycine, Fmoc-D-allylglycine, DL-2-amino-4-pentenoic acid, D-2-amino-4-bromopentenoic acid, etc. .
满足式3b的第二异氰酸酯类化合物例如可以选自对4-甲氧基苯异氰酸酯、3,4-二氯苯异氰酸酯、4-甲氧苄基异氰酸酯、2-苯乙基异氰酸酯、4-溴-3-甲苯基异氰酸酯、2-(甲氧基羰基)苯基异氰酸酯、异氰酸-4-溴-2-氯苯酯、异氰酸-2,3,5-二甲基苯酯、2-甲氧基-4-异氰酸硝基苯、4-氯-3-异氰酸硝基苯、异氰酸-2-氯-5-(三氟甲基)苯酯、异氰酸-2,5-二氟苯酯、4-氰基苯异氰酸酯、6-氟-1H-1,3-苯并二氧(杂)芑-8-基异氰酸酯、4-异氰基-3-甲基-5-苯基异噁唑、α-甲基异氰酸苄酯、2-甲基-3-异氰酸硝基苯、4-三氟甲基硫代苯基异氰酸酯、2-硝基苯酚异丁酸酯、4-异氰酰基苯甲酸甲酯、4-异硫氰四羟基-1-(2H)-吡啶甲酸苄酯、2-噻吩异氰酸酯、异氰酸-3-氯-4-甲氧苯酯、2,3-二氢-1-苯并呋喃-5-基异氰酸酯、2-氟-4-异氰酸基-1-甲氧基苯、3-异氰酸基噻吩-2-羧酸甲酯、3-溴苯基异氰酸酯、异氰酸-4-(甲硫基)苯酯、L-赖氨酸二异氰酸酯、十八烷基异氰酸酯、三甲基己二异氰酸酯、3-异氰酸酯基丙基三甲氧基硅烷、十二烷基异氰酸酯、叔辛基异氰酸酯、2-(全氟辛基)异氰酸乙酯、3-氯丙基异氰酸酯、3-溴异氰酸丙酯、2-己基异氰酸酯、(R)-(-)-2-壬基异氰酸酯、(R)-(-)-3-甲基-2-丁基异氰酸酯、(S)-(+)-2-庚基异氰酸酯、(S)-(+)-2-壬基异氰酸酯、(S)-(+)-3-甲基-2-丁基异氰酸酯、三溴甲基异氰酸酯、三氯乙酰异氰酸酯、三甲基硅基异氰酸酯、十六烷基异氰酸酯、正辛基异氰酸酯、十二烷基异氰酸酯、癸基异氰酸酯、十六烷基异氰酸酯、三甲基硅基异氰酸酯、正辛基异氰酸酯、1,6-己二异氰酸酯、聚六亚甲基二异氰酸酯、异氰酸酯丙烯酸乙酯、异氰酸基甲酸乙酯、3-乙氧基-2-丙烯酰基异氰酸酯、N-(氯甲酰)异氰酸酯、(R)-(-)-2-庚基异氰酸酯、氯乙酰异氰酸酯、二氯乙酰基异氰酸酯、4-正丁氧基苯酚异氰酸酯、异氰酸2-乙基己酯、异氰酸2-乙基己酯、、异氰酸异丙酯、异氰酸乙酯、三丁基锡乙氰酸酯、异氰酸乙烯酯、正丁基异氰酸乙酸酯、2-异氰酰丙酸乙酯、异氰酸十四酯、异氰酸十八酯、异氰酸丙酯、3-异氰酸丙烯、异氰酰乙酸乙酯、异氰酸十一烷酯、异氰酸异丁酯、异氰酸戊酯、甲基丙烯酸异氰基乙酯等中的至少一种。The second isocyanate compound satisfying formula 3b can be selected from, for example, p-4-methoxyphenylisocyanate, 3,4-dichlorophenylisocyanate, 4-methoxybenzylisocyanate, 2-phenylethylisocyanate, 4-bromo- 3-Tolyl isocyanate, 2-(methoxycarbonyl)phenyl isocyanate, 4-bromo-2-chlorophenyl isocyanate, 2,3,5-dimethylphenyl isocyanate, 2- Methoxy-4-nitrobenzene isocyanate, 4-chloro-3-nitrobenzene isocyanate, 2-chloro-5-(trifluoromethyl)phenyl isocyanate, 2-isocyanate , 5-difluorophenyl ester, 4-cyanobenzene isocyanate, 6-fluoro-1H-1,3-benzodiox (hetero)an-8-yl isocyanate, 4-isocyano-3-methyl- 5-phenylisoxazole, α-methyl benzyl isocyanate, 2-methyl-3-nitrobenzene isocyanate, 4-trifluoromethylthiophenyl isocyanate, 2-nitrophenol isocyanate Butyrate, methyl 4-isocyanatobenzoate, benzyl 4-isothiocyanatetetrahydroxy-1-(2H)-picolinate, 2-thiophene isocyanate, 3-chloro-4-methoxyisocyanate Phenyl ester, 2,3-dihydro-1-benzofuran-5-ylisocyanate, 2-fluoro-4-isocyanato-1-methoxybenzene, 3-isocyanatothiophene-2-carboxy methyl ester, 3-bromophenyl isocyanate, 4-(methylthio)phenyl isocyanate, L-lysine diisocyanate, octadecyl isocyanate, trimethylhexamethylene diisocyanate, 3-isocyanate group Propyltrimethoxysilane, dodecyl isocyanate, tert-octyl isocyanate, 2-(perfluorooctyl) ethyl isocyanate, 3-chloropropyl isocyanate, 3-bromopropyl isocyanate, 2- Hexyl isocyanate, (R)-(-)-2-nonyl isocyanate, (R)-(-)-3-methyl-2-butyl isocyanate, (S)-(+)-2-heptyl isocyanate, (S)-(+)-2-nonyl isocyanate, (S)-(+)-3-methyl-2-butyl isocyanate, tribromomethyl isocyanate, trichloroacetyl isocyanate, trimethylsilyl isocyanate , hexadecyl isocyanate, n-octyl isocyanate, dodecyl isocyanate, decyl isocyanate, hexadecyl isocyanate, trimethylsilyl isocyanate, n-octyl isocyanate, 1,6-hexamethylene diisocyanate, polyhexa Methylene diisocyanate, ethyl isocyanate acrylate, ethyl isocyanatoformate, 3-ethoxy-2-acryloyl isocyanate, N-(chloroformyl)isocyanate, (R)-(-)-2- Heptyl isocyanate, chloroacetyl isocyanate, dichloroacetyl isocyanate, 4-n-butoxyphenol isocyanate, 2-ethylhexyl isocyanate, 2-ethylhexyl isocyanate, isopropyl isocyanate , ethyl isocyanate, tributyltin acetocyanate, vinyl isocyanate, n-butyl isocyanate acetate, ethyl 2-isocyanatopropionate, tetradecyl isocyanate, octadecyl isocyanate ester, propyl isocyanate, 3-propylene isocyanate, ethyl isocyanatoacetate, undecyl isocyanate, isobutyl isocyanate, amyl isocyanate, isocyanoethyl methacrylate At least one of esters and the like.
在上述两种制备实施方式中，反应体系除了包括异氰酸酯类化合物和胺类化合物之外，还包括溶剂。其中，溶剂可选水、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、二甲基亚砜中的至少一种。In the above two preparation embodiments, the reaction system also includes a solvent in addition to the isocyanate compound and the amine compound. Wherein, the solvent may be at least one of water, N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, toluene, and dimethyl sulfoxide.
在反应过程中，为了使反应充分进行同时避免其他杂质的生成，可控制异氰酸酯类 化合物和胺类化合物的摩尔比为1:1。同时，反应可以在30～60℃下反应完成，反应时间一般为2～30h。During the reaction, in order to make the reaction fully proceed and avoid the generation of other impurities, the molar ratio of the isocyanate compound and the amine compound can be controlled to be 1:1. At the same time, the reaction can be completed at 30-60°C, and the reaction time is generally 2-30 hours.
可以理解的是，为了加快式1所示化合物的制备效率，可以通过控制搅拌转速使两种原料充分混合后再进行反应，混合转速为l200～2000r/min，混合时间为30～400min，混合可在惰性气氛下进行。It can be understood that, in order to speed up the preparation efficiency of the compound shown in formula 1, the two raw materials can be fully mixed by controlling the stirring speed before reacting. The mixing speed is 1200-2000r/min, and the mixing time is 30-400min. Do this under an inert atmosphere.
