WO2025043390A1 - 电解液、电化学装置和电子装置 - Google Patents

电解液、电化学装置和电子装置 Download PDF

Info

Publication number
WO2025043390A1
WO2025043390A1 PCT/CN2023/114966 CN2023114966W WO2025043390A1 WO 2025043390 A1 WO2025043390 A1 WO 2025043390A1 CN 2023114966 W CN2023114966 W CN 2023114966W WO 2025043390 A1 WO2025043390 A1 WO 2025043390A1
Authority
WO
WIPO (PCT)
Prior art keywords
additive
electrolyte
lithium
iii
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2023/114966
Other languages
English (en)
French (fr)
Inventor
徐晴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningde Amperex Technology Ltd
Original Assignee
Ningde Amperex Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningde Amperex Technology Ltd filed Critical Ningde Amperex Technology Ltd
Priority to CN202380010866.8A priority Critical patent/CN117397085A/zh
Priority to PCT/CN2023/114966 priority patent/WO2025043390A1/zh
Publication of WO2025043390A1 publication Critical patent/WO2025043390A1/zh
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/0567—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
    • H01M10/056—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
    • 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 application relates to the field of electrochemical energy storage, and in particular to electrolytes, electrochemical devices and electronic devices.
  • Electrochemical devices e.g., lithium-ion batteries
  • high energy storage density high open circuit voltage
  • low self-discharge rate low self-discharge rate
  • long cycle life long cycle life
  • good safety With the widespread use of electronic devices, research on electrochemical devices with high energy density as power sources has been actively carried out.
  • additive I is at least one additive selected from the group consisting of a compound represented by formula 1a, a compound represented by formula 1b or lithium difluorophosphate,
  • Additive II is at least one additive selected from the group consisting of lithium fluorosulfonate, bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide;
  • Additive III is at least one additive selected from the group consisting of lithium difluorooxalatoborate, lithium bis(oxalatoborate) and At least one additive in the group consisting of lithium tetrafluoroborate.
  • the electrolyte additive provided in the present application can form a uniform solid electrolyte interface (SEI) film and a positive electrode electrolyte (CEI) film, and has good low temperature performance, low impedance and thickness expansion rate.
  • SEI solid electrolyte interface
  • CEI positive electrode electrolyte
  • additive I includes a compound represented by formula 1a, and additive II includes lithium fluorosulfonate. In some embodiments, additive I includes a compound represented by formula 1a, and additive II includes bisfluorosulfonyl imide. In some embodiments, additive I includes a compound represented by formula 1a, and additive II includes bistrifluoromethanesulfonyl imide. In some embodiments, additive I includes a compound represented by formula 1a, and additive III includes lithium difluorooxalate borate. In some embodiments, additive I includes a compound represented by formula 1a, and additive III includes lithium bisoxalate borate.
  • additive I includes a compound represented by formula 1a, and additive III includes lithium tetrafluoroborate.
  • additive I includes a compound represented by formula 1b, and additive II includes lithium fluorosulfonate.
  • additive I includes a compound represented by formula 1b, and additive II includes bisfluorosulfonyl imide.
  • additive I includes a compound represented by formula 1b, and additive II includes bistrifluoromethanesulfonyl imide.
  • additive I includes a compound represented by formula 1b, and additive III includes lithium difluorooxalate borate.
  • additive I includes a compound represented by formula 1b, and additive III includes lithium bisoxalate borate. In some embodiments, additive I includes a compound represented by formula 1b, and additive III includes lithium tetrafluoroborate. In some embodiments, additive I includes lithium difluorophosphate, and additive II includes lithium fluorosulfonate. In some embodiments, additive I includes lithium difluorophosphate, and additive II includes bisfluorosulfonyl imide. In some embodiments, additive I includes lithium difluorophosphate, and additive II includes bistrifluoromethanesulfonyl imide. In some embodiments, additive I includes lithium difluorophosphate, and additive III includes lithium difluorooxalate borate.
  • additive I includes lithium difluorophosphate
  • additive III includes lithium bisoxalate borate.
  • additive I includes lithium difluorophosphate
  • additive III includes lithium tetrafluoroborate.
  • Conventional additive ingredients may not be fully decomposed under low or high temperature conditions, and electrolytes including the above additives can ensure that electrochemical devices have good low temperature performance, lower impedance and lower thickness expansion rate.
  • the mass content of additive I in the electrolyte is a, 0.01% ⁇ a ⁇ 5%. In some embodiments, the mass content of additive II in the electrolyte is b, 0.01% ⁇ b ⁇ 5%. In some embodiments, the mass content of additive III in the electrolyte is c, 0.01% ⁇ c ⁇ 5%. In some embodiments, a is 0.1%, 0.2%, 0.3%, 1%, 1.6%, 2.5%, 3%, 3.2% or a range between any two of these values. In some embodiments, b is 0.05%, 0.1%, 0.2%, 0.3%, 1%, 1.3%, 2%, or a range between any two of these values.
  • c is 0.05%, 0.1%, 0.2%, or a range between any two of these values.
  • the content of the additive in the electrolyte is within the above range, the low-temperature capacity retention rate of the electrochemical device can be significantly improved through the SEI and CEI membranes with multiple components, and the effect of reducing impedance and thickness expansion rate is better.
  • electrolyte additive I and additive II when the electrolyte includes additive I and additive II, 0.1 ⁇ a/b ⁇ 50. In some embodiments, when the electrolyte includes additive II and additive III, 0.1 ⁇ b/c ⁇ 50. In some embodiments, when the electrolyte includes additive I and additive III, 0.1 ⁇ a/c ⁇ 50. In some embodiments, when the electrolyte includes additive I and additive II, 0.1 ⁇ a/b ⁇ 40. In some embodiments, when the electrolyte includes additive II and additive III, 0.1 ⁇ b/c ⁇ 40. In some embodiments, when the electrolyte includes additive I and additive III, 0.5 ⁇ a/c ⁇ 45. Electrolyte additive components that satisfy the above content relationship can further avoid the occurrence of side reactions, and the SEI and CEI film thicknesses are moderate, thereby improving the cycle performance of the electrochemical device and reducing impedance.
  • the electrolyte further comprises an organic solvent, and the organic solvent comprises at least one of ethyl propionate or propyl propionate.
  • the mass content of ethyl propionate in the electrolyte is 20% to 60%. In some embodiments, the mass content of propyl propionate in the electrolyte is 32% to 47%.
  • the electrolyte further comprises an additive IV as shown in Formula 2,
  • X1 is CH or N
  • Ra is a substituted or unsubstituted C1 - C20 alkyl group.
  • additive I is selected from at least one additive in the group consisting of a compound represented by formula 1a, a compound represented by formula 1b, or lithium difluorophosphate,
  • additive II is selected from at least one additive in the group consisting of lithium fluorosulfonate, bisfluorosulfonyl imide and bistrifluoromethanesulfonyl imide.
