WO2022222420A1 - 取代硅基磷酸酯类化合物的新用途及电解液、锂离子电池 - Google Patents

取代硅基磷酸酯类化合物的新用途及电解液、锂离子电池 Download PDF

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WO2022222420A1
WO2022222420A1 PCT/CN2021/128543 CN2021128543W WO2022222420A1 WO 2022222420 A1 WO2022222420 A1 WO 2022222420A1 CN 2021128543 W CN2021128543 W CN 2021128543W WO 2022222420 A1 WO2022222420 A1 WO 2022222420A1
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electrolyte
lithium
alkene
additive
propyl
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English (en)
French (fr)
Chinese (zh)
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郑德培
范伟贞
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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    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
    • 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
    • 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 invention relates to the technical field of lithium ion batteries, in particular to new uses of substituted silicon-based phosphate compounds, electrolytes and lithium ion batteries.
  • Lithium-ion batteries have the advantages of high operating voltage, high specific energy density, long cycle life, low self-discharge rate, no memory effect, and low environmental pollution. They have been widely used in various consumer electronics and power battery markets. With the wide application of lithium-ion batteries, consumers' usage environment and demand for lithium-ion batteries are constantly improving, and at the same time, they have higher and higher requirements for the endurance of electronic devices, which requires lithium-ion batteries to have higher energy density.
  • lithium ion secondary batteries with higher energy density are being sought, and one of the methods is to use positive and negative electrode materials with high gram capacity.
  • ternary high-nickel cathode materials and silicon-based anode materials are potential high-energy-density materials for lithium-ion batteries.
  • materials with high nickel content are easy to absorb water.
  • the decomposition of the Ni-O bond structure on the surface leads to the precipitation of lithium to form alkaline substances such as lithium hydroxide and lithium carbonate, which reduces the stability of the electrolyte. Severe swelling.
  • silicon-based anode materials also have obvious shortcomings.
  • silicon particles are accompanied by volume expansion and contraction when lithium is deintercalated, resulting in particle pulverization and falling off, resulting in structural collapse and battery capacity attenuation; the second is The volume effect of the silicon-based anode material causes the SEI film to be continuously damaged and repaired. At the same time, the electrolyte is continuously consumed and the internal resistance of the battery gradually increases, which eventually leads to the diving of the battery.
  • the use of additives in the electrolyte is an efficient weapon to solve the above problems.
  • Many researchers improve the quality of the SEI film by adding different film-forming additives (such as vinylene carbonate, fluoroethylene carbonate, and ethylene ethylene carbonate) into the electrolyte, thereby improving the performance of the battery.
  • film-forming additives such as vinylene carbonate, fluoroethylene carbonate, and ethylene ethylene carbonate
  • the battery is likely to generate gas during high-temperature storage, causing the battery to swell and increase the impedance, which seriously affects the high-temperature performance of the battery. Therefore, there is an urgent need to develop a lithium-ion battery electrolyte with a high energy density system that can suppress gas swelling and reduce impedance.
  • substituted silicon-based phosphate compounds are used as an electrolyte additive, which can inhibit the gas swelling of the battery and reduce the impedance of a high energy density system.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from: C 1-8 alkyl, C 2-8 alkene or C 2- 8 alkynes;
  • R 1 , R 2 and R 3 is a C 1-8 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 4 , R 5 and R 6 is a C 1-8 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 7 , R 8 and R 9 is a C 1-8 alkyl group, and one of them is a C 2-8 alkene or a C 2-8 alkyne.
  • An electrolyte comprising an additive, the additive comprising a substituted silicon-based phosphate compound of the structure shown in formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from: C 1-6 alkyl, C 2-6 alkene or C 2- 6 alkynes;
  • R 1 , R 2 and R 3 is a C 1-6 alkyl group, and one of them is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 4 , R 5 and R 6 is a C 1-6 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 7 , R 8 and R 9 is a C 1-6 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne.
  • a lithium ion battery includes a positive electrode, a negative electrode and the above electrolyte.