如前述，本申请不限定第二单体的种类及结构，例如可以选自二乙烯基苯、1，3-二异丙烯基苯、邻乙烯丁烯基苯、p,p’-二乙烯基-1,2-二苯基乙烷、9,10-二乙烯蒽、1,3-二乙烯苯、1,2,4-三乙基环己烷或丁二烯、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、十二氟-1,9-癸二烯或1,4-二乙烯基全氟丁烷中的至少一种。进一步的，还可以是含硅交联剂和/或含氟交联剂。其中，含硅交联剂选自二乙烯基二甲基硅烷、1,3-二乙烯基四乙氧基二硅烷、1,3-二乙烯基-1,3-二甲基-1,3-二氯二硅烷、1,5-二乙烯基-3,3-二苯基-1,1,5,5-四甲基三硅烷、四甲基二乙烯基二硅氧烷、1,3-二乙烯基四苯基二硅氧烷、1,3-二乙烯基-1,1,3,3-四甲基二硅氮烷、1,3-二乙烯基-1,3-二甲基-1,3-二苯基二硅氧烷、二乙烯基四甲基二硅烷、1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙烷、1,4-双(乙烯基二甲基硅)苯、1,3-二乙烯基-1,3-二苯基-1,3-二甲基二硅氮烷、1,1,3,5,5-五甲基-3-苯基-1,5-二乙烯基三硅氧烷、1,1,3,3,5,5-六甲基-1,5-二乙烯基三硅氧烷、1,5-二乙烯基-六甲基三硅氧烷、1,1,1,7,7,7-六甲基-3,5-双(三甲基硅氧基)-3,5-二乙烯基四硅氧烷、二乙氧基二-2-丙烯-1-基-硅烷、1,5-二乙烯基-3,3-二苯基-1,1,5,5-四甲基三硅烷、1,4-二乙烯基-1,1,4,4-四甲基二甲硅烷基乙烷、1,7-二乙烯基-八甲基四硅氧烷、6,6-二乙烯基-2,5,7,10-四氧杂-6-硅杂十一烷、甲基丙烯酰氧丙基三(乙烯基二甲基硅氧基)硅烷、三(乙烯基二甲基硅氧基)甲基硅烷、三(乙烯基二甲基甲硅烷氧基)苯基硅烷、三乙烯基三甲基环三硅氮烷、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、三乙烯基氯硅烷、三(乙烯基二甲基硅氧基)甲基硅烷、1,3,5-三乙烯基-1,1,3,5,5-五甲基三硅烷、1,3,5-三乙烯基-1,3,5-三甲基环三硅氧烷、三乙烯基硅烷、三乙烯基乙氧基硅烷、三乙烯基甲基硅烷、三(乙烯基二甲基甲硅烷氧基)苯基硅烷、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、苯基三乙烯基硅烷、甲基三[(1-甲基乙烯基)氧基]硅烷、甲基丙烯酰氧丙基三(乙烯基二甲基硅氧基)硅烷、六乙烯基二硅氧烷、1,1,3,3-四乙烯基二甲基二硅氧烷、1,1,3,3-四乙烯基二甲基二硅氧烷、甲基丙烯酰氧丙基三(乙烯基二甲基硅氧基)硅烷、三(异烯丙氧基)乙烯基硅烷、四甲基四乙烯基环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷、四乙烯硅烷、1,3-二甲基-1,1,3,3-四乙烯二硅氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基环四硅氮烷、四(二甲基乙烯基硅氧基)硅烷、五甲基五乙烯基环五硅氧烷或1,3,5,7,9,11-六甲基-1,3,5,7,9,11-六乙烯基环六硅氧烷中的至少一种。As mentioned above, the application does not limit the type and structure of the second monomer, for example, it can be selected from divinylbenzene, 1,3-diisopropenylbenzene, o-vinylbutenylbenzene, p,p'-divinyl -1,2-diphenylethane, 9,10-divinyl anthracene, 1,3-divinylbenzene, 1,2,4-triethylcyclohexane or butadiene, polyethylene glycol diacrylic acid At least one of ester, polyethylene glycol dimethacrylate, dodecafluoro-1,9-decadiene or 1,4-divinylperfluorobutane. Further, it may also be a silicon-containing crosslinking agent and/or a fluorine-containing crosslinking agent. Among them, the silicon-containing crosslinking agent is selected from divinyldimethylsilane, 1,3-divinyltetraethoxydisilane, 1,3-divinyl-1,3-dimethyl-1,3 -Dichlorodisilane, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisilane, tetramethyldivinyldisiloxane, 1,3 -Divinyltetraphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3-dimethyl Divinyl-1,3-diphenyldisiloxane, divinyltetramethyldisilane, 1,4-divinyl-1,1,4,4-tetramethyldisilylethane, 1 ,4-bis(vinyldimethylsilyl)benzene, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisilazane, 1,1,3,5, 5-pentamethyl-3-phenyl-1,5-divinyltrisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane , 1,5-divinyl-hexamethyltrisiloxane, 1,1,1,7,7,7-hexamethyl-3,5-bis(trimethylsiloxy)-3,5 -Divinyltetrasiloxane, diethoxydi-2-propen-1-yl-silane, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetra Methyltrisilane, 1,4-divinyl-1,1,4,4-tetramethyldisilylethane, 1,7-divinyl-octamethyltetrasiloxane, 6,6 -divinyl-2,5,7,10-tetraoxa-6-silaundecane, methacryloxypropyltris(vinyldimethylsiloxy)silane, tris(vinyldi Methylsilyloxy)methylsilane, Tris(vinyldimethylsiloxy)phenylsilane, Trivinyltrimethylcyclotrisilazane, 2,4,6-trivinyl-2, 4,6-Trimethylcyclotrisiloxane, Trivinylchlorosilane, Tris(vinyldimethylsiloxy)methylsilane, 1,3,5-trivinyl-1,1,3, 5,5-pentamethyltrisilane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, trivinylsilane, trivinylethoxysilane, triethylene phenylmethylsilane, tris(vinyldimethylsiloxy)phenylsilane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, phenyltriethylene methylsilane, methyltris[(1-methylvinyl)oxy]silane, methacryloxypropyltris(vinyldimethylsiloxy)silane, hexavinyldisiloxane, 1, 1,3,3-tetravinyldimethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, methacryloxypropyltri(vinyldimethyldisiloxane Siloxy)silane, Tri(isoallyloxy)vinylsilane, Tetramethyltetravinylcyclotetrasiloxane, 2,4,6,8-Tetramethyl-2,4,6,8- Tetravinylcyclotetrasiloxane, tetravinylsilane, 1,3-dimethyl-1,1,3,3-tetraethylenedisiloxane, 1,3,5,7-tetramethyl-1, 3,5,7-tetravinylcyclotetrasilazane, tetrakis(dimethyl Vinylsiloxy)silane, pentamethylpentavinylcyclopentasiloxane or 1,3,5,7,9,11-hexamethyl-1,3,5,7,9,11-hexaethylene at least one of cyclohexasiloxanes.
具体在应用过程在中，可以选用数均分子量小于2000的多烯烃交联剂，分子量＞2000时，交联剂中活性基团活性较低，发生反应难度系数较大，不利于聚合物的制备。Specifically, in the application process, a polyene crosslinking agent with a number average molecular weight of less than 2000 can be selected. When the molecular weight is greater than 2000, the activity of the active group in the crosslinking agent is low, and the degree of difficulty in the reaction is relatively large, which is not conducive to the preparation of polymers. .
进一步地，本申请固态电解质中的聚合物，除了包括第一结构单元和第二结构单元外，还可以包括其他不含有取代或未取代的脲基基团、且并非来自多烯烃交联剂的结构 单元，本申请称此类结构单元为第三结构单元。需要说明的是，聚合物中可以含有多个不同的第三结构单元。例如，第三结构单元可以来自于丙烯酸、丙烯酸酯、聚乙二醇甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯腈、二乙烯苯、聚乙二醇二丙烯酸酯、氨基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、对苯二丙烯酸、乙烯基硅材料中的至少一种。Further, in addition to the first structural unit and the second structural unit, the polymer in the solid electrolyte of the present application may also include other ureido groups that do not contain substituted or unsubstituted ureido groups and are not derived from polyene crosslinking agents. Structural unit, this application refers to this kind of structural unit as the third structural unit. It should be noted that the polymer may contain multiple different third structural units. For example, the third structural unit can be derived from acrylic acid, acrylate, polyethylene glycol methacrylate, methyl methacrylate, acrylonitrile, divinylbenzene, polyethylene glycol diacrylate, aminoacrylate, trihydroxy At least one of methyl propane trimethacrylate, terephthalic acid, and vinyl silicon.
进一步地，聚合物的数均分子量为3000-100000。Further, the number average molecular weight of the polymer is 3,000-100,000.
其中，当聚合物仅包括第一结构单元和第二结构单元时，第一结构单元在聚合物中的质量占比为10％-99.5％，第二结构单元在聚合物中的质量占比为0.5％-90.0％。Wherein, when the polymer only includes the first structural unit and the second structural unit, the mass proportion of the first structural unit in the polymer is 10%-99.5%, and the mass proportion of the second structural unit in the polymer is 0.5%-90.0%.
当聚合物还包括第三结构单元时，第一结构单元在聚合物中的质量占比为10％-95％，第二结构单元在聚合物中的质量占比为0.5％-85％，第三结构单元在聚合物中的质量占比为0.1％-20％。When the polymer further includes a third structural unit, the mass proportion of the first structural unit in the polymer is 10%-95%, and the mass proportion of the second structural unit in the polymer is 0.5%-85%. The mass proportion of the three structural units in the polymer is 0.1%-20%.
在上述基础上，通过控制第一结构单元和第二结构单元在聚合物中的比例，有利于进一步保证聚合物对固态电解质安全性能的优化。On the basis of the above, by controlling the ratio of the first structural unit and the second structural unit in the polymer, it is beneficial to further ensure the optimization of the safety performance of the polymer for the solid electrolyte.
本申请的聚合物的制备方法与本领域聚合物制备方法无其他特殊，例如，将包括单体和引发剂的溶剂体系在惰性气体的保护下加热到一定温度引发聚合反应，在反应过程中可以实时监测反应体系的聚合度判断反应的进展，从而有利于得到符合目标分子量的聚合物。The preparation method of the polymer of the present application has no other particularity with the polymer preparation method in this field, for example, the solvent system comprising monomer and initiator is heated to a certain temperature under the protection of inert gas to initiate polymerization reaction, and can be Real-time monitoring of the degree of polymerization of the reaction system to judge the progress of the reaction, which is beneficial to obtain a polymer that meets the target molecular weight.
