WO2022193554A1 - 电解液添加剂、电解液及锂离子电池 - Google Patents

电解液添加剂、电解液及锂离子电池 Download PDF

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WO2022193554A1
WO2022193554A1 PCT/CN2021/115026 CN2021115026W WO2022193554A1 WO 2022193554 A1 WO2022193554 A1 WO 2022193554A1 CN 2021115026 W CN2021115026 W CN 2021115026W WO 2022193554 A1 WO2022193554 A1 WO 2022193554A1
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electrolyte
additive
lithium
substituted
carbonate
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PCT/CN2021/115026
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English (en)
French (fr)
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曹哥尽
范伟贞
范超君
信勇
赵经纬
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广州天赐高新材料股份有限公司
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Priority to EP21931129.7A priority Critical patent/EP4290636A4/en
Priority to KR1020237031474A priority patent/KR20230140593A/ko
Publication of WO2022193554A1 publication Critical patent/WO2022193554A1/zh
Priority to US18/244,698 priority patent/US20230420738A1/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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of batteries, in particular to electrolyte additives, electrolytes and lithium ion batteries.
  • Lithium-ion battery electrolytes generally consist of lithium salts, solvents and additives.
  • Lithium hexafluorophosphate as a lithium salt widely used in commercialization, has the advantages of good solubility and high electrical conductivity.
  • lithium hexafluorophosphate has poor thermal stability, and is prone to decomposition reaction (LiPF 6 ⁇ LiF+PF 5 ) in high temperature environment, and the generated phosphorus pentafluoride, phosphorus pentafluoride is chemically active, and can react with trace impurities in the electrolyte.
  • the electrolyte solution additive having both film-forming properties and properties of suppressing the rise in acidity and chromaticity of the electrolyte solution.
  • a kind of electrolyte additive has the structure shown in formula (I):
  • One of X 1 , X 2 , X 3 and X 4 is N, and the rest are CR 1 ;
  • R 1 is selected from: H, 5-6-membered aryl, 5-6-membered heteroaryl, C 1-8 alkyl, C 2-8 alkenyl, C 0-8 alkylsilyl, R 0 substituted 5- 6-membered aryl, R 0 substituted 5-6 membered heteroaryl, R 0 substituted C 1-8 alkyl, R 0 substituted C 2-8 alkenyl, or R 0 substituted C 0-8 alkylsilyl;
  • R is selected from: 5-6-membered aryl, 5-6-membered heteroaryl, C 1-8 alkyl, C 2-8 alkenyl, C 0-8 alkylsilyl, R 0 substituted 5-6-membered aryl base, R 0 substituted 5-6-membered heteroaryl, R 0 substituted C 1-8 alkyl, R 0 substituted C 2-8 alkenyl, or R 0 substituted C 0-8 alkylsilyl;
  • R 0 is selected from: C 1-6 alkyl, C 1-6 alkoxy or halogen.
  • An electrolyte solution includes an additive, the additive includes a first additive, and the first additive is the above-mentioned electrolyte additive.
  • a lithium ion battery includes a positive electrode material, a negative electrode material and the above-mentioned electrolyte.
  • the electrolyte additive containing the nitrogen-containing five-membered heterocyclic sulfonic acid ester compound of the structure represented by the formula (I) By using the electrolyte additive containing the nitrogen-containing five-membered heterocyclic sulfonic acid ester compound of the structure represented by the formula (I), the increase of the acidity and chromaticity of the electrolyte can be effectively suppressed, and the stability of the electrolyte at high temperature can be improved, In addition, these compounds have excellent film-forming properties, and during the first charging process of the battery, they can reduce the negative electrode to form a stable SEI film, so the cycle performance of the battery can be effectively improved.
  • the principle that can produce the above-mentioned technical effect is as follows:
  • the nitrogen-containing five-membered heterocyclic ring in the compound represented by the formula (I) contains a nitrogen atom with a lone electron pair, so that the compound exhibits a weak Lewis basicity in the electrolyte, and can form a hexa-ligand with PF 5 .
  • the complex reduces the Lewis acidity and reactivity of PF 5 , thereby effectively suppressing the increase in the acidity of the electrolyte and the increase in chroma caused by the reaction between PF 5 and trace impurities in the electrolyte.
  • the above compounds have good compatibility with the graphite negative electrode, and when added to the electrolyte, they can react to form a film on the surface of the electrode.
  • the alkylated lithium sulfate produced by the decomposition of the above compounds introduces S element into the SEI film, increasing the ionic conductivity. Therefore, the cycle performance of the lithium-ion battery can be effectively improved.
  • Fig. 1 is comparative example 1, comparative example 2, embodiment 4, embodiment 6, embodiment 7 and embodiment 8 electrolyte before and after storage;
  • FIG. 2 is a graph of dQ/dV curves of Comparative Example 1, Comparative Example 2 and Example 4.
  • FIG. 2 is a graph of dQ/dV curves of Comparative Example 1, Comparative Example 2 and Example 4.
  • alkyl refers to a saturated hydrocarbon containing primary (normal) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, for example, "C1-8 alkyl” refers to an alkyl group containing 1 to 8 carbon atoms.
  • Suitable examples include, but are not limited to: methyl (Me, -CH3 ), ethyl (Et, -CH2CH3), 1 -propyl (n-Pr, n - propyl, -CH2CH2CH ) 3 ), 2-propyl (i-Pr, i-propyl, -CH(CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ) , 2-methyl-1-propyl (i-Bu, i-butyl, -CH 2 CH(CH 3 ) 2 ), 2-butyl (s-Bu, s-butyl, -CH(CH 3 ) )CH 2 CH 3 ), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH 3 ) 3 ), 1-pentyl (n-pentyl, -CH 2 CH 2 ) CH 2 CH 2 CH 3 ), 2-p
  • Heteroaryl means that on the basis of an aryl group, at least one carbon atom is replaced by a non-carbon atom, and the non-carbon atom can be N atom, O atom, S atom and the like. Suitable examples include, but are not limited to: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrrolo imidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furanofuran, thienofuran, benzisoxazole, benziisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine , triazine, quinoline,
  • Halogen or "halogen atom” refers to F, Cl, Br or I.