  • additive III is selected from at least one additive in the group consisting of lithium difluorooxalatoborate, lithium bisoxalatoborate and lithium tetrafluoroborate.
  • the effect of forming a solid electrolyte interface (SEI) on the positive electrode surface and the negative electrode surface can be improved, thereby enhancing the interface passivation effect, thereby improving the low temperature characteristics, impedance and thickness expansion rate of the electrochemical device.
  • SEI solid electrolyte interface
  • the electrolyte includes additive I and additive II, additive I includes a compound represented by formula 1a, and additive II includes lithium fluorosulfonate. In some embodiments, the electrolyte includes additive I and additive II, additive I includes a compound represented by formula 1a, and additive II includes bisfluorosulfonyl imide. In some embodiments, the electrolyte includes additive I and additive II, additive I includes a compound represented by formula 1a, and additive II includes bistrifluoromethanesulfonyl imide. In some embodiments, the electrolyte includes additive I and additive III, additive I includes a compound represented by formula 1a, and additive III includes lithium difluorooxalatoborate.
  • the electrolyte includes additive I and additive III, Additive I includes a compound represented by Formula 1a, and additive III includes lithium bis(oxalatoborate). In some embodiments, the electrolyte includes additive I and additive III, additive I includes a compound represented by Formula 1a, and additive III includes lithium tetrafluoroborate. In some embodiments, the electrolyte includes additive I and additive II, additive I includes a compound represented by Formula 1b, and additive II includes lithium fluorosulfonate. In some embodiments, the electrolyte includes additive I and additive II, additive I includes a compound represented by Formula 1b, and additive II includes bis(trifluoromethanesulfonylimide).
  • the electrolyte includes additive I and additive III, additive I includes a compound represented by Formula 1b, and additive II includes bis(trifluoromethanesulfonylimide). In some embodiments, the electrolyte includes additive I and additive III, additive I includes a compound represented by Formula 1b, and additive III includes lithium difluorooxalatoborate. In some embodiments, the electrolyte includes additive I and additive III, additive I includes a compound represented by Formula 1b, and additive III includes lithium bis(oxalatoborate). In some embodiments, the electrolyte includes additive I and additive III, additive I includes a compound represented by Formula 1b, and additive III includes lithium tetrafluoroborate.
  • the electrolyte includes additives I and additives II, additive I includes lithium difluorophosphate, and additive II includes lithium fluorosulfonate. In some embodiments, the electrolyte includes additives I and additives II, additive I includes lithium difluorophosphate, and additive II includes bisfluorosulfonyl imide. In some embodiments, the electrolyte includes additives I and additives II, additive I includes lithium difluorophosphate, and additive II includes bistrifluoromethanesulfonyl imide. In some embodiments, the electrolyte includes additives I and additives III, additive I includes lithium difluorophosphate, and additive III includes lithium difluorooxalate borate.
  • the electrolyte includes additives I and additives III, additive I includes lithium difluorophosphate, and additive III includes lithium bisoxalate borate. In some embodiments, the electrolyte includes additives I and additives III, additive I includes lithium difluorophosphate, and additive III includes lithium tetrafluoroborate.
  • the above additive combination can enhance film formation stability, improve interface passivation effect, further reduce the occurrence of side reactions, and is beneficial to improving the low temperature characteristics, impedance and thickness expansion rate of electrochemical devices.
  • the mass content of additive I in the electrolyte is a, 0.01% ⁇ a ⁇ 5%. In some embodiments, the mass content of additive II in the electrolyte is b, 0.01% ⁇ b ⁇ 5%. In some embodiments, the mass content of additive III in the electrolyte is c, 0.01% ⁇ c ⁇ 5%.
  • the mass content of additive I in the electrolyte is a, and a is 0.1%, 0.2%, 0.3%, 1%, 1.6%, 2.5%, 3%, 3.2% or a range between any two of these values.
  • the mass content of additive II in the electrolyte is b, and b is 0.05%, 0.1%, 0.2%, 0.3%, 1%, 1.3%, 2% or a range between any two of these values.
  • the mass content of additive III in the electrolyte is c, and c is 0.05%, 0.1%, 0.2% or a range between any two of these values.
  • additives By regulating the mass content of additive I, additive II or additive III within the above range, different additives can be made to work synergistically to form SEI and CEI films with diverse and uniform components, so that the electrochemical device has better low-temperature characteristics, impedance and thickness expansion rate.
  • the electrolyte when the electrolyte includes additives I and II, 0.1 ⁇ a/b ⁇ 50. By limiting the mass content of additives I and II to the above ratio, it is beneficial to improve the low temperature characteristics, impedance and thickness expansion rate of the electrochemical device. In some embodiments, when the electrolyte includes additives II and III, 0.1 ⁇ b/c ⁇ 50. By limiting the mass content of additives II and III to the above ratio, it is beneficial to improve the low temperature characteristics, impedance and thickness expansion rate of the electrochemical device. In some embodiments, when the electrolyte includes additives I and III, 0.1 ⁇ a/c ⁇ 50.
  • additives I and III By limiting the mass content of additives I and III to the above ratio, it is beneficial to improve the low temperature characteristics, impedance and thickness expansion rate of the electrochemical device.
  • the electrolyte when the electrolyte includes additives I and II, 0.1 ⁇ a/b ⁇ 40. In some embodiments, when the electrolyte includes additives II and III, 0.1 ⁇ b/c ⁇ 40. In some embodiments, when the electrolyte includes additives I and III, 0.5 ⁇ a/c ⁇ 45.
  • the electrolyte further comprises an organic solvent, and the organic solvent comprises at least one of ethyl propionate (EP) or propyl propionate (PP).
  • the mass content of ethyl propionate in the electrolyte is 20% to 60%.
  • the mass content of propyl propionate in the electrolyte is 32% to 47%.
  • the electrolyte further comprises an additive IV as shown in Formula 2,
  • X1 is CH or N
  • Ra is a substituted or unsubstituted C1 - C20 alkyl.
  • the alkyl group can be a straight chain or branched chain alkyl group.
  • straight chain alkyl groups include substituted or unsubstituted
  • the substituted alkyl radicals include substituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl, substituted or unsubstituted decyl, substituted or unsubstituted dodecyl, etc.
  • Non-limiting examples of branched alkyl radicals include substituted or unsubstituted isopropyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted neopentyl, substituted or unsubstituted isopentyl, etc.
  • the substituted alkyl radicals may be fluorine-substituted alkyl radicals.
  • the substituted alkyl radicals may be substituted in the middle of the alkyl radicals or at the ends of the alkyl radicals. That is, the substituted alkyl radicals are alkyl radicals in which at least one hydrogen is substituted by fluorine, for example, -(CF 2 ) n -CF 3 (n is an integer from 0 to 20).