具体地，引发剂加入量为聚合物单体总质量的0.01～0.5％。引发剂可用本领域常用的引发剂，包括但不限于偶氮二异丁腈、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中的至少一种。Specifically, the amount of the initiator added is 0.01-0.5% of the total mass of the polymer monomers. The initiator can be an initiator commonly used in the art, including but not limited to azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tertiary benzoyl peroxide At least one of butyl ester, ethyl 4-(N,N-dimethylamino)benzoate, and methyl o-benzoylbenzoate.
本申请不限定固态电解质的制备方法，在一种具体实施方式中，可以将聚合物、锂盐、助剂在溶剂中混合分散制备浆料，随后将浆料涂布在基板上，经过干燥、辊压后，得到本申请的固态电解质。This application does not limit the preparation method of the solid electrolyte. In a specific embodiment, the polymer, lithium salt, and additives can be mixed and dispersed in a solvent to prepare a slurry, and then the slurry is coated on the substrate, dried, After rolling, the solid electrolyte of the present application is obtained.
或者，将制备聚合物的单体、锂盐、助剂在溶剂中混合分散制备前驱浆料，随后将前驱浆料涂布在基板上后引发，经过干燥、辊压后，得到本申请的固态电解质。Alternatively, mix and disperse the monomers, lithium salts, and additives for preparing polymers in a solvent to prepare a precursor slurry, and then apply the precursor slurry on the substrate to initiate, and after drying and rolling, the solid state of the present application is obtained. electrolyte.
本申请第二方面提供一种锂离子电池，该锂离子电池包括正极片、负极片以及设置在正负极片之间的第一方面的固态电解质。The second aspect of the present application provides a lithium-ion battery, which includes a positive electrode sheet, a negative electrode sheet, and the solid electrolyte of the first aspect arranged between the positive and negative electrode sheets.
本申请的锂离子电池在高温安全方面具有突出表现。The lithium ion battery of the present application has outstanding performance in terms of high temperature safety.
本申请不限定锂离子电池的制备方法，例如可以通过将正极片、固态电解质、负极片依次叠放后封装制备获得。也可以将正极片、隔膜、负极片依次叠放形成基础电芯，随后向其中注入前驱液，充分浸润后，经过烘烤得到本申请的锂离子电池。其中，前驱液为聚合物单体、锂盐、助剂、引发剂在溶剂中的分散体系。The present application does not limit the preparation method of the lithium-ion battery, for example, it can be prepared by stacking the positive electrode sheet, the solid electrolyte, and the negative electrode sheet sequentially and then encapsulating them. The positive electrode sheet, separator, and negative electrode sheet can also be stacked in sequence to form a basic battery cell, and then the precursor liquid is injected into it, and after being fully soaked, the lithium ion battery of the present application can be obtained by baking. Wherein, the precursor solution is a dispersion system of polymer monomers, lithium salts, additives, and initiators in a solvent.
本申请的锂离子电池中的正极片和负极片相对于本领域现有的正极片和负极片无特殊要求。The positive electrode sheet and the negative electrode sheet in the lithium ion battery of the present application have no special requirements compared with the existing positive electrode sheet and negative electrode sheet in the art.
本申请第三方面提供一种正极片，该正极片包括第一方面所述的固态电解质；所述正极片包括正极活性层，所述正极活性层的内部和/或表面具有所述固态电解质。The third aspect of the present application provides a positive electrode sheet, the positive electrode sheet includes the solid electrolyte described in the first aspect; the positive electrode sheet includes a positive electrode active layer, and the interior and/or surface of the positive electrode active layer has the solid electrolyte.
本申请不限定正极片的制备方法，在一种具体实施方式中，可以将正极活性材料、固态电解质、导电剂以及粘结剂等在溶剂中混合分散制备正极浆料，随后将正极浆料涂布在正极集流体的至少一个功能表面，经过干燥、辊压后，得到本申请的内部包括固态电解质的正极片；进一步地，还可以制备包括固态电解质的分散液，将该分散液涂布在上述正极片的表面，得到内部和表面均包括固态电解质的正极片。This application does not limit the preparation method of the positive electrode sheet. In a specific embodiment, the positive electrode slurry can be prepared by mixing and dispersing the positive electrode active material, solid electrolyte, conductive agent, and binder in a solvent, and then coating the positive electrode slurry Distributed on at least one functional surface of the positive electrode current collector, after drying and rolling, the positive electrode sheet containing the solid electrolyte in the application is obtained; further, a dispersion liquid containing the solid electrolyte can also be prepared, and the dispersion liquid can be coated on the On the surface of the above-mentioned positive electrode sheet, a positive electrode sheet including a solid electrolyte is obtained both inside and on the surface.
或者，将正极活性材料、导电剂以及粘结剂等在溶剂中混合分散制备正极浆料，同时还可以制备包括固态电解质的分散液。随后将正极浆料涂布在正极集流体的至少一个功能表面，经过干燥后，再将分散液涂布在干燥后的表面上，再次干燥后辊压，得到本申请表面包括固态电解质的正极片。Alternatively, the positive electrode slurry is prepared by mixing and dispersing the positive electrode active material, the conductive agent, the binder, etc. in a solvent, and at the same time, a dispersion liquid including a solid electrolyte can also be prepared. Then apply the positive electrode slurry on at least one functional surface of the positive electrode current collector, and after drying, apply the dispersion liquid on the dried surface, and roll it after drying again to obtain the positive electrode sheet of the present application that includes a solid electrolyte on the surface .
上述制备过程中的干燥包括在80～120℃下处理12～48小时。The drying in the above preparation process includes treatment at 80-120° C. for 12-48 hours.
本申请对正极活性材料、导电剂以及粘结剂不做特殊限定，例如，正极活性材料选自磷酸铁锂(LiFePO4)、钴酸锂(LiCoO2)、镍钴锰酸锂(LizNixCoyMn1-x-yO2，其中0.95≤z≤1.05，x>0，y>0，0<x+y<1)、锰酸锂(LiMnO2)、镍钴铝酸锂(LizNixCoyAl1-x-yO2，其中0.95≤z≤1.05，x>0，y>0，0.8≤x+y<1)、镍钴锰铝酸锂(LizNixCoyMnwAl1-x-y-wO2，其中0.95≤z≤1.05，x>0，y>0，w>0，0.8≤x+y+w<1)、镍钴铝钨材料、富锂锰基固溶体正极材料(xLi2MnO3·(1-x)LiMO2，其中M＝Ni/Co/Mn，0＜x＜1)、镍钴酸锂(LiNixCoyO2，其中x>0，y>0，x+y＝1)、镍钛镁酸锂(LiNixTiyMgzO2，其中，x>0，y>0，z>0，x+y+z＝1)、镍酸锂(Li2NiO2)、尖晶石锰酸锂(LiMn2O4)、镍钴钨材料中的一种或几种的组合；导电剂选自导电炭黑、科琴黑、导电纤维、导电聚合物、乙炔黑、碳纳米管、石墨烯、鳞片石墨、导电氧化物、金属颗粒中的至少一种；粘结剂选自聚偏氟乙烯及其共聚衍生物、聚四氟乙烯及其共聚衍生物、聚丙烯酸及其共聚衍生物、聚六氟丙烯及其共聚衍生物中的至少一种。The application does not specifically limit the positive electrode active material, conductive agent and binding agent, for example, the positive electrode active material is selected from lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium nickel cobalt manganese oxide (LizNixCoyMn1-x-yO2 , where 0.95≤z≤1.05, x>0, y>0, 0<x+y<1), lithium manganate (LiMnO2), lithium nickel cobalt aluminate (LizNixCoyAl1-x-yO2, where 0.95≤z≤1.05 , x>0, y>0, 0.8≤x+y<1), lithium nickel cobalt manganese aluminate (LizNixCoyMnwAl1-x-y-wO2, where 0.95≤z≤1.05, x>0, y>0, w>0, 0.8≤x+y+w<1), nickel-cobalt-aluminum-tungsten materials, lithium-rich manganese-based solid solution cathode materials (xLi2MnO3·(1-x)LiMO2, where M=Ni/Co/Mn, 0<x<1), Lithium nickel cobalt oxide (LiNixCoyO2, where x>0, y>0, x+y=1), lithium nickel titanium magnesium oxide (LiNixTiyMgzO2, where x>0, y>0, z>0, x+y+z =1), lithium nickelate (Li2NiO2), spinel lithium manganese oxide (LiMn2O4), nickel-cobalt-tungsten material or a combination of several; the conductive agent is selected from conductive carbon black, Ketjen black, conductive fiber, At least one of conductive polymers, acetylene black, carbon nanotubes, graphene, flake graphite, conductive oxides, metal particles; the binder is selected from polyvinylidene fluoride and its copolymer derivatives, polytetrafluoroethylene and its At least one of copolymerization derivatives, polyacrylic acid and its copolymerization derivatives, polyhexafluoropropylene and its copolymerization derivatives.
进一步地，正极片按照质量百分含量包括：75-98.5％正极活性材料、0.5-5％固态电解质、0.5-10％导电剂以及0.5-10％粘结剂。Further, the positive electrode sheet includes: 75-98.5% positive electrode active material, 0.5-5% solid electrolyte, 0.5-10% conductive agent and 0.5-10% binder according to mass percentage.
本申请的正极片包括第一方面的固态电解质，除了有利于锂离子的传导之外，还有利于提升高温情况下正极片安全性能。The positive electrode sheet of the present application includes the solid electrolyte of the first aspect, which is not only conducive to the conduction of lithium ions, but also conducive to improving the safety performance of the positive electrode sheet under high temperature conditions.
