WO2021128002A1 - 二次电池及含有该二次电池的装置 - Google Patents

二次电池及含有该二次电池的装置 Download PDF

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Publication number
WO2021128002A1
WO2021128002A1 PCT/CN2019/127985 CN2019127985W WO2021128002A1 WO 2021128002 A1 WO2021128002 A1 WO 2021128002A1 CN 2019127985 W CN2019127985 W CN 2019127985W WO 2021128002 A1 WO2021128002 A1 WO 2021128002A1
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Prior art keywords
secondary battery
electrolyte
additive
battery according
unsubstituted
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PCT/CN2019/127985
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English (en)
French (fr)
Chinese (zh)
Inventor
吴则利
韩昌隆
付成华
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN201980098409.2A priority Critical patent/CN114207899B/zh
Priority to EP19957704.0A priority patent/EP3913717B1/en
Priority to PCT/CN2019/127985 priority patent/WO2021128002A1/zh
Priority to JP2022520094A priority patent/JP7337267B2/ja
Priority to KR1020227009816A priority patent/KR102651812B1/ko
Publication of WO2021128002A1 publication Critical patent/WO2021128002A1/zh
Priority to US17/506,142 priority patent/US12191449B2/en
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
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    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/04—Seven-membered rings not condensed with other rings
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • 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

  • This application relates to the field of battery technology, and in particular to a secondary battery and a device containing the secondary battery.
  • the use of silicon-based materials with high specific capacity as the negative electrode active material of the secondary battery can effectively increase the energy density of the secondary battery, but during the charge and discharge cycle, the reversible formation and decomposition of Li-Si alloy is accompanied by a volume change of more than 100% , Causing a sharp drop in the electrochemical performance of the secondary battery.
  • the present application provides a secondary battery and a device containing the secondary battery.
  • the secondary battery can simultaneously take into account good high temperature cycle performance and high temperature under the premise of higher energy density. Storage performance and low DC internal resistance.
  • the first aspect of the present application provides a secondary battery, the secondary battery includes a negative electrode piece and an electrolyte, the negative electrode piece includes a negative electrode current collector and is arranged on at least one surface of the negative electrode current collector And includes a negative electrode membrane of a negative electrode active material, the electrolyte includes an electrolyte salt, an organic solvent, and additives; wherein, the negative electrode active material includes a silicon-based material; the organic solvent includes ethylene carbonate (EC) and diethyl carbonate Ester (DEC), the mass proportion of the ethylene carbonate (EC) in the organic solvent ⁇ 20%, and the mass proportion of the diethyl carbonate (DEC) in the organic solvent ⁇ 20%;
  • the additive includes additive A and additive B; the additive A is selected from one or more of the compounds represented by formula 1 and formula 2;
  • n 1 is 0, 1, 2, 3, 4, or 5
  • n 2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , and R 24 are each independently selected from H, F, Cl, Br, I, substituted or unsubstituted C1-C10 chain alkane groups, substituted or Unsubstituted C1-C10 alkene group, substituted or unsubstituted C1-C10 alkynyl group, C1-C10 aliphatic group, substituted or unsubstituted C3-C9 cyclic alkane group, substituted Or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 aryl hetero group, the substituent is selected from F, Cl, Br One or more of the additives; the additive B
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 and R 49 are each independently selected from substituted or unsubstituted C1-C20 alkane groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted
  • the substituent is selected from one or more of F, Cl, and Br.
  • a second aspect of the present application provides a device including the secondary battery according to the first aspect of the present application.
  • the negative electrode active material includes silicon-based materials
  • the electrolyte contains a specific type and content of organic solvents
  • the additives include both A and B.
  • the secondary The battery can take into account good high-temperature cycle performance, high-temperature storage performance and low DC impedance at the same time.
  • the device of the present application includes the secondary battery, and thus has at least the same advantages as the secondary battery.
  • FIG. 1 is a schematic diagram of an embodiment of a secondary battery.
  • Fig. 2 is a schematic diagram of an embodiment of a battery module.
  • Fig. 3 is a schematic diagram of an embodiment of a battery pack.
  • Fig. 4 is an exploded view of Fig. 3.
  • Fig. 5 is a schematic diagram of an embodiment of a device in which a secondary battery is used as a power source.
  • the secondary battery includes a negative pole piece and an electrolyte
  • the negative pole piece includes a negative electrode current collector and a negative electrode disposed on at least one surface of the negative electrode current collector and including a negative electrode active material
  • the membrane, the electrolyte includes an electrolyte salt, an organic solvent, and additives; wherein the negative active material includes a silicon-based material; the organic solvent includes ethylene carbonate (EC) and diethyl carbonate (DEC), and The mass proportion of ethylene carbonate (EC) in the organic solvent is ⁇ 20%, and the mass proportion of diethyl carbonate (DEC) in the organic solvent is ⁇ 20%; the additives include additives A and Additive B.