  • Formula 2 may be Formula 2a or Formula 2b as shown below:
  • the additive IV shown in Formula 2 can be decomposed to form a stable passivation film on the surface of the negative electrode, which has improved lithium ion transport performance and is stable under low-temperature and room-temperature storage, thereby suppressing gas generation and showing improved expansion performance.
  • the mass content of additive IV in the electrolyte is 0.01% to 4%.
  • the mass content of additive IV in the electrolyte is 1.2% to 1.9%. At this time, the impedance and thickness expansion rate of the electrochemical device are better.
  • the electrolyte further includes an ionizable lithium salt
  • the ionizable lithium salt includes at least one of LiPF 6 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN(C 2 F 5 SO 2 ) 2 , CF 3 SO 3 Li, LiC(CF 3 SO 2 ) 3 or LiC 4 BO 8.
  • the concentration of the ionizable lithium salt in the electrolyte is not particularly limited, and is preferably 0.5 mol/L or more, more preferably 0.8 mol/L or more, and further preferably 1.0 mol/L or more.
  • the concentration of these ionizable lithium salts is preferably 3 mol/L or less, more preferably 2 mol/L or less, further preferably 1.8 mol/L or less, and particularly preferably 1.6 mol/L or less. If the concentration of these ionizable lithium salts is too low, the conductivity of the electrolyte may be insufficient. On the other hand, if the concentration of these ionizable lithium salts is too high, the viscosity of the electrolyte may increase, thereby reducing the conductivity, which may lead to reduced performance of the electrochemical device.
  • the electrolyte further comprises at least one of fluoroether, fluoroethylene carbonate or ether nitrile.
  • the electrolyte may further comprise a non-aqueous solvent.
  • the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents or a combination thereof.
  • the carbonate compound may be a linear carbonate compound, a cyclic carbonate compound, a fluorinated carbonate compound or a combination thereof.
  • chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) and combinations thereof.
  • chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) and combinations thereof.
  • Examples of cyclic carbonate compounds are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate (VEC) or combinations thereof.
  • fluorocarbonate compounds are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate or combinations thereof.
  • FEC fluoroethylene carbonate
  • 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
  • 1,1,2-trifluoroethylene carbonate 1,1,2,2-tetrafluoroethylene carbonate
  • 1-fluoro-2-methylethylene carbonate 1-fluoro-1-methylethylene carbonate
  • 1,2-difluoro-1-methylethylene carbonate 1,1,2-trifluoro-2-methylethylene carbonate
  • trifluoromethylethylene carbonate trifluoromethylethylene carbonate
  • carboxylic acid ester compound examples include methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, methyl formate, or a combination thereof.
  • ether compound examples include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or a combination thereof.
  • organic solvents examples include dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphoric acid esters or combinations thereof.
  • the present application also provides an electrochemical device, comprising the above-mentioned electrolyte.
  • the electrochemical device further comprises a positive electrode sheet, a negative electrode sheet and a separator, wherein the positive electrode sheet and the negative electrode sheet are separated by a separator disposed therebetween.
  • the positive electrode sheet comprises a positive current collector and a positive electrode active material layer disposed on the positive current collector, the positive electrode active material layer may include a positive electrode active material, the negative electrode sheet comprises a negative current collector and a negative electrode active material layer disposed on the negative current collector, the negative electrode active material layer may include a negative electrode active material.
  • the negative electrode plate may include a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the negative electrode active material layer may be disposed on one side or both sides of the negative electrode current collector.
  • the negative electrode current collector may be at least one of a copper foil, a nickel foil, or a carbon-based current collector.
  • the thickness of the negative electrode current collector may be 1 ⁇ m to 200 ⁇ m.
  • the negative electrode active material layer may be coated only on a partial area of the negative electrode current collector.
  • the thickness of the negative electrode active material layer may be 10 ⁇ m to 500 ⁇ m. It should be understood that these are exemplary only and other suitable thicknesses may be used.
  • the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode active material includes at least one of natural graphite, artificial graphite, or a silicon-based material.
  • the silicon-based material includes at least one of silicon, a silicon-oxygen compound, a silicon-carbon compound, or a silicon alloy.
  • the negative electrode active material layer may also include a negative electrode conductor and/or a negative electrode binder.
  • the negative electrode conductor may include at least one of carbon black, acetylene black, Ketjen black, graphene, carbon nanotubes, or carbon fibers.
  • the negative electrode binder may include at least one of carboxymethyl cellulose (CMC), polyacrylic acid, polyacrylate, polyacrylate, polyvinyl pyrrolidone, polyimide, polysiloxane, or styrene-butadiene rubber. It should be understood that the materials disclosed above are only exemplary, and the negative electrode active material layer may be made of any other suitable material.
  • the mass ratio of the negative electrode active material, the negative electrode conductor, and the negative electrode binder in the negative electrode active material layer may be (80-99): (0.5-10): (0.5-10), and it should be understood that this is only exemplary and not intended to limit the present application.
  • the positive electrode plate includes a positive current collector and a positive active material layer disposed on the positive current collector.
  • the positive active material layer may be located on one or both sides of the positive current collector.
  • the positive current collector may be made of aluminum foil, and of course, other positive current collectors commonly used in the art may also be used.
  • the thickness of the positive current collector may be 1 ⁇ m to 200 ⁇ m.
  • the positive active material layer may be coated only on a partial area of the positive current collector.
  • the thickness of the positive active material layer may be 10 ⁇ m to 500 ⁇ m. It should be understood that these are exemplary only, and other suitable thicknesses may be used.
  • the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode active material may include at least one of lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or lithium nickel manganese oxide, and the positive electrode active material may be doped and/or coated.
  • the positive electrode active material layer also includes a positive electrode binder and a positive electrode conductor.
  • the positive electrode binder may include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-acrylate copolymer, styrene-butadiene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl ether, polytetrafluoroethylene or polyhexafluoropropylene.
  • the positive electrode conductor may include at least one of conductive carbon black, acetylene black, Ketjen black, graphene, carbon nanotubes or carbon fibers.
  • the mass ratio of the positive active material, positive electrode conductor and positive electrode binder in the positive electrode active material layer may be (80-98): (0.5-10): (0.5-10). It should be understood that the above is only an example, and the positive electrode active material layer may adopt any other suitable material, thickness and mass ratio.
  • the isolation film includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide or aramid.
  • polyethylene includes at least one selected from high-density polyethylene, low-density polyethylene or ultra-high molecular weight polyethylene.
  • polyethylene and polypropylene have a good effect on preventing short circuits and can improve the safety of the battery through the shutdown effect.
  • the thickness of the isolation film is in the range of about 3 ⁇ m to 500 ⁇ m.