本申请第四方面提供一种负极片，该负极片包括第一方面所述的固态电解质；所述负极片包括负极基体，所述负极基体的内部和/或表面具有所述固态电解质。The fourth aspect of the present application provides a negative electrode sheet, the negative electrode sheet includes the solid electrolyte described in the first aspect; the negative electrode sheet includes a negative electrode matrix, and the interior and/or surface of the negative electrode matrix has the solid electrolyte.
上述负极基体根据负极片的组成有所不同，当负极片为非锂金属负极片时，负极基体是指集流体和位于集流体至少一功能表面的负极活性层；当负极片为锂金属负极片时，负极基体是指锂金属。The above-mentioned negative electrode substrate is different according to the composition of the negative electrode sheet. When the negative electrode sheet is a non-lithium metal negative electrode sheet, the negative electrode substrate refers to the current collector and the negative electrode active layer located on at least one functional surface of the current collector; when the negative electrode sheet is a lithium metal negative electrode sheet , the negative electrode matrix refers to lithium metal.
本申请不限定负极片的制备方法，当负极基体包括集流体和位于集流体至少一功能表面的负极活性层时，在一种具体实施方式中，可以将负极活性材料、固态电解质、导电剂以及粘结剂等在溶剂中混合分散制备负极浆料，随后将负极浆料涂布在负极集流体的至少一个功能表面，经过干燥、辊压后，得到本申请的内部包括固态电解质的负极片；进一步地，还可以制备包括固态电解质的分散液，将该分散液涂布在上述负极片的表面， 得到内部和表面均包括固态电解质的负极片。The present application does not limit the preparation method of the negative electrode sheet. When the negative electrode matrix includes a current collector and a negative active layer located on at least one functional surface of the current collector, in a specific embodiment, the negative electrode active material, solid electrolyte, conductive agent and Mix and disperse the binder and the like in a solvent to prepare the negative electrode slurry, and then apply the negative electrode slurry on at least one functional surface of the negative electrode current collector, and after drying and rolling, obtain the negative electrode sheet of the present application including a solid electrolyte inside; Furthermore, it is also possible to prepare a dispersion liquid including a solid electrolyte, and apply the dispersion liquid on the surface of the above-mentioned negative electrode sheet to obtain a negative electrode sheet including a solid electrolyte inside and on the surface.
或者，将负极活性材料、导电剂以及粘结剂等在溶剂中混合分散制备正极浆料，同时还可以制备包括固态电解质的分散液。随后将负极浆料涂布在负极集流体的至少一个功能表面，经过干燥后，再将分散液涂布在干燥后的表面上，再次干燥后辊压，得到本申请表面包括固态电解质的负极片。Alternatively, the positive electrode slurry is prepared by mixing and dispersing the negative electrode active material, the conductive agent, the binder, etc. in a solvent, and at the same time, a dispersion liquid including a solid electrolyte can also be prepared. Then apply the negative electrode slurry on at least one functional surface of the negative electrode current collector, and after drying, apply the dispersion liquid on the dried surface, and roll it after drying again to obtain the negative electrode sheet of the application whose surface includes a solid electrolyte .
其中，负极活性材料选自纳米硅、SiOx(0<x<2)、铝硅合金、镁硅合金、硼硅合金、磷硅合金、锂硅合金、人造石墨、天然石墨、硬碳、软碳、中间相微球、富勒烯、石墨烯、锂金属、硼及其衍生物(如硼粉、氧化硼)、铝及其衍生物(如铝粉、锂铝合金)、镁及其衍生物(如镁、镁铝合金)、铋及其衍生物(如铋、锂铋合金)、镍及其衍生物(如镍、锂镍合金、氮镍化锂)、银及其衍生物(如银粉、锂银合金)、锌及其衍生物(如锌粉、锌锂合金、氮化锌)、钛及其衍生物(如钛粉、钛酸锂、二氧化钛、锂钛合金等)、镓及其衍生物(如镓、锂镓合金)、铟及其衍生物(如铟粉、锂铟合金)、锡及其衍生物(如锡粉、氧化亚锡、氧化锡、硫酸锡)、氮化锂、氮化铜中的至少一种；导电剂选自导电炭黑、科琴黑、导电纤维、导电聚合物、乙炔黑、碳纳米管、石墨烯、鳞片石墨、导电氧化物、金属颗粒中的至少一种；粘结剂选自聚偏氟乙烯及其共聚衍生物、聚四氟乙烯及其共聚衍生物、聚丙烯酸及其共聚衍生物、聚乙烯醇及其共聚衍生物、聚丁苯橡胶及其共聚衍生物、聚酰亚胺及其共聚衍生物、聚乙烯亚胺及其共聚衍生物、聚丙烯酸酯及其共聚衍生物、羧甲基纤维素钠及其共聚衍生物中的至少一种。Among them, the negative electrode active material is selected from nano-silicon, SiOx (0<x<2), aluminum-silicon alloy, magnesium-silicon alloy, boron-silicon alloy, phosphorus-silicon alloy, lithium-silicon alloy, artificial graphite, natural graphite, hard carbon, soft carbon , mesophase microspheres, fullerene, graphene, lithium metal, boron and its derivatives (such as boron powder, boron oxide), aluminum and its derivatives (such as aluminum powder, lithium aluminum alloy), magnesium and its derivatives (such as magnesium, magnesium aluminum alloy), bismuth and its derivatives (such as bismuth, lithium bismuth alloy), nickel and its derivatives (such as nickel, lithium nickel alloy, lithium nickel nitride), silver and its derivatives (such as silver powder , lithium-silver alloy), zinc and its derivatives (such as zinc powder, zinc-lithium alloy, zinc nitride), titanium and its derivatives (such as titanium powder, lithium titanate, titanium dioxide, lithium-titanium alloy, etc.), gallium and its Derivatives (such as gallium, lithium gallium alloy), indium and its derivatives (such as indium powder, lithium indium alloy), tin and its derivatives (such as tin powder, stannous oxide, tin oxide, tin sulfate), lithium nitride , at least one of copper nitride; the conductive agent is selected from conductive carbon black, Ketjen black, conductive fiber, conductive polymer, acetylene black, carbon nanotubes, graphene, flake graphite, conductive oxide, metal particles At least one; the binder is selected from polyvinylidene fluoride and its copolymer derivatives, polytetrafluoroethylene and its copolymer derivatives, polyacrylic acid and its copolymer derivatives, polyvinyl alcohol and its copolymer derivatives, polystyrene butadiene rubber At least one of polyimide and its copolymer derivatives, polyimide and its copolymer derivatives, polyethyleneimine and its copolymer derivatives, polyacrylate and its copolymer derivatives, carboxymethylcellulose sodium and its copolymer derivatives kind.
进一步地，负极片按照质量百分含量包括：75-98.5％负极活性材料、0.5-5％固态电解质、0.5-10％导电剂以及0.5-10％粘结剂。Further, the negative electrode sheet includes: 75-98.5% negative electrode active material, 0.5-5% solid electrolyte, 0.5-10% conductive agent and 0.5-10% binder according to mass percentage.
当负极片为锂金属负极片时，将分散有固态电解质的浆液直接涂覆在金属负极片的表面并烘干，即可得到本申请的表面包括固态电解质的锂金属负极片。When the negative electrode sheet is a lithium metal negative electrode sheet, the slurry dispersed with a solid electrolyte is directly coated on the surface of the metal negative electrode sheet and dried to obtain the lithium metal negative electrode sheet of the present application including a solid electrolyte on the surface.
本申请的负极片包括第一方面的固态电解质，除了有利于锂离子的传导之外，还有利于提升负极片高温安全性能。The negative electrode sheet of the present application includes the solid electrolyte of the first aspect, which is not only beneficial to the conduction of lithium ions, but also conducive to improving the high-temperature safety performance of the negative electrode sheet.
本申请第五方面提供一种锂离子电池，该锂离子电池包括第三方面的正极片和/或第四方面的负极片。A fifth aspect of the present application provides a lithium-ion battery, which includes the positive electrode sheet of the third aspect and/or the negative electrode sheet of the fourth aspect.
本申请的锂离子电池可以是液态锂离子电池(电解质为电解液)或者固态锂离子电池(电解质为固态电解质)，通过正负极片均能够实现对锂离子电池安全性能的改善。The lithium-ion battery of the present application can be a liquid lithium-ion battery (the electrolyte is an electrolyte) or a solid-state lithium-ion battery (the electrolyte is a solid electrolyte), and the safety performance of the lithium-ion battery can be improved through positive and negative plates.
下文将结合具体实施例对本申请做更进一步的详细说明。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。The present application will be further described in detail below in conjunction with specific embodiments. The experimental methods used in the following examples are conventional methods unless otherwise specified.
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 reagents and materials used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例1-9Examples 1-9
本实施例的锂离子电池的制备方法包括以下步骤：The preparation method of the lithium ion battery of the present embodiment comprises the following steps:
1)固态电解质的制备1) Preparation of solid electrolyte
将聚合物、锂盐、助剂分散在乙腈中得到浆液，将浆液涂布在基板表面依次经过干 燥、辊压，得到固态电解质。The polymer, lithium salt, and additives are dispersed in acetonitrile to obtain a slurry, and the slurry is coated on the surface of the substrate, followed by drying and rolling to obtain a solid electrolyte.