  • the additive A is selected from one or more of the compounds represented by formula 1 and formula 2, wherein the value of n 1 is 0, 1, 2, 3. , 4 or 5; the value of n 2 is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are each independently selected from H, F, Cl, Br, I, substituted or unsubstituted C1-C10 chain alkene groups, substituted or unsubstituted C1-C10 chain alkene groups, substituted or unsubstituted C1-C10 chain alkene groups A substituted C1-C10 chain alkynyl group, a substituted or unsubstituted C3-C9 cyclic alkane group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C6-C20 aryl group,
  • the additive B is selected from one or more of the compounds represented by formula 3, wherein R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , and R 49 are each independently selected from substituted or unsubstituted C1 ⁇ C20 One of the alkane group, substituted or unsubstituted C2-C20 alkene group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C6-C20 aryl group, the substituent is selected from F, One or more of Cl and Br.
  • the additive A may be selected from one or more of the following compounds.
  • the additive B may be selected from tris(trimethylsilyl) phosphate, tris(triethylsilyl) phosphate, tris(vinyldimethylsilyl) One or more of silyl phosphate; more preferably, the additive B is selected from tris(trimethylsilyl) phosphate.
  • the researchers of the present application have discovered through a lot of research that when the negative electrode active material of the secondary battery includes silicon-based materials, the electrolyte simultaneously satisfies organic solvents including ethylene carbonate (EC) and diethyl carbonate (DEC).
  • organic solvents including ethylene carbonate (EC) and diethyl carbonate (DEC).
  • the mass proportion of (EC) in the organic solvent is ⁇ 20%
  • the mass proportion of diethyl carbonate (DEC) in the organic solvent is ⁇ 20%
  • the additives include additive A and additive B
  • the mass ratio of the ethylene carbonate (EC) in the organic solvent is 10%-20%.
  • the content of the ethylene carbonate (EC) within this range can better improve the high temperature cycle performance of the battery.
  • the mass ratio of the diethyl carbonate (DEC) in the organic solvent is 10%-20%.
  • the content of the diethyl carbonate (DEC) within this range can better reduce the gas production of the secondary battery and improve the high-temperature storage performance of the battery.
  • the mass ratio of the additive A in the electrolyte is ⁇ 1%.
  • the content of additive A is within the given range, it can effectively improve the high-temperature cycle performance and high-temperature storage performance of the battery; if the content of additive A is too high, the impedance of the passivation film formed on the surface of the positive and negative electrodes will increase significantly , It will also affect the high temperature storage performance of the battery. More preferably, the mass proportion of the additive A in the electrolyte is 0.1% to 0.5%.
  • the mass ratio of the additive B in the electrolyte is ⁇ 2%.
  • the content of additive B is within the given range, it can effectively reduce the impedance of the battery; if the content of additive B is too high, it will generate more LiPO 3 and (CH 3 ) 3 SiF on the surface of the negative electrode, which will affect the second High temperature storage performance of the secondary battery.
  • the mass ratio of the additive B in the electrolyte is 0.1% to 1%.
  • the organic solvent further includes ethyl methyl carbonate (EMC), and the mass ratio of the ethyl methyl carbonate (EMC) in the organic solvent is greater than 50 %; More preferably, the mass ratio of the ethyl methyl carbonate (EMC) in the organic solvent is 55%-65%.
  • EMC ethyl methyl carbonate
  • the additive further includes fluoroethylene carbonate (FEC), and the mass ratio of the fluoroethylene carbonate (FEC) in the electrolyte is ⁇ 8%; more preferably, the mass ratio of the fluoroethylene carbonate (FEC) in the electrolyte is 5%-8%.
  • FEC fluoroethylene carbonate
  • the additive further includes vinyl sulfate (DTD), 1,3-propane sultone (PS), 1,3-propenyl-sultone (PST), one or more of lithium difluorooxalate borate (LiDFOB), and lithium difluorobisoxalate phosphate (LiDFOP).
  • DTD vinyl sulfate
  • PS 1,3-propane sultone
  • PST 1,3-propenyl-sultone
  • LiDFOB lithium difluorooxalate borate
  • LiDFOP lithium difluorobisoxalate phosphate
  • the electrolyte salt includes one or more of lithium hexafluorophosphate, lithium bisfluorosulfonimide, lithium tetrafluoroborate, and lithium perchlorate; more preferably The electrolyte salt includes one or more of lithium hexafluorophosphate and lithium bisfluorosulfonimide.