  • the surface of the isolation membrane may further include a porous layer, which is disposed on at least one surface of the isolation membrane, and the porous layer includes at least one of inorganic particles or a binder, wherein the inorganic particles are selected from aluminum oxide ( Al2O3 ), silicon oxide ( SiO2 ), magnesium oxide (MgO), titanium oxide, (TiO 2 ), hafnium dioxide (HfO 2 ), tin oxide (SnO 2 ), cerium dioxide (CeO 2 ), nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO 2 ), yttrium oxide (Y 2 O 3 ), silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the pores of the isolation membrane have a diameter in the range of about 0.01 ⁇ m to 1 ⁇ m.
  • the binder of the porous layer is selected from at least one of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polytetrafluoroethylene or polyhexafluoropropylene.
  • the porous layer on the surface of the isolation membrane can improve the heat resistance, oxidation resistance and electrolyte wetting performance of the isolation membrane, and enhance the adhesion between the isolation membrane and the pole piece.
  • the electrochemical device is a lithium-ion battery, but the present application is not limited thereto.
  • the positive electrode sheet, the isolation membrane, and the negative electrode sheet are wound or stacked in sequence to form an electrode assembly, and then placed in a shell such as an aluminum-plastic film for packaging, and the electrolyte is injected, formed, and packaged to make a lithium-ion battery.
  • Embodiments of the present application also provide electronic devices including the above-mentioned electrochemical devices.
  • the electronic devices of the embodiments of the present application are not particularly limited, and they can be any electronic devices known in the prior art.
  • the electronic device can include, but is not limited to, a laptop computer, a pen-input computer, a mobile computer, an e-book player, a portable phone, a portable fax machine, a portable copier, a portable printer, a head-mounted stereo headset, a video recorder, an LCD TV, a portable cleaner, a portable CD player, a mini-disc, a transceiver, an electronic notepad, a calculator, a memory card, a portable recorder, a radio, a backup power supply, a motor, a car, a motorcycle, a power-assisted bicycle, a bicycle, a lighting fixture, a toy, a game console, a clock, an electric tool, a flashlight, a camera, a large household battery and a lithium
  • positive electrode sheet The positive electrode active material lithium cobalt oxide, conductive agent conductive carbon black, and binder polyvinylidene fluoride (PVDF) were mixed in a weight ratio of 96.6:1.5:1.9, and N-methylpyrrolidone (NMP) was added and stirred evenly under the action of a vacuum mixer to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry was 75wt%.
  • the positive electrode slurry was evenly coated on one side of a positive electrode current collector aluminum foil with a thickness of 10 ⁇ m, and dried at 120°C to obtain a single-sided positive electrode active material coated with a thickness of 80 ⁇ m.
  • negative electrode sheet artificial graphite, conductive carbon black, styrene-butadiene rubber (SBR), and carboxymethyl cellulose sodium (CMC) are mixed at a weight ratio of 96.5:1.5:1:1, deionized water is added, and the mixture is stirred evenly under the action of a vacuum mixer to obtain a negative electrode slurry, wherein the solid content of the negative electrode slurry is 75wt%.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose sodium
  • the negative electrode slurry is evenly coated on one side of the negative electrode current collector copper foil, and dried at 120°C to obtain a negative electrode sheet coated with a negative electrode active material layer with a thickness of 90 ⁇ m on one side, and the above steps are repeated on the other side of the negative electrode current collector copper foil to obtain a negative electrode sheet coated with a negative electrode active material layer on both sides, and then after cold pressing, cutting, and slitting, a negative electrode sheet with a specification of 476mm ⁇ 93.5mm is obtained.
  • isolation membrane A 10 ⁇ m thick polyethylene (PE) microporous membrane was selected as the isolation membrane.
  • the specific types of additives and the mass percentage content in the electrolyte are shown in Tables 1 to 4 below, and the content of the additives is the mass percentage calculated based on the total mass of the electrolyte.
  • the abbreviations of some of the additives are as follows: lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorooxalatoborate (LiDFOB), lithium bis(oxalatoborate) (LiBOB), lithium tetrafluoroborate (LiBF 4 ), lithium fluorosulfonate (LiSO 3 F), lithium bis(trifluoromethanesulfonyl imide) (LiTFSI), and bis(trifluorosulfonyl imide) (LiFSI).
  • Preparation of lithium-ion batteries stack the positive electrode sheet, separator, and negative electrode sheet in order, so that the separator is between the positive electrode sheet and the negative electrode sheet to play an isolating role, and wind them to obtain an electrode assembly. After welding the pole ears, place the electrode assembly in an outer packaging aluminum-plastic film, remove moisture at 80°C, inject the above-mentioned electrolyte, and obtain a lithium-ion battery through vacuum packaging, standing, formation, shaping, capacity testing and other processes.
  • the test method is as follows:
  • the lithium-ion battery was charged at a constant current of 0.7C to 4.48V, then charged at a constant voltage of 4.48V to a current of 82.5mAh, and then discharged at a constant current of 0.2C for 4h, so that the state of charge (SOC) of the lithium-ion battery was 20%; after the lithium-ion battery cycle was completed, the lithium-ion battery was discharged to 20% SOC according to the same charge and discharge steps as above, and the DC internal resistance (DCR) was tested respectively.
  • SOC state of charge
  • DCR DC internal resistance
  • Test method 0.1C discharge for 10s, get voltage V0; 1C discharge for 1s, get voltage V1.
  • DCR (V0-V1)/0.1C.
  • the DCR change rate of 20% SOC after 1000 cycles at 25°C is: (DCR (1000 cycles at 25°C)/DCR (initial state at 25°C)-1) ⁇ 100%.
  • Table 1 shows various parameters and evaluation results of Examples 1 to 8 and Comparative Examples 1 to 10.
  • Additive I can form a strong SEI on the positive electrode and the negative electrode, and is used to improve the low temperature characteristics, impedance and thickness expansion rate of the electrochemical device; Additive II is used to improve the low temperature characteristics of the electrolyte; Additive III is used to improve the low temperature characteristics of the electrolyte.
  • Table 2 shows various parameters and evaluation results of Examples 9 to 19 and Comparative Examples 11 to 25.
  • Examples 9 to 13 it can be seen that as a/b increases, the capacity of the lithium-ion battery first increases and then decreases, the cycle impedance growth rate first decreases and then increases, and the thickness expansion first decreases and then increases.
  • Examples 14 to 16 it can be seen that as b/c increases, the capacity of the lithium-ion battery first increases and then decreases, the cycle impedance growth rate first decreases and then increases, and the thickness expansion first decreases and then increases.
  • Examples 17 to 19 it can be seen that as a/c increases, the capacity of the lithium-ion battery first increases and then decreases, the cycle impedance growth rate first decreases and then increases, and the thickness expansion first decreases and then increases.
  • Table 3 shows various parameters and evaluation results of Examples 20 to 34.
  • an organic solvent EP or PP was additionally added.