  • Halo-substituted or halo means that an optional position, optional number of H on the corresponding group is substituted with a halogen, such as fluoromethyl, including monofluoromethyl, difluoromethyl, trifluoromethyl; for example Fluoroethyl groups include, but are not limited to, CH3CH2F , CH2FCH2F , CF2HCH3 , CF3CH3 , CF3CF3 , and the like .
  • R can be a group acceptable in the art, such as: C 1-8 alkyl (preferably C 1-6 alkyl, more preferably C 1-4 alkyl), H or halogen (preferably F) ; wherein a plurality of R may be the same or different from each other.
  • C 0-8 alkylsilyl means In, R is C 0-8 alkyl, understandably, when R is C 0 alkyl, it means R does not contain carbon atoms, that is, R is H, which is equivalent to
  • Halogen substituted C 0-8 alkylsilyl means wherein R is halogen substituted C 0-8 alkyl, when R is C 0 alkyl, it means R does not contain carbon atoms, R is H or halogen, and at least one halogen, such as fluoro-C 0 alkylsilyl, is equivalent to
  • One embodiment of the present invention provides an electrolyte additive, which has the structure shown in formula (I):
  • One of X 1 , X 2 , X 3 and X 4 is N, and the rest are CR 1 ;
  • R 1 is selected from: H, 5-6-membered aryl, 5-6-membered heteroaryl, C 1-8 alkyl, C 2-8 alkenyl, C 0-8 alkylsilyl, R 0 substituted 5-6 aryl, R 0 substituted 5-6 membered heteroaryl, R 0 substituted C 1-8 alkyl, R 0 substituted C 2-8 alkenyl, or R 0 substituted C 0-8 alkylsilyl;
  • R is selected from: 5-6-membered aryl, 5-6-membered heteroaryl, C 1-8 alkyl, C 2-8 alkenyl, C 0-8 alkylsilyl, R 0 substituted 5-6-membered aryl , R 0 replaces 5-6-membered heteroaryl, R 0 replaces C 1-8 alkyl, R 0 replaces C 2-8 alkenyl, or R 0 replaces C 0-8 alkylsilyl;
  • R 0 is selected from: C 1-6 alkyl, C 1-6 alkoxy or halogen.
  • X 3 is N and X 1 , X 2 and X 4 are CR 1 .
  • X 3 is N
  • X 1 , X 2 and X 4 are CH, that is, selected from the structure represented by the following general formula:
  • R 1 is selected from: H, C 1-6 alkyl, C 2-6 alkenyl, R 0 substituted C 1-6 alkyl, or R 0 substituted C 2-6 alkenyl.
  • R is selected from: 5-6-membered aryl, 5-6-membered heteroaryl, C 1-6 alkyl, C 2-6 alkenyl, C 0-6 alkylsilyl, R 0 Substituted 5-6-membered aryl, R 0 substituted 5-6-membered heteroaryl, R 0 substituted C 1-6 alkyl, R 0 substituted C 2-6 alkenyl, or R 0 substituted C 0-6 alkylsilyl .
  • the 5-6 membered heteroaryl is selected from: furyl, thienyl, pyrrolyl, pyrazolyl, triazolyl, thiazolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, Pyridazinyl or triazinyl.
  • R 0 is selected from C 1-4 alkyl or halogen; further, R 0 is selected from halogen; further, R 0 is selected from fluorine.
  • R is selected from: phenyl, thienyl, imidazolyl, pyridyl, fluorophenyl, fluorothienyl, fluoroimidazolyl, fluoropyridine, methyl, ethyl, 1- Propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, fluoromethyl, fluoroethyl, fluoro-1-propyl, fluoro-2-propyl fluoro-1-butyl, fluoro-2-methyl-1-propyl, fluoro-2-butyl, vinyl, propenyl, butenyl, fluorovinyl, fluoropropenyl, fluoro Butenyl, trimethylsilyl, triethylsilyl, trifluorosilyl, (trifluoromethyl)dimethylsilyl, bis(trifluoromethyl)methylsilyl, or tris(trifluoromethyl)s
  • R is selected from: phenyl, fluorophenyl, imidazolyl, methyl, vinyl, trifluoromethyl or trimethylsilyl.
  • An embodiment of the present invention provides the application of the nitrogen-containing five-membered heterocyclic sulfonic acid ester compound of the structure shown in formula (I) as an electrolyte additive:
  • An embodiment of the present invention provides the application of the nitrogen-containing five-membered heterocyclic sulfonic acid ester compound represented by formula (I) in the preparation of an electrolyte solution.
  • An embodiment of the present invention provides an electrolyte solution, which includes an additive, and the additive includes a first additive, and the first additive is the above-mentioned electrolyte solution additive.
  • the above-mentioned additive further includes a second additive, and the second additive is selected from: vinylene carbonate, fluoroethylene carbonate, 1,3-propene sultone, 1,3-propane sulfonic acid ester, vinyl sulfate, or at least one of methylene methanedisulfonate.
  • the electrolyte is a non-aqueous electrolyte.
  • the additive in terms of mass percentage, is 0.01%-30%; further, the mass percentage of the electrolyte additive is 0.01%-10%; in one embodiment Among them, the above electrolyte also includes lithium salt and solvent; in one embodiment, in the above electrolyte, in terms of mass percentage, the lithium salt is 5%-20%, and the solvent is 50%-94.9%.
  • the mass percentage content of the first additive in the electrolyte is 0.01%-10%; further, the mass percentage content of the first additive is 0.1%-10%.
  • the mass percentage content of the second additive in the electrolyte is 0.01%-5%.