2)正极片的制备2) Preparation of positive electrode sheet
将90g的镍钴锰三元材料(Li[Ni0.6Co0.2Mn0.2]O2)、2g的导电碳黑、1g聚偏氟乙烯(溶解在100g NMP中)、50gNMP、3g PEO(分子量500W，溶解在乙腈中，固含为3％)、4gLITFSI，均匀混合后，涂布在铝箔集流体表面，经过烘干、辊压、分切后得到正极片；90g of nickel-cobalt-manganese ternary material (Li[Ni0.6Co0.2Mn0.2]O2), 2g of conductive carbon black, 1g of polyvinylidene fluoride (dissolved in 100g of NMP), 50g of NMP, 3g of PEO (molecular weight 500W, Dissolved in acetonitrile, with a solid content of 3%), 4g LITFSI, uniformly mixed, coated on the surface of the aluminum foil current collector, dried, rolled, and cut to obtain the positive electrode sheet;
3)负极片的制备3) Preparation of negative electrode sheet
将天津中能锂业提供的50微米铜基复合锂作为负极，其中铜箔厚度10微米，锂层为20微米；The 50 micron copper-based composite lithium provided by Tianjin Zhongneng Lithium Industry Co., Ltd. is used as the negative electrode, in which the thickness of the copper foil is 10 microns, and the lithium layer is 20 microns;
4)将上述得到的正极片、固态电解质、负极片依次通过叠片方式制备固态电池。4) The positive electrode sheet, solid electrolyte, and negative electrode sheet obtained above are sequentially stacked to prepare a solid-state battery.
对比例1a-9aComparative Examples 1a-9a
本对比例的锂离子电池的制备方法分别与实施例1-9一一对应，不同处在于与实施例的步骤1)中的聚合物(聚合单体中不含有第一单体，且聚合单体的质量等于实施例的单体总质量)不同。The preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 1-9 respectively, the difference lies in the polymer in the step 1) of the example (the polymerized monomer does not contain the first monomer, and the polymerized monomer The quality of body is equal to the monomer total mass of embodiment) different.
对比例1b-9bComparative Examples 1b-9b
本对比例的锂离子电池的制备方法分别与实施例1-9一一对应，不同处在于与实施例的步骤1)中的聚合物(聚合单体中仅含有第一单体，且第一单体的质量等于实施例中单体质量之和)不同。The preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to Examples 1-9 respectively, and the difference lies in the polymer (the polymerized monomer only contains the first monomer in the step 1) of the example, and the first The quality of the monomer is equal to the sum of the monomer quality in the embodiment) different.
对比例1c-9cComparative Examples 1c-9c
本对比例的锂离子电池的制备方法分别与实施例1-9一一对应，不同处在于将实施例中的聚合物替换为等质量的聚氧化乙烯PEO。The preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to Examples 1-9, the difference is that the polymer in the examples is replaced by polyethylene oxide PEO of equal mass.
上述实施例和对比例的锂离子电池的固态电解质的相关参数见表1。See Table 1 for the relevant parameters of the solid electrolytes of the lithium-ion batteries of the above-mentioned examples and comparative examples.
表1Table 1
 the 聚合物/质量gPolymer/mass g 锂盐/质量gLithium salt/mass g 助剂/质量gAuxiliary/mass g 固态电解质厚度μmSolid electrolyte thickness μm
实施例1Example 1 聚合物1/84Polymer 1/84 LiTFSI：LiBOB(质量比3:1)/30LiTFSI: LiBOB (mass ratio 3:1)/30 N-甲基乙酰胺/5N-Methylacetamide/5 100100
对比例1aComparative Example 1a 聚合物1a/84Polymer 1a/84 LiTFSI：LiBOB(质量比3:1)/30LiTFSI: LiBOB (mass ratio 3:1)/30 N-甲基乙酰胺/5N-Methylacetamide/5 100100
对比例1bComparative Example 1b 聚合物1b/84Polymer 1b/84 LiTFSI：LiBOB(质量比3:1)/30LiTFSI: LiBOB (mass ratio 3:1)/30 N-甲基乙酰胺/5N-Methylacetamide/5 100100
对比例1cComparative example 1c PEO/84PEO/84 LiTFSI：LiBOB(质量比3:1)/30LiTFSI: LiBOB (mass ratio 3:1)/30 N-甲基乙酰胺/5N-Methylacetamide/5 100100
实施例2Example 2 聚合物2/90Polymer 2/90 LiTFSI/15LiTFSI/15 3,3'-偶氮甲苯/13,3'-Azotoluene/1 150150
对比例2aComparative Example 2a 聚合物2a/90Polymer 2a/90 LiTFSI/15LiTFSI/15 3,3'-偶氮甲苯/13,3'-Azotoluene/1 150150
对比例2bComparative example 2b 聚合物2b/90Polymer 2b/90 LiTFSI/15LiTFSI/15 3,3'-偶氮甲苯/13,3'-Azotoluene/1 150150
对比例2cComparative example 2c PEO//90PEO//90 LiTFSI/15LiTFSI/15 3,3'-偶氮甲苯/13,3'-Azotoluene/1 150150
实施例3Example 3 聚合物3/100Polymer 3/100 LiTFSI：LiFSI(质量比5:1)/10LiTFSI: LiFSI (mass ratio 5:1)/10 3,4,5-三氟苯乙腈/83,4,5-Trifluorophenylacetonitrile/8 5050
对比例3aComparative Example 3a 聚合物3a/100Polymer 3a/100 LiTFSI：LiFSI(质量比5:1)/10LiTFSI: LiFSI (mass ratio 5:1)/10 3,4,5-三氟苯乙腈/83,4,5-Trifluorophenylacetonitrile/8 5050
对比例3bComparative example 3b 聚合物3b/100Polymer 3b/100 LiTFSI：LiFSI(质量比5:1)/10LiTFSI: LiFSI (mass ratio 5:1)/10 3,4,5-三氟苯乙腈/83,4,5-Trifluorophenylacetonitrile/8 5050
对比例3cComparative example 3c PEO/100PEO/100 LiTFSI：LiFSI(质量比5:1)/10LiTFSI: LiFSI (mass ratio 5:1)/10 3,4,5-三氟苯乙腈/83,4,5-Trifluorophenylacetonitrile/8 5050
实施例4Example 4 聚合物4/84Polymer 4/84 LiTFSI：LiBF 4(质量比6:1)/20 LiTFSI: LiBF 4 (mass ratio 6:1)/20 1,2-萘二甲腈/61,2-naphthalene dicarbonitrile/6 200200
对比例4aComparative Example 4a 聚合物4a/84Polymer 4a/84 LiTFSI：LiBF 4(质量比6:1)/20 LiTFSI: LiBF 4 (mass ratio 6:1)/20 1,2-萘二甲腈/61,2-naphthalene dicarbonitrile/6 200200
对比例4bComparative example 4b 聚合物4b/84Polymer 4b/84 LiTFSI：LiBF 4(质量比6:1)/20 LiTFSI: LiBF 4 (mass ratio 6:1)/20 1,2-萘二甲腈/61,2-naphthalene dicarbonitrile/6 200200
对比例4cComparative example 4c PEO/84PEO/84 LiTFSI：LiBF 4(质量比6:1)/20 LiTFSI: LiBF 4 (mass ratio 6:1)/20 1,2-萘二甲腈/61,2-naphthalene dicarbonitrile/6 200200
实施例5Example 5 聚合物5/84Polymer 5/84 LiTFSI：LiMOB(质量比8:1)/30LiTFSI: LiMOB (mass ratio 8:1)/30 甲基脲/3Methylurea/3 100100
对比例5aComparative Example 5a 聚合物5a/84Polymer 5a/84 LiTFSI：LiMOB(质量比8:1)/30LiTFSI: LiMOB (mass ratio 8:1)/30 甲基脲/3Methylurea/3 100100
对比例5bComparative Example 5b 聚合物5b/84Polymer 5b/84 LiTFSI：LiMOB(质量比8:1)/30LiTFSI: LiMOB (mass ratio 8:1)/30 甲基脲/3Methylurea/3 100100
对比例5cComparative Example 5c PEO/84PEO/84 LiTFSI：LiMOB(质量比8:1)/30LiTFSI: LiMOB (mass ratio 8:1)/30 甲基脲/3Methylurea/3 100100
实施例6Example 6 聚合物6/84Polymer 6/84 LiTFSI：LiBMB(质量比10:1)/25LiTFSI: LiBMB (mass ratio 10:1)/25 磷酸硅锂/5Lithium silicon phosphate/5 8080
对比例6aComparative Example 6a 聚合物6a/84Polymer 6a/84 LiTFSI：LiBMB(质量比10:1)/25LiTFSI: LiBMB (mass ratio 10:1)/25 磷酸硅锂/5Lithium silicon phosphate/5 8080
对比例6bComparative Example 6b 聚合物6b/84Polymer 6b/84 LiTFSI：LiBMB(质量比10:1)/25LiTFSI: LiBMB (mass ratio 10:1)/25 磷酸硅锂/5Lithium silicon phosphate/5 8080
对比例6cComparative example 6c PEO/84PEO/84 LiTFSI：LiBMB(质量比10:1)/25LiTFSI: LiBMB (mass ratio 10:1)/25 磷酸硅锂/5Lithium silicon phosphate/5 8080
实施例7Example 7 聚合物7/84Polymer 7/84 LiTFSI:LiCF 3SO 3(质量比5:2)/19 LiTFSI:LiCF 3 SO 3 (mass ratio 5:2)/19 ---- 4040
对比例7aComparative Example 7a 聚合物7a/84Polymer 7a/84 LiTFSI:LiCF 3SO 3(质量比5:2)/19 LiTFSI:LiCF 3 SO 3 (mass ratio 5:2)/19 ---- 4040
对比例7bComparative Example 7b 聚合物7b/84Polymer 7b/84 LiTFSI:LiCF 3SO 3(质量比5:2)/19 LiTFSI:LiCF 3 SO 3 (mass ratio 5:2)/19 ---- 4040
对比例7cComparative Example 7c PEO/84PEO/84 LiTFSI:LiCF 3SO 3(质量比5:2)/19 LiTFSI:LiCF 3 SO 3 (mass ratio 5:2)/19 ---- 4040
实施例8Example 8 聚合物8/84Polymer 8/84 LiTFSI/25LiTFSI/25 乙基脲/12Ethyl urea/12 100100
对比例8aComparative Example 8a 聚合物8a/84Polymer 8a/84 LiTFSI/25LiTFSI/25 乙基脲/12Ethyl urea/12 100100
对比例8bComparative example 8b 聚合物8b/84Polymer 8b/84 LiTFSI/25LiTFSI/25 乙基脲/12Ethyl urea/12 100100
对比例8cComparative example 8c PEO/84PEO/84 LiTFSI/25LiTFSI/25 乙基脲/12Ethyl urea/12 100100
实施例9Example 9 聚合物9/84Polymer 9/84 LiTFSI/40LiTFSI/40 钛酸镧锂/20Lithium lanthanum titanate/20 5050
对比例9aComparative Example 9a 聚合物9a/84Polymer 9a/84 LiTFSI/40LiTFSI/40 钛酸镧锂/20Lithium lanthanum titanate/20 5050
对比例9bComparative Example 9b 聚合物9b/84Polymer 9b/84 LiTFSI/40LiTFSI/40 钛酸镧锂/20Lithium lanthanum titanate/20 5050
对比例9cComparative Example 9c PEO/84PEO/84 LiTFSI/40LiTFSI/40 钛酸镧锂/20Lithium lanthanum titanate/20 5050
表1中，实施例1中的聚合物1的制备方法包括以下步骤：In table 1, the preparation method of polymer 1 in embodiment 1 comprises the following steps:
S1：在惰性气氛下，将甲基丙烯酰异氰酸酯与N,N-二乙基乙二胺加入苯中，在80℃以400r/min的转速搅拌5h后，除去溶剂得到单体1(含有脲基基团的单烯烃化合物，即第一单体)，单体1的结构见表3。S1: Under an inert atmosphere, add methacryloyl isocyanate and N,N-diethylethylenediamine to benzene, stir at 80°C at a speed of 400r/min for 5h, remove the solvent to obtain monomer 1 (containing urea The monoolefin compound of the base group, i.e. the first monomer), the structure of the monomer 1 is shown in Table 3.