  • the low-temperature capacity retention rate, cycle impedance growth rate and thickness expansion rate of lithium-ion batteries can be further improved by introducing organic solvents ethyl propionate or propyl propionate.
  • Table 4 shows various parameters and evaluation results of Examples 35 to 42. In Examples 35 to 42, Additive IV was additionally added.
  • the low temperature capacity retention rate, cycle impedance growth rate and thickness expansion rate of lithium-ion batteries can be further improved by introducing additive IV, because additive IV can be decomposed to form a stable passivation film on the surface of the negative electrode, which has good lithium ion transmission performance and is stable under low and high temperature conditions, thereby inhibiting the generation of gas and showing improved cycle performance and expansion performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

一种电解液、电化学装置和电子装置。电解液包括添加剂Ⅰ、添加剂Ⅱ和添加剂Ⅲ中的至少两种。添加剂Ⅰ选自由如下式1a表示的化合物、式1b表示的化合物或二氟磷酸锂组成的组中的至少一种添加剂，添加剂Ⅱ选自由氟磺酸锂、双氟磺酰亚胺和双三氟甲烷磺酰亚胺组成的组中的至少一种添加剂；添加剂Ⅲ选自由二氟草酸硼酸锂、双草酸硼酸锂和四氟硼酸锂组成的组中的至少一种添加剂。该电解液能够改善电化学装置的低温特性、阻抗和厚度膨胀率。

Description

电解液、电化学装置和电子装置 技术领域
本申请涉及电化学储能领域，具体地涉及电解液、电化学装置和电子装置。
背景技术
电化学装置(例如，锂离子电池)具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性好等优点，随着电子装置的普遍使用，已积极地进行了作为电源的具有高能量密度的电化学装置的研究。
常规非水电解质溶液因形成非均匀的固体电解质界面(SEI)膜而难以获得良好的低温输出特性和高温稳定性。而且，在电解液中包括电解质添加剂的情况下，可能发生因电解质添加剂所致的副反应，导致电化学装置的不可逆容量增加。
发明内容
本申请提供了一种电解液，电解液包括添加剂I、添加剂II和添加剂III中的至少两种。添加剂I选自由如下式1a表示的化合物、式1b表示的化合物或二氟磷酸锂组成的组中的至少一种添加剂，
添加剂II选自由氟磺酸锂、双氟磺酰亚胺和双三氟甲烷磺酰亚胺组成的组中的至少一种添加剂；添加剂III选自由二氟草酸硼酸锂、双草酸硼酸锂和 四氟硼酸锂组成的组中的至少一种添加剂。本申请提供的电解液添加剂可以形成均匀的固体电解质界面(SEI)膜和正极电解质(CEI)膜，具有良好的低温性能，较低的阻抗和厚度膨胀率。
在一些实施例中，添加剂I包括式1a表示的化合物，添加剂II包括氟磺酸锂。在一些实施例中，添加剂I包括式1a表示的化合物，添加剂II包括双氟磺酰亚胺。在一些实施例中，添加剂I包括式1a表示的化合物，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，添加剂I包括式1a表示的化合物，添加剂III包括二氟草酸硼酸锂。在一些实施例中，添加剂I包括式1a表示的化合物，添加剂III包括双草酸硼酸锂。在一些实施例中，添加剂I包括式1a表示的化合物，添加剂III包括四氟硼酸锂。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂II包括氟磺酸锂。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂II包括双氟磺酰亚胺。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂III包括二氟草酸硼酸锂。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂III包括双草酸硼酸锂。在一些实施例中，添加剂I包括式1b表示的化合物，添加剂III包括四氟硼酸锂。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂II包括氟磺酸锂。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂II包括双氟磺酰亚胺。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂III包括二氟草酸硼酸锂。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂III包括双草酸硼酸锂。在一些实施例中，添加剂I包括二氟磷酸锂，添加剂III包括四氟硼酸锂。常规的添加剂成分在低温或高温条件下可能无法充分分解，包括上述添加剂的电解液可以确保电化学装置具有良好的低温性能，较低的阻抗和较低的厚度膨胀率。
在一些实施例中，电解液中的添加剂I的质量含量为a，0.01％≤a≤5％。在一些实施例中，电解液中的添加剂II的质量含量为b，0.01％≤b≤5％。在一些实施例中，电解液中的添加剂III的质量含量为c，0.01％≤c≤5％。在一些实施例中，a为0.1％、0.2％、0.3％、1％、1.6％、2.5％、3％、3.2％或为其中任两个数值之间的范围。在一些实施例中，b为0.05％、0.1％、0.2％、0.3％、 1％、1.3％、2％或为其中任两个数值之间的范围。在一些实施例中，c为0.05％、0.1％、0.2％或为其中任两个数值之间的范围。电解液中添加剂含量在上述范围内，可通过成分多元的SEI和CEI膜显著提高电化学装置的低温容量保持率，并且降低阻抗和厚度膨胀率的效果更佳。
在一些实施例中，当电解液包括添加剂I和添加剂II时，0.1≤a/b≤50。在一些实施例中，当电解液包括添加剂II和添加剂III时，0.1≤b/c≤50。在一些实施例中，当电解液包括添加剂I和添加剂III时，0.1≤a/c≤50。在一些实施例中，当电解液包括添加剂I和添加剂II时，0.1≤a/b≤40。在一些实施例中，当电解液包括添加剂II和添加剂III时，0.1≤b/c≤40。在一些实施例中，当电解液包括添加剂I和添加剂III时，0.5≤a/c≤45。满足上述含量关系的电解液添加剂成分可以进一步避免副反应的发生，且SEI和CEI膜厚度适中，从而提高电化学装置的循环性能，降低阻抗。
在一些实施例中，电解液还包括有机溶剂，有机溶剂包括丙酸乙酯或丙酸丙酯中的至少一种。在一些实施例中，电解液中的丙酸乙酯的质量含量为20％至60％。在一些实施例中，电解液中的丙酸丙酯的质量含量为32％至47％。满足上述条件的电解液可以有效抑制过渡金属的离解和溶出，并且降低电化学装置在不同温度下的性能波动。