  • the content of the first additive is too low, the SEI film formed on the negative electrode will be incomplete, and the effect of improving the subsequent cycle of the battery will be poor. Thickness will increase the internal resistance of the battery, which will negatively affect the battery performance. Therefore, by controlling the additive content within the above range, the stability of the electrolyte and the film-forming effect can be ensured, thereby achieving the purpose of improving the battery cycle performance.
  • the lithium salt is at least selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis-oxalate borate, lithium difluorophosphate, lithium difluorooxalate phosphate and lithium bisfluorosulfonimide A sort of.
  • the solvent includes a ring type solvent and/or a linear type solvent; wherein, the ring type solvent is selected from: ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, phenyl acetate , at least one of 1,4-butyl sultone and 3,3,3-trifluoropropylene carbonate; the linear solvent is selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, acetic acid Ethyl ester, methyl propyl carbonate, propyl propionate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 2,2-difluoroethylacetic acid At least one of ester, 2,2-difluoroethyl propionate and 2,2-difluoroethyl methyl carbonate.
  • the ring type solvent is selected from: ethylene carbonate, propylene carbonate, ⁇ -butyrolact
  • An embodiment of the present invention provides an energy storage device, including the above-mentioned electrolyte.
  • the electrolyte is as described above, and details are not described herein again.
  • the energy storage device is a lithium-ion battery.
  • the positive electrode material of the lithium ion battery includes Li 1+a (Nix Co y M 1-xy ) O 2 , Li(Ni p Mn q Co 2-pq )O 4 and LiM h (PO 4 ) One or more of m ; wherein 0 ⁇ a ⁇ 0.3, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1; 0 ⁇ p ⁇ 2, 0 ⁇ q ⁇ 2, 0 ⁇ p+q ⁇ 2;0 ⁇ h ⁇ 5,0 ⁇ m ⁇ 5; M is Fe, Ni, Co, Mn, Al or V.
  • the negative electrode material of the lithium ion battery includes at least one of metal lithium, lithium alloy, carbon, silicon-based negative electrode material and tin-based negative electrode material.
  • the above-mentioned lithium ion battery adopts the electrolyte solution containing the above-mentioned nitrogen-containing five-membered heterocyclic sulfonic acid ester compound, which can effectively suppress the increase of the acidity and chromaticity of the electrolyte solution, and the above-mentioned electrolyte solution additive is compatible with the graphite negative electrode.
  • the surface of the electrode reacts to form a film, and the alkylated lithium sulfate produced by the decomposition of the electrolyte additive introduces the S element into the SEI film, which increases the ionic conductivity and improves the cycle performance of the lithium-ion battery.
  • the compound represented by formula (I1) accounts for 0.3% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte %;
  • the solvent is a solvent obtained by mixing ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2; the electrolyte of Example 1 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 1.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by formula (I3) accounts for 0.3% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte %;
  • the solvent is a mixture of ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2;
  • the electrolyte of Example 2 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 2.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by formula (I5) accounts for 0.3% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte %;
  • the solvent is a mixture of ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2;
  • the electrolyte of Example 3 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 3.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by formula (I1) accounts for 0.5% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, and the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte.
  • the solvent is a solvent formed by mixing ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2;
  • the electrolyte of Example 4 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 4.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by the formula (I1) accounts for 10% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, and the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte.
  • the solvent is a solvent obtained by mixing ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2;
  • the electrolyte of Example 5 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 5. Assemble the pouch battery according to the conventional method.
  • the compound represented by formula (I1) accounts for 0.5% of the weight of the electrolyte;
  • the conventional additive is VC, VC accounts for 1% of the weight of the electrolyte, and the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for 13% of the weight of the electrolyte.
  • the solvent is a mixture of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a weight ratio of 3:5:2;
  • the electrolyte of Example 6 is prepared according to a conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 6.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by formula (I1) accounts for 0.5% of the weight of the electrolyte;
  • the conventional additives are VC and DTD, VC and DTD each account for 1% of the weight of the electrolyte, the lithium salt is lithium hexafluorophosphate, and the lithium salt accounts for the electrolyte. 13% of the weight of the liquid;
  • the solvent is a solvent in which ethylene carbonate and ethyl methyl carbonate are mixed in a weight ratio of 1:2;
  • the electrolyte of Example 7 is prepared according to the conventional electrolyte preparation method.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 7.
  • the pouch battery is assembled according to the conventional method.
  • the compound represented by formula (I1) accounts for 0.5% of the weight of the electrolyte;
  • the conventional additives are VC and DTD, VC and DTD each account for 1% of the weight of the electrolyte, and the lithium salts are lithium hexafluorophosphate and bisfluorosulfonyl Lithium imide, lithium hexafluorophosphate and lithium bisfluorosulfonimide account for 12% and 1% of the weight of the electrolyte respectively;
  • the solvent is a mixture of ethylene carbonate and ethyl methyl carbonate in a weight ratio of 1:2; according to The conventional electrolyte preparation method was used to prepare the electrolyte of Example 8.
  • the positive electrode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ; the negative electrode material is artificial graphite; the separator is a polyethylene film; and the electrolyte is the electrolyte of Example 8.
  • the pouch battery is assembled according to the conventional method.
  • Comparative Example 1 Compared with Example 1, the difference of Comparative Example 1 is that the electrolyte does not contain a sulfonate compound.
  • Example 2 Compared with Example 1, the difference of Comparative Example 2 is that the electrolyte additive of Example 1 is replaced with a vinyl sulfate additive of 1% by weight of the electrolyte.
  • Example 3 Compared with Example 1, the difference of Comparative Example 3 is that the electrolyte additive of Example 1 is replaced with a triphenyl phosphite additive of 0.05% by weight of the electrolyte.
  • Example 7 Compared with Example 7, the difference of Comparative Example 6 is that the electrolyte additive of Example 7 is replaced with a triphenyl phosphite additive which accounts for 0.05% by weight of the electrolyte.
