WO2023046091A1 - Électrolyte solide et son utilisation - Google Patents

Électrolyte solide et son utilisation 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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solid electrolyte
substituted
unsubstituted
polymer
electrode sheet
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PCT/CN2022/120961
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English (en)
Chinese (zh)
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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/fr

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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.

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Abstract

La présente invention concerne un électrolyte solide et son utilisation. L'électrolyte solide comprend un polymère, qui comprend une première unité structurale dérivée d'un composé de monooléfine contenant un groupe uréido substitué ou non substitué et une seconde unité structurale dérivée d'un agent de réticulation de polyoléfine. L'électrolyte solide est avantageux pour améliorer davantage les performances de sécurité d'une batterie au lithium-ion, et présente en particulier de bonnes performances en termes de sécurité à haute température.
PCT/CN2022/120961 2021-09-26 2022-09-23 Électrolyte solide et son utilisation WO2023046091A1 (fr)

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