在一些实施例中，电解液还包括式2所示的添加剂IV，
其中，X1为CH或N，Ra为取代或未取代的C1-C20烷基。
在一些实施例中，电解液中的添加剂IV的质量含量为0.01％至4％。在一些实施例中，电解液中的添加剂IV的质量含量为1.2％至1.9％。添加剂IV具有良好的低温和高温稳定性，带来正面作用的同时不增加电解液的粘度，能够进一步降低阻抗。在一些实施例中，电解液还包括LiPF6、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、CF3SO3Li、LiC(CF3SO2)3或LiC4BO8中的至少一种。
本申请还提供了一种电化学装置，包括上述电解液。
本申请还提供了一种电子装置，包括上述的电化学装置。
本申请提供的电解液能够改善在正极表面和负极表面上形成固体电解质界面(SEI)的效果，进而增强界面钝化作用，并且在低温和高温条件下都具有较好的稳定性，可改善电化学装置的低温特性、阻抗和厚度膨胀率。
具体实施方式
下面的实施例可以使本领域技术人员更全面地理解本申请，但不以任何方式限制本申请。
本申请提供了一种电解液，电解液包括添加剂I、添加剂II和添加剂III中的至少两种。在一些实施例中，添加剂I选自由如下式1a表示的化合物、式1b表示的化合物或二氟磷酸锂组成的组中的至少一种添加剂，
在一些实施例中，添加剂II选自由氟磺酸锂、双氟磺酰亚胺和双三氟甲烷磺酰亚胺组成的组中的至少一种添加剂。在一些实施例中，添加剂III选自由二氟草酸硼酸锂、双草酸硼酸锂和四氟硼酸锂组成的组中的至少一种添加剂。通过在电解液中采用添加剂I、添加剂II和添加剂III中的至少两种，能够改善在正极表面和负极表面上形成固体电解质界面(SEI)的效果，进而提升界面钝化效果，因而可改善电化学装置的低温特性、阻抗和厚度膨胀率。
在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1a表示的化合物，添加剂II包括氟磺酸锂。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1a表示的化合物，添加剂II包括双氟磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1a表示的化合物，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括式1a表示的化合物，添加剂III包括二氟草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III， 添加剂I包括式1a表示的化合物，添加剂III包括双草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括式1a表示的化合物，添加剂III包括四氟硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1b表示的化合物，添加剂II包括氟磺酸锂。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1b表示的化合物，添加剂II包括双氟磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括式1b表示的化合物，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括式1b表示的化合物，添加剂III包括二氟草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括式1b表示的化合物，添加剂III包括双草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括式1b表示的化合物，添加剂III包括四氟硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括二氟磷酸锂，添加剂II包括氟磺酸锂。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括二氟磷酸锂，添加剂II包括双氟磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂II，添加剂I包括二氟磷酸锂，添加剂II包括双三氟甲烷磺酰亚胺。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括二氟磷酸锂，添加剂III包括二氟草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括二氟磷酸锂，添加剂III包括双草酸硼酸锂。在一些实施例中，电解液包括添加剂I和添加剂III，添加剂I包括二氟磷酸锂，添加剂III包括四氟硼酸锂。以上添加剂组合能够增强成膜稳定性，提升界面钝化效果，进一步减少副反应的发生，有利于改善电化学装置的低温特性、阻抗和厚度膨胀率。
在一些实施例中，电解液中的添加剂I的质量含量为a，0.01％≤a≤5％。在一些实施例中，电解液中的添加剂II的质量含量为b，0.01％≤b≤5％。在一些实施例中，电解液中的添加剂III的质量含量为c，0.01％≤c≤5％。通过控制添加剂I、添加剂II、添加剂III的质量含量在上述范围内，能够提高电化学装置的稳定性，改善电化学装置的低温特性、阻抗和厚度膨胀率。
在一些实施例中，电解液中的添加剂I的质量含量为a，a为0.1％、0.2％、0.3％、1％、1.6％、2.5％、3％、3.2％或为其中任两个数值之间的范围。在一 些实施例中，电解液中的添加剂II的质量含量为b，b为0.05％、0.1％、0.2％、0.3％、1％、1.3％、2％或为其中任两个数值之间的范围。在一些实施例中，电解液中的添加剂III的质量含量为c，c为0.05％、0.1％、0.2％或为其中任两个数值之间的范围。通过调控添加剂I、添加剂II或添加剂III的质量含量在上述范围内，可以使得不同添加剂协同作用，形成成分多元且均匀的SEI和CEI膜，因此电化学装置具有更优的低温特性、阻抗和厚度膨胀率。
在一些实施例中，当电解液包括添加剂I和添加剂II时，0.1≤a/b≤50。通过将添加剂I和添加剂II的质量含量限定为上述比例，有利于改善电化学装置的低温特性、阻抗和厚度膨胀率。在一些实施例中，当电解液包括添加剂II和添加剂III时，0.1≤b/c≤50。通过将添加剂II和添加剂III的质量含量限定为上述比例，有利于改善电化学装置的低温特性、阻抗和厚度膨胀率。在一些实施例中，当电解液包括添加剂I和添加剂III时，0.1≤a/c≤50。通过将添加剂I和添加剂III的质量含量限定为上述比例，有利于改善电化学装置的低温特性、阻抗和厚度膨胀率。在一些实施例中，当电解液包括添加剂I和添加剂II时，0.1≤a/b≤40。在一些实施例中，当电解液包括添加剂II和添加剂III时，0.1≤b/c≤40。在一些实施例中，当电解液包括添加剂I和添加剂III时，0.5≤a/c≤45。通过将添加剂I、添加剂II和添加剂III的质量含量限定为上述比例，电化学装置的低温特性、阻抗和厚度膨胀率更优。
在一些实施例中，电解液还包括有机溶剂，有机溶剂包括丙酸乙酯(EP)或丙酸丙酯(PP)中的至少一种。在一些实施例中，电解液中的丙酸乙酯的质量含量为20％至60％。在一些实施例中，电解液中的丙酸丙酯的质量含量为32％至47％。通过电解液中的丙酸乙酯或丙酸丙酯的质量含量限定在上述范围内，能够提高电化学装置的低温特性、阻抗和厚度膨胀率。
在一些实施例中，电解液还包括式2所示的添加剂IV，