  • Example 4 Compared with Example 4, the difference of Comparative Example 5 is that the electrolyte additive of Example 4 is replaced with phenyl benzenesulfonate additive which accounts for 0.5% by weight of the electrolyte.
  • Electrolyte stability test The lithium ion battery electrolytes prepared in the above-mentioned Examples 1 to 8 and Comparative Examples 1 to 5 were respectively placed in imported sealed aluminum bottles, and the aluminum bottles were vacuum-sealed with aluminum-plastic films, and the electrolyte samples were placed at the same time. Stored in an incubator with a set temperature of 45°C. Samples were taken in the glove box before storage, 7 days, 14 days, 30 days and 60 days after storage to detect the acidity and chromaticity of the electrolyte. The acidity was tested with a potentiometric titrator. , the acidity value is converted into HF, the unit is ppm, the chromaticity adopts the platinum-cobalt colorimetric, and the chromaticity unit is Hazen.
  • Example 1 Numbering before storage 7 days 14 days 30 days 60 days
  • Example 1 5.5 20.3 25.2 29.8 33.3
  • Example 2 5.4 19.9 23.4 30.2 35.5
  • Example 4 5.4 19.8 24.3 26.9 31.1
  • Example 5 4.4 16.7 20.3 25.8 28.4
  • Example 6 7.3 21.3 25.6 27.4 31.9
  • Example 7 7.5 24.4 30.5 38.9 46.3
  • Example 8 6.8 23.1 27.9 35.0 42.4
  • Comparative Example 1 14.4 32.9 36.6 38.0 45.4
  • Comparative Example 2 15.1 97.5 111.8 126.3 139.0
  • Comparative Example 3 13.9 28.5 30.2 32.5 39.0
  • Comparative Example 4 14.6 31.6 41.2 58.6 86.3 Comparative Example 5 14.1 33.2 35.4 39.3 46.7
  • Example 6 10 10 10 10 20 45 Example 7 10 20 30 40 60
  • Example 8 10 10 20 40 60 Comparative Example 1 10 20 40 70 90 Comparative Example 2 10 50 80 150 300 Comparative Example 3 10 10 20 40 70 Comparative Example 4 10 20 40 50 100 Comparative Example 5 10 20 50 80 100
  • Battery high temperature cycle performance test The lithium-ion batteries prepared in the above-mentioned Examples 1 to 8 and Comparative Examples 1 to 5 were placed in an incubator at 45°C, charged to 4.2V with a current, constant current and constant voltage of 1C, and then charged at a constant current and voltage of 1C to 4.2V. The current was discharged to 3.0V at a constant current and cycled for 700 cycles to measure the capacity retention rate of the lithium-ion battery.
  • Example 1 90.5%
  • Example 2 90.1%
  • Example 3 90.6%
  • Example 4 91.7%
  • Example 5 89.9%
  • Example 6 91.6%
  • Example 7 92.5%
  • Example 8 93.3% Comparative Example 1 86.6% Comparative Example 2 89.5% Comparative Example 3 86.1% Comparative Example 4 89.4% Comparative Example 5 88.9%
  • Fig. 1 is comparative example 1, comparative example 2, embodiment 4-embodiment 8 electrolyte before and after storage, as can be seen from Fig. 1, the color of embodiment 4-embodiment 8 basically does not change, and comparative example 1 and contrast
  • the color of the scale 2 is noticeably darker, especially the comparative scale 2. It is illustrated that the electrolyte additives in Examples 1 to 8 can effectively suppress the rise of the acidity and chromaticity of the electrolyte, and the stability of the electrolyte containing the electrolyte additives is enhanced under high temperature conditions.