S2：在惰性气氛下，将S1中单体1、聚乙二醇二甲基丙烯酸酯(第二单体)、TBPB加入到密闭容器中，以700r/min的转速搅拌12h后，将混合物均匀混合，在80℃下反应200min，得到聚合物1。S2: Under an inert atmosphere, add monomer 1, polyethylene glycol dimethacrylate (second monomer), and TBPB in S1 into a closed container, stir at a speed of 700r/min for 12h, and then mix the mixture uniformly Mix and react at 80°C for 200min to obtain Polymer 1.
表1中，对比例1a中的聚合物1a的制备方法包括以下步骤：In table 1, the preparation method of polymer 1a in comparative example 1a comprises the following steps:
S1：在惰性气氛下，将与制备聚合物1的单体等质量的聚乙二醇二甲基丙烯酸酯(第 二单体)、0.15gTBPB加入到密闭容器中，以700r/min的转速搅拌12h后，将混合物均匀混合，在80℃下反应200min，得到聚合物1a。S1: Under an inert atmosphere, add polyethylene glycol dimethacrylate (second monomer) and 0.15g TBPB of the same mass as the monomer used to prepare polymer 1 into a closed container, and stir at a speed of 700r/min After 12 hours, the mixture was uniformly mixed and reacted at 80°C for 200 minutes to obtain polymer 1a.
表1中，对比例1b中的聚合物1b的制备方法包括以下步骤：In table 1, the preparation method of polymer 1b in comparative example 1b comprises the following steps:
S1：在惰性气氛下，将甲基丙烯酰异氰酸酯与N,N-二乙基乙二胺加入苯中，在80℃以400r/min的转速搅拌5h后，除去溶剂得到单体1(含有脲基基团的单烯烃化合物，即第一单体)，第一单体的结构见表3。S1: Under an inert atmosphere, add methacryloyl isocyanate and N,N-diethylethylenediamine to benzene, stir at 80°C at a speed of 400r/min for 5h, remove the solvent to obtain monomer 1 (containing urea The monoolefin compound of the base group, i.e. the first monomer), the structure of the first monomer is shown in Table 3.
S2：在惰性气氛下，将与制备聚合物1的单体等质量的单体1、TBPB加入到密闭容器中，以700r/min的转速搅拌12h后，将混合物均匀混合，在80℃下反应200min，得到聚合物1b。S2: Under an inert atmosphere, add monomer 1 and TBPB of the same mass as the monomer used to prepare polymer 1 into a closed container, stir at a speed of 700r/min for 12h, mix the mixture uniformly, and react at 80°C After 200 min, polymer 1b was obtained.
其他实施例和对比例中的聚合物的制备方步骤分别与聚合物1、聚合物1a以及聚合物1b的制备步骤大致相似，不同处是第一单体的制备原料、第二单体和引发剂的选择、聚合工艺有所差异，具体见表2及表3。The preparation steps of the polymers in other examples and comparative examples are roughly similar to the preparation steps of polymer 1, polymer 1a and polymer 1b, except that the raw materials for the preparation of the first monomer, the second monomer and the trigger The selection of the agent and the polymerization process are different, see Table 2 and Table 3 for details.
表2中所有实施例中的第一单体的结构式见表4。See Table 4 for the structural formulas of the first monomers in all the examples in Table 2.
表2Table 2
Figure PCTCN2022120961-appb-000008
Figure PCTCN2022120961-appb-000008
Figure PCTCN2022120961-appb-000009
Figure PCTCN2022120961-appb-000009
表3table 3
Figure PCTCN2022120961-appb-000010
Figure PCTCN2022120961-appb-000010
表4Table 4
Figure PCTCN2022120961-appb-000011
Figure PCTCN2022120961-appb-000011
Figure PCTCN2022120961-appb-000012
Figure PCTCN2022120961-appb-000012
实施例10-11Examples 10-11
本实施例的锂离子电池的制备方法包括以下步骤：The preparation method of the lithium ion battery of the present embodiment comprises the following steps:
1)前驱浆液的制备1) Preparation of precursor slurry
将第一单体、第二单体、引发剂、锂盐、助剂分散在第一溶剂中得到前驱浆液；Dispersing the first monomer, the second monomer, the initiator, the lithium salt, and the auxiliary agent in the first solvent to obtain a precursor slurry;
2)正极片的制备2) Preparation of positive electrode sheet
与实施例1相同。Same as Example 1.
3)负极片的制备3) Preparation of negative electrode sheet
与实施例1相同。Same as Example 1.
4)将上述得到的正极片、隔膜、负极片依次通过叠片方式组装后向其中注入前驱浆液，加热引发聚合反应，得到锂离子电池。具体参数见表5。4) Assemble the above-obtained positive electrode sheet, separator, and negative electrode sheet sequentially by lamination, inject the precursor slurry into it, and heat to initiate a polymerization reaction to obtain a lithium-ion battery. The specific parameters are shown in Table 5.
对比例10a-11aComparative Examples 10a-11a
本对比例的锂离子电池的制备方法分别与实施例10-11一一对应，不同处在于步骤1)中不含有第一单体。具体参数见表5。The preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 10-11, the difference is that the first monomer is not contained in the step 1). The specific parameters are shown in Table 5.
对比例10b-11bComparative Examples 10b-11b
本对比例的锂离子电池的制备方法分别与实施例10-11一一对应，不同处在于步骤1)中不含有第二单体。具体参数见表5。The preparation method of the lithium-ion battery of this comparative example is one-to-one corresponding to the examples 10-11, the difference is that the second monomer is not contained in the step 1). The specific parameters are shown in Table 5.
表5table 5
Figure PCTCN2022120961-appb-000013
Figure PCTCN2022120961-appb-000013
Figure PCTCN2022120961-appb-000014
Figure PCTCN2022120961-appb-000014
实施例12Example 12
本实施例的锂离子电池的制备方法包括以下步骤：The preparation method of the lithium ion battery of the present embodiment comprises the following steps:
1)固态电解质的制备1) Preparation of solid electrolyte
在惰性气氛下，将12g单体1、72g聚乙二醇二甲基丙烯酸酯(第二单体)、0.15gTBPB(引发剂)、5g N-甲基乙酰胺、30g LiTFSI和LiBOB(其中LiTFSI：LiBOB质量比为3:1)加入到密闭容器中，以600r/min的转速搅拌12h后，将混合物均匀混合，得到前驱体反应液；将前驱体反应液涂布在基板表面依次经过干燥、辊压，得到厚度为100μm固态电解质。Under an inert atmosphere, 12g of monomer 1, 72g of polyethylene glycol dimethacrylate (second monomer), 0.15g of TBPB (initiator), 5g of N-methylacetamide, 30g of LiTFSI and LiBOB (wherein LiTFSI : LiBOB mass ratio is 3:1) into the airtight container, after stirring for 12h with the rotating speed of 600r/min, the mixture is uniformly mixed to obtain the precursor reaction solution; the precursor reaction solution is coated on the surface of the substrate through drying, Roll pressing to obtain a solid electrolyte with a thickness of 100 μm.
2)正极片的制备2) Preparation of positive electrode sheet
与实施例1相同。Same as Example 1.
3)负极片的制备3) Preparation of negative electrode sheet
与实施例1相同。Same as Example 1.