其中，X1为CH或N，Ra为取代或未取代的C1-C20烷基。在一些实施例中，烷基可以为直链或支链烷基。直链烷基的非限制性例子包括取代的或未 取代的甲基、取代的或未取代的乙基、取代的或未取代的丙基、取代的或未取代的丁基、取代的或未取代的戊基、取代的或未取代的己基、取代的或未取代的庚基、取代的或未取代的辛基、取代的或未取代的壬基、取代的或未取代的癸基、取代的或未取代的十二烷基等。支链烷基的非限制性例子包括取代的或未取代的异丙基、取代的或未取代的仲丁基、取代的或未取代的异丁基、取代的或未取代的新戊基、取代的或未取代的异戊基等。另外，取代的烷基可为氟取代的烷基。取代的烷基可在烷基的中间取代或在烷基的末端取代。也就是说，取代的烷基为其中至少一个氢被氟取代的烷基，例如，-(CF2)n-CF3(n为0至20的整数)。
在一些实施例中，式2的具体示例可以为如下所示的式2a或式2b：
式2所示的添加剂IV可以分解而在负极的表面上形成稳定的钝化膜，该钝化膜具有改善的锂离子传输性能，并且在低温和常温存储下是稳定的，从而抑制气体的产生，并表现出改善的膨胀性能。
在一些实施例中，电解液中的添加剂IV的质量含量为0.01％至4％。通过调控添加剂IV的质量含量在上述范围内，能够明显提高电化学装置的低温特性和阻抗，并且减小电化学装置的厚度膨胀率。在一些实施例中，电解液中的添加剂IV的质量含量为1.2％至1.9％。此时，电化学装置的阻抗和厚度膨胀率更优。
在一些实施例中，电解液还包括可离子化的锂盐，可离子化的锂盐包括LiPF6、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、CF3SO3Li、LiC(CF3SO2)3或LiC4BO8中的至少一种。电解液中的可离子化的锂盐的浓度并无特殊限制，优选为0.5摩尔/升以上、更优选为0.8摩尔/升以上、进一步优选为1.0摩尔/升以上。另外，优选为3摩尔/升以下、更优选为2摩尔/升以下、进一步优选为1.8摩尔/升以下、特别优选为1.6摩尔/升以下。如果这些可离子化的锂盐的浓度过低，则可能导致电解液的电导率不足，另一方面，如果这些可离子化的锂盐的浓度过高，则可能导致电解液的粘度上升，因而电导率下降，可能导致电化学装置的性能降低。
在一些实施例中，电解液还包括氟醚、氟代碳酸乙烯酯或醚腈中至少一种。在一些实施例中，电解液还可以包括非水溶剂。非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
链状碳酸酯化合物的实例为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。
羧酸酯化合物的实例为乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯、甲酸甲酯或者其组合。
醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。
其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯或者其组合。
本申请还提供了一种电化学装置，包括上述电解液。在一些实施例中，电化学装置还包括正极极片、负极极片和隔离膜，其中正极极片和负极极片由设置在它们之间的隔离膜间隔开。在一些实施例中，正极极片包括正极集流体和设置在正极集流体上的正极活性材料层，正极活性材料层可以包括正极活性材料，负极极片包括负极集流体和设置在负极集流体上的负极活性材料层，负极活性材料层可以包括负极活性材料。
在一些实施例中，负极极片可以包括负极集流体和设置在负极集流体上的负极活性材料层。负极活性材料层可以设置在负极集流体的一侧或两侧上。在一些实施例中，负极集流体可以采用铜箔、镍箔或碳基集流体中的至少一种。在一些实施例中，负极集流体的厚度可以为1μm至200μm。在一些实施例中，负极活性材料层可以仅涂覆在负极集流体的部分区域上。在一些实施例中，负极活性材料层的厚度可以为10μm至500μm。应该理解，这些仅是示例性的，可以采用其他合适的厚度。
在一些实施例中，如上所述，负极活性材料层包括负极活性材料。在一些实施例中，负极活性材料包括天然石墨、人造石墨或硅基材料中的至少一种。在一些实施例中，硅基材料包括硅、硅氧化合物、硅碳化合物或硅合金中的至少一种。
在一些实施例中，负极活性材料层中还可以包括负极导电剂和/或负极粘结剂。负极导电剂可以包括炭黑、乙炔黑、科琴黑、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中，负极粘结剂可以包括羧甲基纤维素(CMC)、聚丙烯酸、聚丙烯酸盐、聚丙烯酸酯、聚乙烯基吡咯烷酮、聚酰亚胺、聚硅氧烷或丁苯橡胶中的至少一种。应该理解，以上公开的材料仅是示例性，负极活性材料层可以采用任何其他合适的材料。在一些实施例中，负极活性材料层中的负极活性材料、负极导电剂和负极粘结剂的质量比可以为(80～99):(0.5～10):(0.5～10)，应该理解，这仅是示例性的，而不用于限制本申请。
在一些实施例中，正极极片包括正极集流体和设置在正极集流体上的正极活性材料层。正极活性材料层可以位于正极集流体一侧或两侧上。在一些实施例中，正极集流体可以采用铝箔，当然，也可以采用本领域常用的其他正极集流体。在一些实施例中，正极集流体的厚度可以为1μm至200μm。在一些实施例中，正极活性材料层可以仅涂覆在正极集流体的部分区域上。在一些实施例中，正极活性材料层的厚度可以为10μm至500μm。应该理解，这些仅是示例性的，可以采用其他合适的厚度。
在一些实施例中，如上所述，正极活性材料层包括正极活性材料。在一些实施例中，正极活性材料可以包括钴酸锂、锰酸锂、磷酸铁锂、磷酸锰铁锂、镍钴锰酸锂、镍钴铝酸锂或镍锰酸锂中的至少一种，上述正极活性材料可以经过掺杂和/或包覆处理。
在一些实施例中，正极活性材料层还包括正极粘结剂和正极导电剂。在一些实施例中，正极粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-丁二烯共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚醋酸乙烯酯、聚乙烯呲咯烷酮、聚乙烯醚、聚四氟乙烯或聚六氟丙烯中的至少一种。在一些实施例中，正极导电剂可以包括导电炭黑、乙炔黑、科琴黑、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中，正极活性材料层中的正极活性材料、正极导电剂和正极粘结剂的质量比可以为(80～98):(0.5～10):(0.5～10)。应该理解，以上所述仅是示例，正极活性材料层可以采用任何其他合适的材料、厚度和质量比。
在一些实施例中，隔离膜包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电池的安全性。在一些实施例中，隔离膜的厚度在约3μm至500μm的范围内。
在一些实施例中，隔离膜表面还可以包括多孔层，多孔层设置在隔离膜的至少一个表面上，多孔层包括无机颗粒或粘结剂中的至少一种，无机颗粒选自氧化铝(Al2O3)、氧化硅(SiO2)、氧化镁(MgO)、氧化钛 (TiO2)、二氧化铪(HfO2)、氧化锡(SnO2)、二氧化铈(CeO2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO2)、氧化钇(Y2O3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中，隔离膜的孔具有在约0.01μm至1μm的范围的直径。多孔层的粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚四氟乙烯或聚六氟丙烯中的至少一种。隔离膜表面的多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解质浸润性能，增强隔离膜与极片之间的粘接性。