  • FIG. 2 is the dQ/dV curves of Comparative Example 1, Comparative Example 2 and Example 4. It can be seen from FIG. 2 that the cycle performance of Example 4 is significantly better than that of Comparative Example 1 and Comparative Example 2. It is illustrated that the electrolyte additives in Examples 1 to 8 can form a stable SEI film on the surface of the negative electrode, thereby achieving the purpose of improving the high temperature cycle performance of the lithium ion battery.

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Abstract

一种电解液添加剂、电解液及锂离子电池，其中电解液添加剂具有式(I)所示结构： > 该电解液添加剂兼具成膜特性与抑制电解液酸度和色度上升的特性，能够有效地提高电池的循环性能。

Description

电解液添加剂、电解液及锂离子电池 技术领域
本发明涉及电池技术领域，特别涉及电解液添加剂、电解液及锂离子电池。
背景技术
锂离子电池电解液一般由锂盐、溶剂和添加剂组成。六氟磷酸锂作为目前商业化大量使用的锂盐，具有溶解性好、电导率高等优点。然而，六氟磷酸锂热稳定性差，高温环境下容易发生分解反应(LiPF 6→LiF+PF 5)，生成的五氟化磷，五氟化磷化学性质活泼，能与电解液中存在的微量杂质发生反应，进而引起电解液酸度和色度的快速上升，恶化电解液品质、降低电池容量和循环性能。常用的碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、硫酸乙烯酯(DTD)等添加剂具有良好的成膜效果，但对电解液稳定性没有改善效果，而DTD这种成膜添加剂，本身的稳定性较差，高温下反而会进一步加剧电解液品质的恶化。行业中常用亚磷酸酯类化合物作为电解液稳定剂，这类添加剂虽然有助于抑制电解液色度上升，但是其与石墨负极兼容性差，即使在几百ppm的微量添加情况下，对电池循环性能也会有轻微的负面影响。
因此，继续开发一类兼具成膜特性与抑制电解液酸度和色度上升特性的电解液添加剂。
发明内容
基于此，有必要提供一种电解液添加剂、电解液及锂离子电池，该电解液添加剂兼具成膜特性与抑制电解液酸度和色度上升的特性。
一种电解液添加剂，具有式(I)所示结构：
Figure PCTCN2021115026-appb-000001
X 1、X 2、X 3和X 4中有一个为N，其余为CR 1；
R 1选自：H、5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷基硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷基硅基；
R选自：5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷基硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷基硅基；
R 0选自：C 1-6烷基、C 1-6烷氧基或卤素。
一种电解液，包括添加剂，所述添加剂包括第一添加剂，所述第一添加剂为上述电解液添加剂。
一种锂离子电池，包括正极材料、负极材料和上述电解液。
本发明具有以下有益效果：
通过采用包含式(I)所示结构的含氮五元杂环磺酸酯类化合物的电解液添加剂，能有效地抑制电解液酸度和色度的上升，提高电解液在高温下的稳定性，且该类化合物具有优异的成膜特性，在电池首次充电过程中，能在负极还原形成稳定的SEI膜，故能够有效地改善电池的循环性能。本发明技术人员推测能够产生上述技术效果的原理如下：
式(I)所示的化合物中的含氮五元杂环中含有具有孤电子对的氮原子，使得该化合物在电解液中呈现较弱的路易斯碱性，能与PF 5形成六配体的配合物， 降低PF 5的路易斯酸性和反应活性，进而有效抑制电解液酸度的上升，以及抑制PF 5与电解液中微量杂质反应引起的色度上升。此外，上述化合物与石墨负极具有较好的兼容性，添加到电解液中可以在电极表面反应成膜，上述化合物分解产生的烷基化硫酸锂给SEI膜引入了S元素，增加离子电导率，故而可以有效地提高锂离子电池循环性能。
附图说明
图1为对比例1、对比例2、实施例4、实施例6、实施例7和实施例8电解液存储前后图；
图2为对比例1、对比例2和实施例4的dQ/dV曲线图。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述，并给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
术语解释
术语“烷基”是指包含伯(正)碳原子、或仲碳原子、或叔碳原子、或季碳原子、或其组合的饱和烃。包含该术语的短语，例如，“C 1- 8烷基”是指包含1～8个 碳原子的烷基。合适的实例包括但不限于：甲基(Me、-CH 3)、乙基(Et、-CH 2CH 3)、1-丙基(n-Pr、n-丙基、-CH 2CH 2CH 3)、2-丙基(i-Pr、i-丙基、-CH(CH 3) 2)、1-丁基(n-Bu、n-丁基、-CH 2CH 2CH 2CH 3)、2-甲基-1-丙基(i-Bu、i-丁基、-CH 2CH(CH 3) 2)、2-丁基(s-Bu、s-丁基、-CH(CH 3)CH 2CH 3)、2-甲基-2-丙基(t-Bu、t-丁基、-C(CH 3) 3)、1-戊基(n-戊基、-CH 2CH 2CH 2CH 2CH 3)、2-戊基(-CH(CH3)CH2CH2CH3)、3-戊基(-CH(CH 2CH 3) 2)、2-甲基-2-丁基(-C(CH 3) 2CH 2CH 3)、3-甲基-2-丁基(-CH(CH 3)CH(CH 3) 2)、3-甲基-1-丁基(-CH 2CH 2CH(CH 3) 2)、2-甲基-1-丁基(-CH 2CH(CH 3)CH 2CH 3)、1-己基(-CH 2CH 2CH 2CH 2CH 2CH 3)、2-己基(-CH(CH 3)CH 2CH 2CH 2CH 3)、3-己基(-CH(CH 2CH 3)(CH 2CH 2CH 3))、2-甲基-2-戊基(-C(CH 3) 2CH 2CH 2CH 3)、3-甲基-2-戊基(-CH(CH 3)CH(CH 3)CH 2CH 3)、4-甲基-2-戊基(-CH(CH 3)CH 2CH(CH 3) 2)、3-甲基-3-戊基(-C(CH 3)(CH 2CH 3) 2)、2-甲基-3-戊基(-CH(CH 2CH 3)CH(CH 3) 2)、2,3-二甲基-2-丁基(-C(CH 3) 2CH(CH 3) 2)、3,3-二甲基-2-丁基(-CH(CH 3)C(CH 3) 3和辛基(-(CH 2) 7CH 3)。