  • the concentration of the electrolyte salt in the electrolyte is 1.0 mol/L-1.3 mol/L, more preferably 1.0 mol/L-1.2 mol/L .
  • the conductivity of the electrolyte at 25°C is 7mS/cm to 9.5mS/cm; more preferably, the conductivity of the electrolyte at 25°C The rate is 7mS/cm ⁇ 8.5mS/cm.
  • the viscosity of the electrolyte at 25° C. is 3 mPa.s to 4.5 mPa.s; more preferably, the viscosity of the electrolyte at 25° C. It is 3mPa.s ⁇ 3.5mPa.s.
  • the electrical conductivity of the electrolyte at 25° C. can be tested by a well-known method in the art, and the testing instrument used can be a lightning electrical conductivity device.
  • the viscosity of the electrolyte at 25° C. can be tested by a well-known method in the art, and the testing instrument used can be a viscometer.
  • the silicon-based material includes one or more of elemental silicon, silicon-carbon composites, silicon-oxygen compounds, silicon-nitrogen compounds, and silicon alloys; preferably, the silicon
  • the base material includes silicon-oxygen compound.
  • the negative electrode active material further includes a carbon material, and the carbon material includes one or more of natural graphite, artificial graphite, soft carbon, and hard carbon; Preferably, the carbon material includes one or more of natural graphite and artificial graphite.
  • the type of the negative electrode current collector is not specifically limited, and can be selected according to actual needs.
  • the negative electrode current collector can be selected from metal foils, such as copper foil.
  • the secondary battery further includes a positive pole piece, the positive pole piece including a positive electrode current collector and a positive electrode active material disposed on at least one surface of the positive electrode current collector Positive diaphragm.
  • the positive electrode active material includes one or more of lithium nickel cobalt manganese oxide compound and lithium nickel cobalt aluminum oxide.
  • Lithium nickel cobalt manganese oxide compound and lithium nickel cobalt aluminum oxide have the advantages of high specific capacity and long cycle life as the positive electrode active material of the secondary battery.
  • the electrochemistry of the battery is further improved. performance.
  • the positive electrode active material includes Li a Ni b Co c M d M'e O f A g or Li a Ni b with a coating layer provided on at least a part of the surface.
  • the coating layer of the above-mentioned positive electrode active material may be a carbon layer, an oxide layer, an inorganic salt layer, or a conductive polymer layer.
  • the cycle performance of the secondary battery can be further improved by coating and modifying the surface of the positive electrode active material.
  • the positive electrode active material may further include lithium nickel oxide (for example, lithium nickelate), lithium manganese oxide (for example, spinel-type lithium manganate, layered Structure lithium manganate, etc.), lithium iron phosphate, lithium manganese phosphate, lithium cobaltate, and one or more of its doped/coated modified compounds.
  • lithium nickel oxide for example, lithium nickelate
  • lithium manganese oxide for example, spinel-type lithium manganate, layered Structure lithium manganate, etc.
  • lithium iron phosphate lithium manganese phosphate
  • lithium cobaltate lithium cobaltate
  • the type of the positive electrode current collector is not specifically limited, and can be selected according to actual needs.
  • the positive electrode current collector may be selected from metal foils, such as aluminum foil.
  • the secondary battery further includes a separator film.
  • a separator film There is no specific limitation on the type of the isolation membrane, and it can be selected according to actual needs.
  • the isolation film can be selected from one or more of polyethylene film, polypropylene film, polyvinylidene fluoride film and their multilayer composite film.
  • the secondary battery may include an outer package for packaging the positive pole piece, the negative pole piece, and the electrolyte.
  • the positive pole piece, the negative pole piece and the separator can be laminated or wound to form an electrode assembly with a laminated structure or an electrode assembly with a wound structure, the electrode assembly is packaged in an outer package; the electrolyte is infiltrated in the electrode assembly .
  • the number of electrode assemblies in the secondary battery can be one or several, which can be adjusted according to requirements.
  • the outer packaging of the secondary battery may be a soft bag, such as a pouch-type soft bag.
  • the material of the soft bag can be plastic, for example, it can include one or more of polypropylene PP, polybutylene terephthalate PBT, polybutylene succinate PBS, and the like.
  • the outer packaging of the secondary battery may also be a hard case, such as an aluminum case.
  • Fig. 1 shows a secondary battery 5 with a square structure as an example.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • Fig. 2 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • Figures 3 and 4 show the battery pack 1 as an example. 3 and 4, the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • a plurality of battery modules 4 can be arranged in the battery box in any manner.