  • the present invention uses substituted silicon-based phosphate compounds as electrolyte additives, such substances contain unsaturated groups, which can polymerize on the surfaces of positive and negative electrodes to form a stable interface film, thereby improving battery cycle performance. It can also inhibit the oxidation reaction of the electrolyte on the surface of the positive electrode, effectively inhibit the dissolution of metal ions, and inhibit the oxidative decomposition of the electrolyte in high temperature environments and gas production during cycling, thereby improving the high-temperature storage performance and high-temperature cycling of lithium-ion batteries. performance, to ensure the excellent performance of lithium-ion batteries. In addition, we also found that the content of unsaturated groups should be kept in a certain range. Too many unsaturated groups will cause the interface film to be too thick, which will increase the internal resistance of the battery and hinder the performance of the battery.
  • FIG. 1 is a performance test chart of the battery of Example 1.
  • FIG. 1 is a performance test chart of the battery of Example 1.
  • 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, each occurrence of which may independently be C1 alkyl, C2 alkyl, C 3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl or C8 alkyl.
  • 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
  • Alkenyl refers to a hydrocarbon containing a normal, secondary, tertiary, or cyclic carbon atom having at least one site of unsaturation, ie, a carbon-carbon sp2 double bond. Phrases containing this term, for example, "C 2-8 alkenyl” refers to an alkenyl group containing 2 to 8 carbon atoms, each occurrence of which may independently be C 2 alkenyl, C 3 alkenyl, C 4 alkenyl, C 5 alkenyl, C 6 alkenyl, C 7 alkenyl or C 8 alkenyl.
  • Alkynyl refers to a hydrocarbon containing a normal, secondary, tertiary, or cyclic carbon atom having at least one site of unsaturation, ie, a carbon-carbon sp triple bond. Phrases containing this term, for example, "C 2-8 alkynyl” refers to an alkynyl group containing 2 to 8 carbon atoms, each occurrence of which may independently be C 2 alkynyl, C 3 alkynyl, C 4 alkynyl, C 5 alkynyl, C 6 alkynyl, C 7 alkynyl or C 8 alkynyl. Suitable examples include, but are not limited to: ethynyl (-C ⁇ CH) and propargyl ( -CH2C ⁇ CH ).
  • One embodiment of the present invention provides the application of the substituted silicon-based phosphate compound of the structure shown in formula (I) as an electrolyte additive:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from: C 1-8 alkyl, C 2-8 alkene or C 2- 8 alkynes;
  • R 1 , R 2 and R 3 is a C 1-8 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 4 , R 5 and R 6 is a C 1-8 alkyl group, and one is a C 2-8 alkene or a C 2-8 alkyne;
  • At least one of R 7 , R 8 and R 9 is a C 1-8 alkyl group, and one of them is a C 2-8 alkene or a C 2-8 alkyne.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from: C 1-6 alkyl, C 2-6 alkene or C 2-6 alkynes.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently selected from: C 1-4 alkyl, C 2-4 alkene or C 2-4 alkynes.
  • R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 are each independently selected from: vinyl, ethynyl, allyl, or propargyl;
  • R 2 , R 5 , R 8 is each independently selected from: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, or 2-butyl.
  • R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 are each independently selected from: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, or 2-butyl;
  • R 2 , R 5 , R 8 are each independently selected from: vinyl, ethynyl, allyl or propargyl.
  • At least two of -SiR 1 R 2 R 3 , -SiR 4 R 5 R 6 , and -SiR 7 R 8 R 9 are identical to each other.
  • -SiR 1 R 2 R 3 , -SiR 4 R 5 R 6 , and -SiR 7 R 8 R 9 are the same as each other.
  • An embodiment of the present invention relates to an electrolyte, including an additive, and the additive includes a substituted silicon-based phosphate compound of the structure represented by formula (I):
  • the additive further includes a second additive, and the second additive is vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl sulfite, vinyl sulfate, and 1,3-propane sulfonic acid one or more of the lactones.
  • the mass percentage of the additive in the electrolyte, is 0.05%-20.0%; further, the mass percentage of the additive is 0.1%-15%; further, the mass percentage of the additive 1%-10%.
  • the compound of formula (I) is the first additive, and in the electrolyte, the mass percentage of the first additive is 0.1%-15%; further, the mass percentage of the first additive is The content is 0.1%-10%; further, the mass percentage content of the first additive is 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • the mass percentage content of the second additive is 0.1%-5%.