“烯基”是指包含具有至少一个不饱和部位，即碳-碳sp 2双键的正碳原子、仲碳原子、叔碳原子或环碳原子的烃。包含该术语的短语，例如，“C 2- 8烯基”是指包含2～8个碳原子的烯基。合适的实例包括但不限于：乙烯基(-CH＝CH 2)、丙烯基(-CH 2CH＝CH 2)、环戊烯基(-C 5H 7)和5-己烯基(-CH 2CH 2CH 2CH 2CH＝CH 2)。
“杂芳基”是指在芳基的基础上至少一个碳原子被非碳原子所替代，非碳原子可以为N原子、O原子、S原子等。合适的实例包括但不限于：呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、 喹唑啉和喹唑啉酮。
“卤素”或“卤原子”是指F、Cl、Br或I。
“卤素取代”或“卤代”表述相应基团上任选位置、任选数量的H被卤素取代，例如氟代甲基，包括一氟甲基、二氟甲基、三氟甲基；例如氟代乙基包括但不限于：CH 3CH 2F、CH 2FCH 2F、CF 2HCH 3、CF 3CH 3、CF 3CF 3等。
“硅基”或“硅烷基”是指
Figure PCTCN2021115026-appb-000002
其中，R可以为本领域可接受的基团，例如：C 1-8烷基(优选为C 1-6烷基，更优选为C 1-4烷基)、H或卤素(优选为F)；其中，多个R可以彼此相同或不同。
“C 0-8烷基硅基”是指
Figure PCTCN2021115026-appb-000003
中，R为C 0-8烷基，可理解的，当R为C 0烷基时，表示
Figure PCTCN2021115026-appb-000004
中R不含有碳原子，即R均为H，相当于为
Figure PCTCN2021115026-appb-000005
“卤素取代C 0-8烷基硅基”是指
Figure PCTCN2021115026-appb-000006
中R为卤素取代C 0-8烷基，当R为C 0烷基时，表示
Figure PCTCN2021115026-appb-000007
中R不含有碳原子，R为H或卤素，且至少有一个卤素，例如氟代C 0烷基硅基，相当于为
Figure PCTCN2021115026-appb-000008
详细解释
本发明一实施方式提供了一种电解液添加剂，具有式(I)所示结构：
Figure PCTCN2021115026-appb-000009
X 1、X 2、X 3和X 4中有一个为N，其余为CR 1；
R 1选自：H、5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷硅基；
R选自：5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷硅基；
R 0选自：C 1-6烷基、C 1-6烷氧基或卤素。
在其中一实施例中，X 3为N，X 1、X 2和X 4为CR 1。
在其中一实施例中，X 3为N，X 1、X 2和X 4为CH，即选自以下通式所示结构：
Figure PCTCN2021115026-appb-000010
在其中一实施例中，R 1选自：H、C 1-6烷基、C 2-6烯基、R 0取代C 1-6烷基、或R 0取代C 2-6烯基。
在其中一实施例中，R选自：5-6元芳基、5-6元杂芳基、C 1-6烷基、C 2-6烯 基、C 0-6烷硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-6烷基、R 0取代C 2-6烯基、或R 0取代C 0-6烷硅基。
在其中一实施例中，5-6元杂芳基选自：呋喃基、噻吩基、吡咯基、吡唑基、三唑基、噻唑基、咪唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基或三嗪基。
在其中一实施例中，R 0选自C 1-4烷基或卤素；进一步地，R 0选自卤素；进一步地，R 0选自氟。
在其中一实施例中，R选自：苯基、噻吩基、咪唑基、吡啶基、氟代苯基、氟代噻吩基、氟代咪唑基、氟代吡啶、甲基、乙基、1-丙基、2-丙基、1-丁基、2-甲基-1-丙基、2-丁基、氟代甲基、氟代乙基、氟代1-丙基、氟代2-丙基、氟代1-丁基、氟代2-甲基-1-丙基、氟代2-丁基、乙烯基、丙烯基、丁烯基、氟代乙烯基、氟代丙烯基、氟代丁烯基、三甲基硅基、三乙基硅基、三氟代硅基、(三氟甲基)二甲基硅基、二(三氟甲基)甲基硅基、或三(三氟甲基)硅基。
在其中一实施例中，R选自：苯基、氟代苯基、咪唑基、甲基、乙烯基、三氟甲基或三甲基硅基。
在其中一实施例中，选自以下任一化合物：
Figure PCTCN2021115026-appb-000011
Figure PCTCN2021115026-appb-000012
上述电解液添加剂的制备可以参见CN105121404A。
本发明一实施方式提供了式(I)所示结构的含氮五元杂环磺酸酯类化合物在作为电解液添加剂中的应用：
Figure PCTCN2021115026-appb-000013
其中，各基团定义如上所述，在此不再进行赘述。
本发明一实施方式提供了式(I)所示的含氮五元杂环磺酸酯类化合物在制备电解液中的应用。
Figure PCTCN2021115026-appb-000014
其中，各基团定义如上所述，在此不再进行赘述。
本发明一实施方式提供了一种电解液，包括添加剂，添加剂包括第一添加剂，第一添加剂为上述电解液添加剂。
在其中一实施例中，上述添加剂还包括第二添加剂，第二添加剂选自：碳酸亚乙烯酯、氟代碳酸乙烯酯、1,3-丙烯磺酸内酯、1,3-丙烷磺酸内酯、硫酸乙烯酯、或甲烷二磺酸亚甲酯中的至少一种。
在其中一实施例中，电解液为非水电解液。
在其中一实施例中，在电解液中，以质量百分含量计，添加剂为0.01％-30％；进一步地，电解液添加剂的质量百分含量为0.01％～10％；在其中一实施例中，上述电解液中，还包括锂盐和溶剂；在其中一实施例中，上述电解液中，以质量百分含量计，锂盐为5％-20％，溶剂为50％-94.9％。
在其中一实施例中，电解液中第一添加剂的质量百分含量为0.01％-10％；进一步地，第一添加剂的质量百分含量为0.1％-10％。
在其中一实施例中，电解液中第二添加剂的质量百分含量为0.01％-5％。
第一添加剂含量太低则在负极形成的SEI膜不完整，对电池后续循环改善效果欠佳，第一添加剂含量过高则会使得还原成膜的能力过强，在负极表面形成的SEI膜过厚，反而会增加电池内阻，进而对电池性能带来负面影响，故通过将添加剂含量控制在上述范围内，可以保证电解液的稳定性与成膜效果，进而达到改善电池循环性能的目的。
在其中一实施例中，上述的电解液中，锂盐选自六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂及双氟磺酰亚胺锂中的至少一种。
在其中一实施例中，上述的电解液中，溶剂包括环型溶剂和/或线型溶剂；其中，环型溶剂选自：碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、乙酸苯酯、1，4-丁基磺酸内酯及3，3，3-三氟碳酸丙烯酯中的至少一种；线型溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、碳酸甲丙酯、丙酸丙酯、1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚、2，2-二氟乙基乙酸酯、2，2-二氟乙基丙 酸酯及2，2-二氟乙基碳酸甲酯中的至少一种。
本发明一实施方式提供了一种储能装置，包括上述电解液，电解液具体如上所述，在此不再进行赘述。在其中一实施例中，储能装置为锂离子电池。