  • a second aspect of the present application provides a device including the secondary battery according to the first aspect of the present application.
  • the secondary battery can be used as a power source of the device, and can also be used as an energy storage unit of the device.
  • the device includes, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a secondary battery, a battery module, or a battery pack according to its usage requirements.
  • Figure 5 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, and the like.
  • the device is generally required to be thin and light, and a secondary battery can be used as a power source.
  • the secondary batteries of Examples 1-31 and Comparative Examples 1-5 were prepared according to the following methods.
  • the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2
  • the conductive agent Super P and the binder polyvinylidene fluoride are mixed in a mass ratio of 98:1:1, and then the solvent N-methylpyrrolidone is added.
  • Stir under the action of a vacuum mixer until the system becomes uniform and transparent to obtain a positive electrode slurry; coat the positive electrode slurry evenly on the positive electrode current collector aluminum foil; dry the aluminum foil at room temperature and transfer it to an oven for drying, then undergo cold pressing and slitting Obtain the positive pole piece.
  • the negative electrode active material silicon oxide and artificial graphite After mixing the negative electrode active material silicon oxide and artificial graphite at a mass ratio of 2:8, they are then mixed with the conductive agent Super P, the thickener sodium carboxymethyl cellulose (CMC-Na), and the binder styrene butadiene rubber (SBR) Mix according to the mass ratio 92:2:2:4, then add deionized water, and obtain the negative electrode slurry under the action of a vacuum mixer; evenly coat the negative electrode slurry on the copper foil of the negative current collector; dry the copper foil at room temperature After drying, it is transferred to an oven for drying, and then cold pressing and slitting are performed to obtain negative pole pieces.
  • the conductive agent Super P the thickener sodium carboxymethyl cellulose (CMC-Na), and the binder styrene butadiene rubber (SBR) Mix according to the mass ratio 92:2:2:4, then add deionized water, and obtain the negative electrode slurry under the action of
  • each organic solvent is a mass percentage calculated based on the total mass of the organic solvent
  • the content of each additive is a mass percentage calculated based on the total mass of the electrolyte.
  • a polyethylene film is used as the isolation film.
  • volume expansion rate of secondary battery after storage at 60°C for 30 days (%) [(V 2 -V 1 )/V 1 ] ⁇ 100%
  • the capacity retention rate (%) of the secondary battery after 800 cycles at 45°C (discharge capacity after 800 cycles of the secondary battery/discharge capacity at the first cycle of the secondary battery) ⁇ 100%.
  • the DC impedance DCR of the secondary battery (U 1 -U 2 )/(I 2 -I 1 ).
  • the organic solvents in the electrolyte of Examples 1-31 of the present application include ethylene carbonate (EC) and diethyl carbonate (DEC), and the ethylene carbonate (EC) and dicarbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the mass proportion of ethyl ester (DEC) in the organic solvent does not exceed 20%, and the additives include both additive A and additive B.
  • the secondary battery of the present application can simultaneously It takes into account good high-temperature cycle performance, high-temperature storage performance and low DC impedance.
  • the electrolyte in Comparative Example 2 only added additive B. Although the DC internal resistance of the battery was relatively improved, only the use of additive B resulted in a relatively high content of (CH 3 ) 3 SiF and LiPOF 3 in the secondary battery. It will deteriorate the high-temperature storage performance and high-temperature cycle performance of the battery.
  • the mass ratio of ethylene carbonate (EC) in the organic solvent in the electrolyte of Comparative Example 3 is more than 20%, which will deteriorate the high-temperature storage performance of the battery.
  • the mass ratio of diethyl carbonate (DEC) in the organic solvent is greater than 20%, which will deteriorate the high-temperature cycle performance of the battery.
  • the additive B in the electrolyte of Comparative Example 5 uses tris(trimethylsilyl) borate, and the overall performance of the battery is poor.
  • the electrolyte of the present application can enable the secondary battery to simultaneously take into account better high-temperature cycle performance, high-temperature storage performance, and lower DC impedance.

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EP19957704.0A EP3913717B1 (en) 2019-12-24 2019-12-24 Secondary battery and device comprising secondary battery
PCT/CN2019/127985 WO2021128002A1 (zh) 2019-12-24 2019-12-24 二次电池及含有该二次电池的装置
JP2022520094A JP7337267B2 (ja) 2019-12-24 2019-12-24 二次電池、及び該二次電池を備えた装置
KR1020227009816A KR102651812B1 (ko) 2019-12-24 2019-12-24 이차 배터리 및 이차 배터리를 포함하는 장치
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