4)将上述得到的正极片、隔膜、负极片依次通过叠片方式组装后向其中注入前驱浆液，加热引发聚合反应，得到锂离子电池。4) Assemble the above-obtained positive electrode sheet, separator, and negative electrode sheet sequentially by lamination, inject the precursor slurry into it, and heat to initiate a polymerization reaction to obtain a lithium-ion battery.
实施例13Example 13
本实施例的锂离子电池的制备方法包括以下步骤：The preparation method of the lithium ion battery of the present embodiment comprises the following steps:
1)正极片的制备1) Preparation of positive electrode sheet
将85g的镍钴锰三元材料(Li[Ni0.6Co0.2Mn0.2]O2)、2g的导电碳黑、1g聚偏氟乙烯(溶解在100g NMP中)、50gNMP、3g聚合物1、4gLITFSI、5g甲基脲均匀混合后，涂布在铝箔的两个功能表面，依次经过干燥、辊压，得到正极片。85g of nickel-cobalt-manganese ternary material (Li[Ni0.6Co0.2Mn0.2]O2), 2g of conductive carbon black, 1g of polyvinylidene fluoride (dissolved in 100g of NMP), 50g of NMP, 3g of polymer 1, 4g of LITFSI and 5g of methylurea were evenly mixed, coated on the two functional surfaces of the aluminum foil, dried and rolled in sequence to obtain the positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode sheet
将天津中能锂业提供的50微米铜基复合锂作为负极，其中铜箔厚度10微米，锂层为20微米；The 50 micron copper-based composite lithium provided by Tianjin Zhongneng Lithium Industry Co., Ltd. is used as the negative electrode, in which the thickness of the copper foil is 10 microns, and the lithium layer is 20 microns;
3)固态电解质的制备3) Preparation of solid electrolyte
将5克聚氧化乙烯(分子量100W)、2克LITFSI、100g无水乙腈，均匀混合后，涂布在光滑表面，在干燥房(露点-50℃)除去溶剂，热压后得到200微米厚固态电解质。Mix 5 grams of polyethylene oxide (molecular weight 100W), 2 grams of LITFSI, and 100 g of anhydrous acetonitrile evenly, and spread it on a smooth surface, remove the solvent in a drying room (dew point -50°C), and obtain a 200 micron thick solid after hot pressing electrolyte.
4)将上述得到的正极片、固态电解质、负极片依次通过叠片方式制备固态电池。4) The positive electrode sheet, solid electrolyte, and negative electrode sheet obtained above are sequentially stacked to prepare a solid-state battery.
实施例14Example 14
本实施例的锂离子电池的制备方法包括以下步骤：The preparation method of the lithium ion battery of the present embodiment comprises the following steps:
1)正极极片的制备1) Preparation of positive electrode sheet
将95g的镍钴锰三元材料(Li[Ni0.6Co0.2Mn0.2]O2)、3g的导电碳黑、3g聚偏氟乙烯(溶解在100g NMP中)、50gNMP均匀混合后，涂布在铝箔的两个功能表面，经过烘干、辊压、分切后得到正极片；After uniformly mixing 95g of nickel-cobalt-manganese ternary material (Li[Ni0.6Co0.2Mn0.2]O2), 3g of conductive carbon black, 3g of polyvinylidene fluoride (dissolved in 100g of NMP), and 50g of NMP, they were coated on The two functional surfaces of the aluminum foil are dried, rolled and cut to obtain the positive electrode sheet;
2)负极片的制备2) Preparation of negative electrode sheet
将85g石墨、3g聚合物1、1g导电炭黑、1g粘结剂聚丁苯橡胶、1g羧甲基纤维素钠、4gLITFSI、5g甲基脲溶解在100g水中，均匀混合后，涂覆于负极集流体铜箔的两个功能表面，经烘干、辊压和模切得到负极片；Dissolve 85g of graphite, 3g of polymer 1, 1g of conductive carbon black, 1g of binder polystyrene butadiene rubber, 1g of sodium carboxymethylcellulose, 4g of LITFSI, and 5g of methylurea in 100g of water, mix evenly, and coat on the negative electrode The two functional surfaces of the current collector copper foil are dried, rolled and die-cut to obtain the negative electrode sheet;
3)固态电解质的制备3) Preparation of solid electrolyte
将5克聚氧化乙烯(分子量100W)、2克LITFSI、100g无水乙腈，均匀混合后，涂布在光滑表面，在干燥房(露点-50℃)除去溶剂，热压后得到200微米厚固态电解质。Mix 5 grams of polyethylene oxide (molecular weight 100W), 2 grams of LITFSI, and 100 g of anhydrous acetonitrile evenly, and spread it on a smooth surface, remove the solvent in a drying room (dew point -50°C), and obtain a 200 micron thick solid after hot pressing electrolyte.
4)将上述得到的负极片、固态电解质、正极片依次通过叠片方式制备固态电池。4) The negative electrode sheet, solid electrolyte, and positive electrode sheet obtained above are sequentially stacked to prepare a solid-state battery.
试验例Test case
1、表1中，实施例的聚合物的数均分子量检测：将聚合物溶于溶剂中，形成均匀液态体系，进行抽滤过有机膜，取样品进入日本岛津GPC-20A凝胶色谱仪进行检测，收集分子量信息；1. In Table 1, the number-average molecular weight detection of the polymer of the embodiment: the polymer is dissolved in a solvent to form a uniform liquid system, which is filtered through an organic membrane, and the sample is taken into a Shimadzu GPC-20A gel chromatograph Perform detection and collect molecular weight information;
具体结果见表6。The specific results are shown in Table 6.
2、固态电解质离子电导率测试方法为：采用交流阻抗法对固态电解质的离子电导率进行测试，所用仪器为上海辰华仪器有限公司CHI660E型号电化学工作站。在氩气手套箱中，按照正极壳、不锈钢垫片、固态聚合物电解质、不锈钢垫片、弹片、负极壳的顺序组装成扣式电池，交流阻抗测试频率为100mHz～1000KHz，振幅电压为5mV、测试温度为30℃。固态电解质离子电导率电导率计算公式：2. The test method for the ionic conductivity of the solid electrolyte is: use the AC impedance method to test the ionic conductivity of the solid electrolyte, and the instrument used is the CHI660E electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd. In an argon glove box, assemble a button battery in the order of the positive electrode case, stainless steel gasket, solid polymer electrolyte, stainless steel gasket, shrapnel, and negative electrode case. The AC impedance test frequency is 100mHz-1000KHz, and the amplitude voltage is 5mV, The test temperature is 30°C. Solid electrolyte ionic conductivity conductivity calculation formula:
ρ＝L/(R·S)ρ=L/(R·S)
其中，R为固态聚合物电解质的本体阻抗(Ω)；L为固态电解质厚度(cm)；S为扣式电池有效接触面积(cm2)。Among them, R is the bulk impedance of the solid polymer electrolyte (Ω); L is the thickness of the solid electrolyte (cm); S is the effective contact area of the button battery (cm2).
实施例13和14的样本相同，组成均为：3g聚合物1、4gLITFSI、5g甲基脲的混合物。The samples of Examples 13 and 14 are the same, and both have the composition: a mixture of 3g of Polymer 1, 4g of LITFSI, and 5g of methylurea.
具体结果见表6。The specific results are shown in Table 6.
3、150℃炉温测试：采用IEC 62133:2002规定的热滥用试验方法，将充满电的电池在室温下稳定后放入一个自然或循环空气对流的恒温恒湿箱中，试验箱以5℃/min±2℃/min的速率升温至150±2℃左右，恒温30min后，观察电池是否发生热失控。具体结果见表7。3. Furnace temperature test at 150°C: adopt the thermal abuse test method specified in IEC 62133:2002, put the fully charged battery into a constant temperature and humidity chamber with natural or circulating air convection after it is stabilized at room temperature, and the temperature of the test chamber is 5°C Raise the temperature at a rate of /min±2°C/min to about 150±2°C, keep the temperature for 30 minutes, and observe whether the battery has thermal runaway. The specific results are shown in Table 7.
4、25℃力学性能测试：按照国标GB/T 3354-2014对实施例和对比例中的固态电解质进行检测，主要区别是温度保持在25℃。具体结果见表7。4. Mechanical properties test at 25°C: The solid electrolytes in the examples and comparative examples were tested according to the national standard GB/T 3354-2014, the main difference being that the temperature was kept at 25°C. The specific results are shown in Table 7.
5、150℃力学性能测试：按照国标GB/T 3354-2014对实施例和对比例中的固态电解质进行检测，主要区别是温度保持在150℃。具体结果见表7。5. Mechanical properties test at 150°C: The solid electrolytes in the examples and comparative examples were tested according to the national standard GB/T 3354-2014, the main difference being that the temperature was kept at 150°C. The specific results are shown in Table 7.
6、锂离子电池电池循环性能测试方法为：将锂离子电池放在蓝电电池充放电测试柜上进行充放电循环测试，测试条件为30℃、0.5C/0.5C充放电，充放电起止电压为3.0-4.55V，记录当容量衰减至首次放电容量的80％时所经历的循环次数。具体结果见表7。6. The battery cycle performance test method of lithium-ion battery is: put the lithium-ion battery on the blue battery charge-discharge test cabinet for charge-discharge cycle test. 3.0-4.55V, record the number of cycles experienced when the capacity decays to 80% of the first discharge capacity. The specific results are shown in Table 7.