在一实施例中，锂离子电池的正极材料包括Li 1+a(Ni xCo yM 1-x-y)O 2、Li(Ni pMn qCo 2-p-q)O 4及LiM h(PO 4) m中的一种或几种；其中0≤a≤0.3，0≤x≤1，0≤y≤1，0＜x+y≤1；0≤p≤2，0≤q≤2，0＜p+q≤2；0＜h＜5，0＜m＜5；M为Fe、Ni、Co、Mn、Al或V。
在一实施例中，锂离子电池的负极材料包括金属锂、锂合金、碳、硅基负极材料及锡基负极材料中的至少一种。
上述锂离子电池的通过采用包含上述含氮五元杂环磺酸酯类化合物的电解液，能够有效地抑制电解液酸度和色度上升，且上述电解液添加剂与石墨负极兼容性好，可以在电极表面反应成膜，电解液添加剂分解产生的烷基化硫酸锂给SEI膜引入了S元素，增加离子电导率，提高锂离子电池循环性能。
下面列举具体实施例来对本发明进行说明，但本发明并不局限于以下实施例。以下实施例中，所使用的试剂、材料以及仪器，若无特殊说明，均可以市售获得。
实施例1
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000015
本实施例中，式(I1)所示化合物占电解液的重量的0.3％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％； 溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例1电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例1电解液。按照常规方法组装成软包电池。
实施例2
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I3)所示。
Figure PCTCN2021115026-appb-000016
本实施例中，式(I3)所示化合物占电解液的重量的0.3％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例2电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例2电解液。按照常规方法组装成软包电池。
实施例3
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I5)所示。
Figure PCTCN2021115026-appb-000017
本实施例中，式(I5)所示化合物占电解液的重量的0.3％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例3电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例3电解液。按照常规方法组装成软包电池。
实施例4
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000018
本实施例中，式(I1)所示化合物占电解液的重量的0.5％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例4电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例4电解液。按照常规方法组装成软包电池。
实施例5
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000019
本实施例中，式(I1)所示化合物占电解液的重量的10％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例5电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例5电解液。按照常规方法组装成软包电池。
实施例6
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000020
本实施例中，式(I1)所示化合物占电解液的重量的0.5％；常规添加剂为VC，VC占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯、碳酸甲乙酯和碳酸二乙酯按重量比为3:5:2混合而成的溶剂；按照常规电解液配制方法配制实施例6电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例6电解液。按照常规方法组装成软包电池。
实施例7
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000021
本实施例中，式(I1)所示化合物占电解液的重量的0.5％；常规添加剂为VC和DTD，VC和DTD各占电解液的重量的1％，锂盐为六氟磷酸锂，锂盐占电解液的重量的13％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例7电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例7电解液。按照常规方法组装成软包电池。
实施例8
(1)电解液组成：
本实施例中的电解液添加剂的结构式如式(I1)所示。
Figure PCTCN2021115026-appb-000022
本实施例中，式(I1)所示化合物占电解液的重量的0.5％；常规添加剂为VC和DTD，VC和DTD各占电解液的重量的1％，锂盐为六氟磷酸锂和双氟磺 酰亚胺锂，六氟磷酸锂和双氟磺酰亚胺锂分别占电解液的重量的12％和1％；溶剂为碳酸乙烯酯和碳酸甲乙酯按重量比为1:2混合而成的溶剂；按照常规电解液配制方法配制实施例8电解液。
(2)组装锂离子电池：
正极材料为LiNi 0.8Co 0.1Mn 0.1O 2；负极材料为人造石墨；隔膜为聚乙烯膜；电解液为实施例8电解液。按照常规方法组装成软包电池。
对比例1
与实施例1相比，对比例1的不同之处在于，电解液中不含磺酸酯化合物。
对比例2
与实施例1相比，对比例2的不同之处在于，将实施例1的电解液添加剂替换为占电解液重量的1％的硫酸乙烯酯添加剂。
对比例3
与实施例1相比，对比例3的不同之处在于，将实施例1的电解液添加剂替换为占电解液重量的0.05％的亚磷酸三苯酯添加剂。
对比例4
与实施例7相比，对比例6的不同之处在于，将实施例7的电解液添加剂替换为占电解液重量的0.05％的亚磷酸三苯酯添加剂。
对比例5
与实施例4相比，对比例5的不同之处在于，将实施例4的电解液添加剂替换为占电解液重量的0.5％的苯磺酸苯酯添加剂。
锂离子电池电解液稳定性与电池高温性能测试
对实施例1～8、对比例1～5中的锂离子电池电解液稳定性与电池进行高温性能测试，测试方法为：
电解液稳定性测试：将上述实施例1～8和对比例1～5制备的锂离子电池电解液分别装到进口密封铝瓶中，铝瓶用铝塑膜抽真空封装，电解液样品同时置于设定温度为45℃的恒温箱中储存，分别在储存前、储存7天、14天、30天和60天后在手套箱中取样检测电解液酸度和色度值，酸度采用电位滴定仪测试，酸度值为折算成HF，单位为ppm，色度采用铂-钴比色，色度单位为Hazen。
测试结果如表1和表2所示：
表1(酸度/ppm)
编号 存储前 7天 14天 30天 60天
实施例1 5.5 20.3 25.2 29.8 33.3
实施例2 5.4 19.9 23.4 30.2 35.5
实施例3 6.7 22.7 28.9 32.1 36.0
实施例4 5.4 19.8 24.3 26.9 31.1