  • the above electrolyte further includes a lithium salt and a solvent, wherein the lithium salt is selected from the group consisting of: lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bisfluorosulfonimide, and One or more of lithium bistrifluoromethanesulfonimide.
  • the lithium salt is selected from the group consisting of: lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate, lithium bisfluorosulfonimide, and One or more of lithium bistrifluoromethanesulfonimide.
  • the concentration of the lithium salt is 0.5M-1.5M; further, the concentration of the lithium salt is 0.5M, 0.75M, 1M, 1.25M, 1.5M.
  • the solvent is selected from one or more of linear carbonate-based solvents, cyclic carbonate-based solvents, and carboxylate-based solvents.
  • the cyclic carbonate-based solvent is selected from: one or more of ethylene carbonate (EC) and propylene carbonate (PC); in some embodiments, the chain-shaped carbonate-based solvent is selected from: One or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC); in some embodiments, the carboxylate solvent is selected from: propyl acetate (PA) , one or more of ethyl acetate (EA) and propyl propionate (PP).
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • the carboxylate solvent is selected from: propyl acetate (PA) , one or more of ethyl acetate (EA) and propyl propionate (PP).
  • the solvent is a combination of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC); further, ethylene carbonate (EC), diethyl carbonate (DEC)
  • EMC ethyl methyl carbonate
  • An embodiment of the present invention also provides a lithium ion battery, including a positive electrode, a negative electrode, and the above-mentioned electrolyte.
  • the electrolyte solution is as described above, and will not be repeated here.
  • the positive electrode material forming the positive electrode includes a lithium transition metal oxide, wherein the lithium transition metal oxide is LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , Li 2 MnO 4 , LiFePO 4 , Li 1+ a Mn 1-x M x O 2 , LiCo 1-x M x O 2 , LiFe 1-x M x PO 4 , Li 2 Mn 1-x O 4 , wherein M is selected from Ni, Co, Mn, Al , one or more of Cr, Mg, Zr, Mo, V, Ti, B, F, 0 ⁇ a ⁇ 0.2, 0 ⁇ x ⁇ 1.
  • the negative electrode material forming the negative electrode includes natural graphite, artificial graphite, mesophase micro-carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composites, Li-Sn alloys, Li- One or more of Sn-O alloy, Sn, SnO, SnO 2 , lithiated TiO 2 -Li 4 Ti 5 O 12 with spinel structure, and Li-Al alloy.
  • MCMB mesophase micro-carbon spheres
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • Lithium cobalt oxide material LiCoO 2 , conductive agent SuperP, binder PVDF and carbon nanotubes (CNT) are uniformly mixed in a mass ratio of 96.8:2:1.2:0.05 to prepare a certain viscosity of lithium
  • the positive electrode slurry for ion battery is coated on the aluminum foil for current collector, and the coating amount is 330 g/m 2 . After drying and rolling, a positive electrode sheet is obtained, and a positive electrode sheet for lithium ion battery that meets the requirements is made.
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • Lithium cobalt oxide material LiCoO 2 , conductive agent SuperP, binder PVDF and carbon nanotubes (CNT) are uniformly mixed in a mass ratio of 96.8:2:1.2:0.05 to prepare a certain viscosity of lithium
  • the positive electrode slurry for ion battery is coated on the aluminum foil for current collector, and the coating amount is 330 g/m 2 . After drying and rolling, a positive electrode sheet is obtained, and a positive electrode sheet for lithium ion battery that meets the requirements is made.
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • Lithium cobalt oxide material LiCoO 2 , conductive agent SuperP, binder PVDF and carbon nanotubes (CNT) are uniformly mixed in a mass ratio of 96.8:2:1.2:0.05 to prepare a certain viscosity of lithium
  • the positive electrode slurry for ion battery is coated on the aluminum foil for current collector, and the coating amount is 330 g/m 2 . After drying and rolling, a positive electrode sheet is obtained, and a positive electrode sheet for lithium ion battery that meets the requirements is made.
  • the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process are made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and a capacity of 2000 mAh. After vacuum baking at 85°C for 48 hours, the above electrolyte was injected to complete the battery fabrication.