表6Table 6
 the 第一结构单元所占比例/％Proportion of the first structural unit/% 第一结构单元所占比例/％Proportion of the first structural unit/% 第三结构单元所占比例/％Proportion of the third structural unit/% 聚合物数均分子量Polymer Number Average Molecular Weight
聚合物1Polymer 1 1010 9090 ------ 30003000
聚合物2Polymer 2 3030 5555 1515 50005000
聚合物3Polymer 3 99.599.5 0.50.5 ------ 100000100000
聚合物4Polymer 4 3535 6565 ------ 4000040000
聚合物5Polymer 5 5555 4545 ------ 1000010000
聚合物6Polymer 6 4040 5050 1010 3000030000
聚合物7Polymer 7 5151 4949 ------ 90009000
聚合物8Polymer 8 3535 6565 ------ 2000020000
聚合物9Polymer 9 7575 2525 ------ 1500015000
表7Table 7
Figure PCTCN2022120961-appb-000015
Figure PCTCN2022120961-appb-000015
Figure PCTCN2022120961-appb-000016
Figure PCTCN2022120961-appb-000016
根据表7可知：本申请的固态电解质在满足锂离子高效传输的同时，更具有优异的安全强度，尤其在高温中能够保证正常的工作状态，避免热失控现象的发生。According to Table 7, it can be seen that the solid electrolyte of the present application not only satisfies the high-efficiency transmission of lithium ions, but also has excellent safety strength, especially at high temperatures, which can ensure normal working conditions and avoid thermal runaway.
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。The embodiments of the present application have been described above. However, this application is not limited to the above-mentioned embodiment. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included within the protection scope of this application.

Claims (15)

  1. 一种固态电解质，其中，所述固态电解质包括聚合物，所述聚合物包括来自于含有取代或未取代的脲基基团的单烯烃化合物的第一结构单元和来自于多烯烃交联剂的第二结构单元。A solid electrolyte, wherein the solid electrolyte comprises a polymer comprising a first structural unit derived from a monoolefin compound containing a substituted or unsubstituted ureido group and a polyolefin crosslinking agent derived from Second structural unit.
  2. 根据权利要求1所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物具有式1所示的结构，The solid electrolyte according to claim 1, wherein the monoolefin compound containing a substituted or unsubstituted ureido group has a structure shown in formula 1,
    Figure PCTCN2022120961-appb-100001
    Figure PCTCN2022120961-appb-100001
    其中，R1、R3、R4分别独立地选自H、卤素、硝基、氰基、取代或未取代的C1～12的烷基、取代或未取代的C1～12的烷氧基、取代或未取代的氨基；R2选自羰基、取代或未取代的(杂)芳基、酯基、取代或未取代的C1～12亚烷基、羧基或者化学键；M1选自H、羰基、取代或未取代的C1～20烷基、取代或未取代的C1～20烷氧基、羟基、卤素、氨基、硝基、三氟甲基、烃硫基、取代或未取代的(杂)芳基；M2、M3分别独立地选自氢、取代或未取代的C4～60(杂)芳基、取代或未取代的C1～20烷基、取代或未取代的C1～20烷氧基、羰基、取代或未取代含有杂环原子的C2～12环烷基、酰基、羧基、酯基、或者M2、M3键结成环。Among them, R1, R3, R4 are independently selected from H, halogen, nitro, cyano, substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C1-12 alkoxy, substituted or unsubstituted Substituted amino; R2 is selected from carbonyl, substituted or unsubstituted (hetero) aryl, ester group, substituted or unsubstituted C1~12 alkylene, carboxyl or chemical bond; M1 is selected from H, carbonyl, substituted or unsubstituted C1~20 alkyl, substituted or unsubstituted C1~20 alkoxy, hydroxyl, halogen, amino, nitro, trifluoromethyl, hydrocarbon thio, substituted or unsubstituted (hetero)aryl; M2, M3 are independently selected from hydrogen, substituted or unsubstituted C4~60 (hetero)aryl, substituted or unsubstituted C1~20 alkyl, substituted or unsubstituted C1~20 alkoxy, carbonyl, substituted or unsubstituted Substituting a C2-12 cycloalkyl group, an acyl group, a carboxyl group, an ester group containing a heterocyclic atom, or M2, M3 are bonded to form a ring.
  3. 根据权利要求1或2所述的固态电解质，其中，所述多烯烃交联剂的数均分子量小于2000。The solid electrolyte according to claim 1 or 2, wherein the number average molecular weight of the polyene crosslinking agent is less than 2000.
  4. 根据权利要求1-3任一项所述的固态电解质，其中，所述聚合物的数均分子量为3000-100000。The solid electrolyte according to any one of claims 1-3, wherein the polymer has a number average molecular weight of 3,000-100,000.
  5. 根据权利要求4所述的固态电解质，其中，所述第一结构单元在所述聚合物中的质量占比为10％-99.5％，所述第二结构单元在所述聚合物中的质量占比为0.5％-90％。The solid electrolyte according to claim 4, wherein the mass proportion of the first structural unit in the polymer is 10%-99.5%, and the mass proportion of the second structural unit in the polymer is The ratio is 0.5%-90%.
  6. 根据权利要求1-4任一项所述的固态电解质，其中，所述聚合物还包括第三结构单元，所述第三结构单元来自于丙烯酸、丙烯酸酯、聚乙二醇甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯腈、氨基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、乙烯基硅材料中的至少一种。The solid electrolyte according to any one of claims 1-4, wherein the polymer further comprises a third structural unit, the third structural unit is derived from acrylic acid, acrylate, polyethylene glycol methacrylate, At least one of methyl methacrylate, acrylonitrile, aminoacrylate, trimethylolpropane trimethacrylate, and vinyl silicon.
  7. 根据权利要求6所述的固态电解质，其中，所述第一结构单元在所述聚合物中的质量占比为10％-95％，所述第二结构单元在所述聚合物中的质量占比为0.5％-85％，所述第三结构单元在所述聚合物中的质量占比为0.1％-20％。The solid electrolyte according to claim 6, wherein the mass proportion of the first structural unit in the polymer is 10%-95%, and the mass proportion of the second structural unit in the polymer is The ratio is 0.5%-85%, and the mass proportion of the third structural unit in the polymer is 0.1%-20%.
  8. 根据权利要求1-7任一项所述的固态电解质，其中，所述固态电解质按照质量百分含量包括：聚合物40％～90％、锂盐10％～40％、助剂0％～20％。The solid electrolyte according to any one of claims 1-7, wherein the solid electrolyte comprises: 40% to 90% of polymer, 10% to 40% of lithium salt, 0% to 20% of additives in terms of mass percentage. %.
  9. 根据权利要求1或2所述的固态电解质，其中，所述含有取代或未取代的脲基 基团的单烯烃化合物的分子量为100-5000。The solid electrolyte according to claim 1 or 2, wherein the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 100-5000.
  10. 根据权利要求9所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物的分子量为150-2000。The solid electrolyte according to claim 9, wherein the molecular weight of the monoolefin compound containing substituted or unsubstituted ureido groups is 150-2000.
  11. 根据权利要求2所述的固态电解质，其中，所述含有取代或未取代的脲基基团的单烯烃化合物按照包括以下过程的方法制备得到：The solid electrolyte according to claim 2, wherein the monoolefin compound containing a substituted or unsubstituted ureido group is prepared according to a method comprising the following process:
    使包含第一异氰酸酯类化合物和第一胺类化合物的溶剂体系，或者包含第二异氰酸酯类化合物和第二胺类化合物的溶剂体系反应，得到所述含有取代或未取代的脲基基团的单烯烃化合物；其中，所述第一异氰酸酯类化合物满足式2a所示的结构，所述第一胺类化合物满足式3a所示的结构，所述第一胺类化合物满足式2b所示的结构，所述第二异氰酸酯类化合物满足式3b所示的结构，式3b中，Mx为M2或者M3，reacting a solvent system comprising a first isocyanate compound and a first amine compound, or a solvent system comprising a second isocyanate compound and a second amine compound, to obtain the mono-containing substituted or unsubstituted ureido group Olefin compounds; wherein, the first isocyanate compound satisfies the structure shown in formula 2a, the first amine compound satisfies the structure shown in formula 3a, and the first amine compound satisfies the structure shown in formula 2b, The second isocyanate compound satisfies the structure shown in formula 3b, in formula 3b, Mx is M2 or M3,
    Figure PCTCN2022120961-appb-100002
    Figure PCTCN2022120961-appb-100002
  12. 一种锂离子电池，其中，包括正极片、负极片以及位于所述正极片和负极片之间的权利要求1-11任一项所述的固态电解质。A lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet and the solid electrolyte according to any one of claims 1-11 between the positive electrode sheet and the negative electrode sheet.
  13. 一种正极片，其中，所述正极片包括权利要求1-11任一项所述的固态电解质；A positive electrode sheet, wherein the positive electrode sheet comprises the solid electrolyte according to any one of claims 1-11;
    所述正极片包括正极活性层，所述正极活性层的内部和/或表面具有所述固态电解质。The positive electrode sheet includes a positive electrode active layer, and the interior and/or surface of the positive electrode active layer has the solid electrolyte.
  14. 一种负极片，其中，所述负极片包括权利要求1-11任一项所述的固态电解质；A negative electrode sheet, wherein the negative electrode sheet comprises the solid electrolyte according to any one of claims 1-11;
    所述负极片包括负极基体，所述负极基体的内部和/或表面具有所述固态电解质。The negative electrode sheet includes a negative electrode matrix, and the interior and/or surface of the negative electrode matrix has the solid electrolyte.
  15. 一种锂离子电池，其中，包括权利要求13所述的正极片，和/或权利要求14所述的负极片。A lithium ion battery, comprising the positive electrode sheet according to claim 13, and/or the negative electrode sheet according to claim 14.
PCT/CN2022/120961 2021-09-26 2022-09-23 Solid electrolyte and use thereof WO2023046091A1 (en)

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