实施例5 4.4 16.7 20.3 25.8 28.4
实施例6 7.3 21.3 25.6 27.4 31.9
实施例7 7.5 24.4 30.5 38.9 46.3
实施例8 6.8 23.1 27.9 35.0 42.4
对比例1 14.4 32.9 36.6 38.0 45.4
对比例2 15.1 97.5 111.8 126.3 139.0
对比例3 13.9 28.5 30.2 32.5 39.0
对比例4 14.6 31.6 41.2 58.6 86.3
对比例5 14.1 33.2 35.4 39.3 46.7
表2(色度/Hazen)
编号 存储前 7天 14天 30天 60天
实施例1 10 10 15 35 50
实施例2 10 10 20 40 50
实施例3 10 15 25 40 60
实施例4 10 10 10 20 45
实施例5 10 10 10 20 40
实施例6 10 10 10 20 45
实施例7 10 20 30 40 60
实施例8 10 10 20 40 60
对比例1 10 20 40 70 90
对比例2 10 50 80 150 300
对比例3 10 10 20 40 70
对比例4 10 20 40 50 100
对比例5 10 20 50 80 100
电池高温循环性能测试：将上述实施例1～8和对比例1～5制备的锂离子电池置于45℃的恒温箱中，以1C的电流恒流恒压充电至4.2V，然后以1C的电流恒流放电至3.0V，循环700周，测定锂离子电池的容量保持率。
测试结果如表3所示：
表3
编号 45℃循环700周后的容量保持率
实施例1 90.5％
实施例2 90.1％
实施例3 90.6％
实施例4 91.7％
实施例5 89.9％
实施例6 91.6％
实施例7 92.5％
实施例8 93.3％
对比例1 86.6％
对比例2 89.5％
对比例3 86.1％
对比例4 89.4％
对比例5 88.9％
由表1～2可知，实施例1～8中的锂离子电池电解液在45℃高温下存储60天，电解液的酸度和色度均低于对比例1～5。图1为对比例1、对比例2、实施例4-实施例8电解液存储前后图，从图1可以看出，实施例4-实施例8的颜色基本没有变化，而对比例1和对比例2的颜色明显加深，特别是对比例2。说明实施例1～8中的电解液添加剂能够有效抑制电解液酸度和色度的上升，含有该电解液添加剂的电解液在高温条件下稳定性得到增强。
由表3可知，实施例1～8中的锂离子电池的高温循环性能优于对比例1～5。图2为对比例1、对比例2和实施例4的dQ/dV曲线图，从图2可以看出，实施例4的循环性能明显优于对比例1和对比例2。说明实施例1～8中的电解液添加剂能够在负极表面形成稳定的SEI膜，进而达到改善锂离子电池的高温循环性能的目的。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种电解液添加剂，其特征在于，具有式(I)所示结构：
    Figure PCTCN2021115026-appb-100001
    X 1、X 2、X 3和X 4中有一个为N，其余为CR 1；
    R 1选自：H、5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷基硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷基硅基；
    R选自：5-6元芳基、5-6元杂芳基、C 1-8烷基、C 2-8烯基、C 0-8烷基硅基、R 0取代5-6元芳基、R 0取代5-6元杂芳基、R 0取代C 1-8烷基、R 0取代C 2-8烯基、或R 0取代C 0-8烷基硅基；
    R 0选自：C 1-6烷基、C 1-6烷氧基或卤素。
  2. 根据权利要求1所述的电解液添加剂，其特征在于，X 3为N，X 1、X 2、和X 4为CH。
  3. 根据权利要求1所述的电解液添加剂，其特征在于，所述5-6元杂芳基选自：呋喃基、噻吩基、吡咯基、吡唑基、三唑基、噻唑基、咪唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基或三嗪基；
    R 0选自：C 1-4烷基或卤素。
  4. 根据权利要求1所述的电解液添加剂，其特征在于，R选自：苯基、噻吩基、咪唑基、吡啶基、氟代苯基、氟代噻吩基、氟代咪唑基、氟代吡啶、甲基、乙基、1-丙基、2-丙基、1-丁基、2-甲基-1-丙基、2-丁基、氟代甲基、氟代乙基、氟代1-丙基、氟代2-丙基、氟代1-丁基、氟代2-甲基-1-丙基、氟代2-丁 基、乙烯基、丙烯基、丁烯基、氟代乙烯基、氟代丙烯基、氟代丁烯基、三甲基硅基、三乙基硅基、三氟代硅基、(三氟甲基)二甲基硅基、二(三氟甲基)甲基硅基、或三(三氟甲基)硅基。
  5. 根据权利要求1所述的电解液添加剂，其特征在于，选自以下任一化合物：
    Figure PCTCN2021115026-appb-100002
  6. 一种电解液，其特征在于，包括添加剂，所述添加剂包括第一添加剂，所述第一添加剂为权利要求1～5中任一项所述电解液添加剂。
  7. 根据权利要求6所述的电解液添加剂，其特征在于，所述添加剂还包括第二添加剂，所述第二添加剂选自：碳酸亚乙烯酯、氟代碳酸乙烯酯、1,3-丙烯磺酸内酯、1,3-丙烷磺酸内酯、硫酸乙烯酯和甲烷二磺酸亚甲酯中的至少一种。
  8. 根据权利要求6或7所述的电解液，其特征在于，还包括锂盐和溶剂，在所述电解液中，以质量百分含量计，所述添加剂为0.01％-30％，所述锂盐为 5％-20％，所述溶剂为50％-94.9％。
  9. 根据权利要求8所述的电解液，其特征在于，所述锂盐选自六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸磷酸锂和双氟磺酰亚胺锂中的至少一种和/或；
    所述溶剂包括环型溶剂和/或线型溶剂；其中，所述环型溶剂选自：碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、乙酸苯酯、1，4-丁基磺酸内酯及3，3，3-三氟碳酸丙烯酯中的至少一种；所述线型溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、碳酸甲丙酯、丙酸丙酯、1，1，2，2-四氟乙基-2，2，3，3-四氟丙基醚、2，2-二氟乙基乙酸酯、2，2-二氟乙基丙酸酯及2，2-二氟乙基碳酸甲酯中的至少一种。
  10. 一种锂离子电池，其特征在于，包括正极材料、负极材料和权利要求4-9任一项所述的电解液。
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CN116888801A (zh) * 2022-09-22 2023-10-13 德山伊莱特拉有限公司 二次电池用电解液添加剂、包含该二次电池用电解液添加剂的锂二次电池用非水电解液、以及包含该锂二次电池用非水电解液的锂二次电池
CN115799631A (zh) * 2022-11-18 2023-03-14 广州天赐高新材料股份有限公司 一种用于磷酸铁锂电池的电解液及磷酸铁锂电池
CN116742124B (zh) * 2023-06-14 2024-02-09 广州天赐高新材料股份有限公司 含氮化合物的新用途、电解液添加剂组合物以及电池电解液

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