  • Example 1 It is basically the same as Example 1, except that Compound 1 in the electrolyte is replaced with Comparative Compound 1.
  • Example 2 It is basically the same as Example 1, except that Compound 1 of the electrolyte is replaced with Comparative Compound 2.
  • Example 2 It is basically the same as Example 1, except that Compound 1 of the electrolyte is deleted.
  • Example 2 It is basically the same as Example 1, except that Compound 1 in the electrolyte is replaced with DTD.
  • Example 2 It is basically the same as Example 1, except that Compound 1 in the electrolyte is replaced by LiPO 2 F 2 .
  • Example 4 It is basically the same as Example 4, except that Compound 1 in the electrolyte is replaced with Comparative Compound 1.
  • Example 4 It is basically the same as Example 4, except that Compound 1 of the electrolyte is replaced with Comparative Compound 2.
  • Example 4 It is basically the same as Example 4, except that Compound 1 of the electrolyte is replaced with Comparative Compound 3.
  • Example 4 It is basically the same as Example 4, the difference is that the compound 1 of the electrolyte is deleted.
  • Example 4 It is basically the same as Example 4, except that Compound 1 in the electrolyte is replaced with DTD.
  • Example 4 It is basically the same as Example 4, except that Compound 1 in the electrolyte is replaced by LiPO 2 F 2 .
  • Example 1 The electrolyte components and battery systems of Example 1-Example 6, Comparative Example 1-Comparative Example 12 are shown in Table 1 below. Table 1
  • the formed battery was charged to 4.2V with 0.02C constant current and constant voltage, the cut-off current was 0.01C, and then discharged to 2.75V with 1C constant current. After N cycles of such charge/discharge, the capacity retention rate after the Nth cycle was calculated to evaluate its high temperature cycling performance.
  • Nth cycle capacity retention rate (%) (Nth cycle discharge capacity/first cycle discharge capacity) ⁇ 100%.
  • the cut-off current is 0.01C, and then discharge it to 2.75V with 1C constant current, measure the initial discharge capacity of the battery, and then use 1C constant current and constant voltage to charge to 2.75V.
  • the cut-off current is 0.01C, measure the initial thickness of the battery, then store the battery at 60°C for N days, measure the thickness of the battery, and then discharge it to 2.75V with a constant current of 1C, measure the holding capacity of the battery, and then use a constant current of 1C.
  • the current is charged to 4.2V with constant voltage, the cut-off current is 0.01C, and then discharged to 2.75V with 1C constant current, and the recovery capacity is measured.
  • the formulas for calculating the capacity retention rate and capacity recovery rate are as follows:
  • Battery capacity retention rate (%) retained capacity / initial capacity ⁇ 100%;
  • Battery thickness swelling rate (%) (thickness after N days-initial thickness)/initial thickness ⁇ 100%
  • the formed battery was subjected to direct current impedance (DCR) test and internal resistance test at room temperature, and then the battery was stored at 60°C for N days, and then DCR and internal resistance test were carried out at room temperature.
  • DCR direct current impedance
  • the calculation formulas of DCR and internal resistance change rate before and after high temperature storage are as follows:
  • Battery DCR change rate (%) (DCR value after N days - DCR value before storage) / DCR value before storage ⁇ 100%
  • Example 1 shows that the technical effects of Example 1-Example 6 are obviously better than those of Comparative Example 1-Comparative Example 12, especially Example 1 and Example 4, that is, when compound 1 is used as an electrolyte additive, in There are significant advantages in reducing cell impedance change and cell swelling rate after high temperature storage. It shows that the electrolyte additive has obvious influence on the capacity retention rate and high temperature cycle of lithium ion battery.
  • the battery's normal temperature and high temperature cycle capacity retention rate and high temperature cycle capacity retention rate can be effectively improved.
  • the battery containing the electrolyte of the present invention can obtain better high-temperature cycle performance, and reduce the thickness expansion of the battery during high-temperature storage, and reduce the impedance change.

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PCT/CN2021/128543 2021-04-21 2021-11-04 取代硅基磷酸酯类化合物的新用途及电解液、锂离子电池 WO2022222420A1 (zh)

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