在一些实施例中，电化学装置为锂离子电池，但是本申请不限于此。
在本申请的一些实施例中，以锂离子电池为例，将正极极片、隔离膜、负极极片按顺序卷绕或堆叠成电极组件，之后装入壳体例如铝塑膜中进行封装，注入电解液，化成、封装，即制成锂离子电池。
本申请的实施例还提供了包括上述电化学装置的电子装置。本申请实施例的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
下面列举了一些具体实施例和对比例以更好地对本申请进行说明，其中，采用锂离子电池作为示例。
锂离子电池的制备
正极极片的制备：将正极活性材料钴酸锂、导电剂导电炭黑、粘结剂聚偏氟二乙烯(PVDF)按照重量比96.6：1.5：1.9进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌均匀，获得正极浆料，其中正极浆料的固含量为75wt％。将正极浆料均匀涂覆于厚度为10μm的正极集流体铝箔的一侧表面上，在120℃下烘干，得到单面涂覆有厚度为80μm的正极活性 材料层的正极极片，在正极集流体铝箔的另一侧表面重复上述步骤，得到双面涂覆有正极活性材料层的正极极片，然后经过冷压、裁片、分切后，得到规格为470mm×92mm的正极极片。
负极极片的制备：将负极活性材料人造石墨、导电剂导电炭黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC)按重量比96.5：1.5：1：1进行混合，加入去离子水，在真空搅拌机作用下搅拌均匀，获得负极浆料，其中负极浆料的固含量为75wt％。将负极浆料均匀涂覆于负极集流体铜箔的一侧表面上，在120℃下烘干，得到单面涂覆有厚度为90μm的负极活性材料层的负极极片，在负极集流体铜箔的另一侧表面重复上述步骤，得到双面涂覆有负极活性材料层的负极极片，然后经过冷压、裁片、分切后，得到规格为476mm×93.5mm的负极极片。
隔离膜的制备：选用10μm厚的聚乙烯(PE)微多孔膜作为隔离膜。
电解液的制备：在含水量小于10ppm的氩气气氛手套箱中，将碳酸乙烯酯(简写为EC)、碳酸丙烯酯(简写为PC)、碳酸二乙酯(简写为DEC)按照质量比1:1:1混合得到基础溶剂，然后向上述基础溶剂中加入锂盐LiPF6及添加剂，混合均匀后得到电解液，其中，基于电解液的质量，LiPF6的质量百分含量为12.5％。各个实施例的区别在于电解液中所用到的添加剂种类和/或含量不同，添加剂的具体种类以及在电解液中的质量百分含量如下表1至4所示，添加剂的含量为基于电解液的总质量计算得到的质量百分数。其中一些添加剂的简写的对应关系如下：二氟磷酸锂(LiPO2F2)、二氟草酸硼酸锂(LiDFOB)、双草酸硼酸锂(LiBOB)、四氟硼酸锂(LiBF4)、氟磺酸锂(LiSO3F)、双三氟甲烷磺酰亚胺锂(LiTFSI)、双氟磺酰亚胺(LiFSI)。
锂离子电池的制备：将正极极片、隔离膜、负极极片按顺序依次叠好，使隔离膜处于正极极片和负极极片之间起到隔离的作用，并卷绕得到电极组件，焊接极耳后将电极组件置于外包装铝塑膜中，在80℃下脱去水分后，注入上述电解液，经过真空封装、静置、化成、整形、容量测试等工序，得到锂离子电池。
测试方法如下：
(1)-10℃低温循环测试：
将锂离子电池置于-10℃恒温箱中，静置30分钟，使锂离子电池达到恒温。将达到恒温的锂离子电池在-10℃下以0.2C恒流充电至4.5V，4.5V下恒压充电至0.05C，静置5分钟，再以0.2C恒流放电至3.0V，静置5分钟，测试初始容量C11；然后再以0.5C恒流充电至4.2V，以4.2V恒压充电至电流为0.3C；再以0.3C恒流充电至4.25V，然后以4.5V恒压充电至电流为0.05C；放置5分钟；接着以0.2C恒流放电至3.0V，静置5分钟；此为一个充放电循环。如此充电/放电，测试锂离子电池循环200圈后的放电容量C12，计算锂离子电池循环200次后的容量保持率。
-10℃循环200圈后的容量保持率＝C12/C11×100％。
(2)直流阻抗(DCR)的测试：
在25℃下，将锂离子电池以0.7C恒流充电至4.48V，再以4.48V恒压充电至电流为82.5mAh，然后以0.2C恒流放电4h，使得锂离子电池荷电状态(SOC)为20％；锂离子电池循环结束后按照上述相同的充放电步骤，将锂离子电池放电至20％SOC，分别测试直流内阻(DCR)。
测试方法：0.1C放电10s，获得电压V0；1C放电1s，获得电压V1。DCR＝(V0-V1)/0.1C。
25℃循环1000圈20％SOC的DCR变化率：(DCR(25℃1000圈)/DCR(25℃初始状态)-1)×100％。
(3)存储厚度膨胀率测试：
将锂离子电池置于25℃恒温箱中，静置30min，使锂离子电池达到恒温。将达到恒温的锂离子电池以0.7C恒流充电至电压为4.48V，然后以4.48V恒压充电至电流为82.5mA，测试锂离子电池的厚度并记为T0；放置到85℃烘箱当中8h，冷却1h，测试锂离子电池的厚度为T1，并实时监控锂离子电池在烘箱中的厚度。锂离子电池85℃存储6h后的厚度膨胀率＝(T1-T0)/T0×100％。
表1示出了实施例1至8和对比例1至10的各项参数和评估结果。
表1


其中，“-”表示未添加该物质。
添加剂I可以在正极和负极上形成牢固的SEI，用于改善电化学装置的低温特性、阻抗和厚度膨胀率；添加剂II用于改善电解液的低温特性；添加剂III用于改善电解液的低温特性。通过比较实施例1至8与对比例1至10可知，相对于未添加添加剂I、添加剂II和添加剂III或仅添加添加剂I、添加剂II和添加剂III中的一种，在电解液中添加添加剂I、添加剂II和添加剂III中的至少两种，可以明显地改善锂离子电池的低温循环容量保持率、循环阻抗增长率和厚度膨胀率。
表2示出了实施例9至19和对比例11至25的各项参数和评估结果。
表2


其中，“-”表示未添加该物质。
通过比较对比例11至16可知，随着电解液中的添加剂I的质量含量的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先减小后增大，厚度膨胀率先减小后增大。通过比较对比例17至21可知，随着电解液中的添加剂II的质量含量的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先减小后增大，厚度膨胀率先减小后增大。通过比较对比例22至25可知，随着电解液中的添加剂III的质量含量的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先增大后减小然后再增大，厚度膨胀率先增大后减小然后再增大。
通过比较实施例9至13可知，随着a/b的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先减小后增大，厚度膨胀率先减小后增大。通过比较实施例14至16可知，随着b/c的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先减小后增大，厚度膨胀率先减小后增大。通过比较实施例17至19可知，随着a/c的增大，锂离子电池的容量保持率先增大后减小，循环阻抗增长率先减小后增大，厚度膨胀率先减小后增大。
表3示出了实施例20至34的各项参数和评估结果。实施例20至34中额外添加了有机溶剂EP或PP。
表3

其中，“-”表示未添加该物质。
通过引入有机溶剂丙酸乙酯或丙酸丙酯可以进一步改善锂离子电池的低温容量保持率、循环阻抗增长率和厚度膨胀率。
表4示出了实施例35至42的各项参数和评估结果。实施例35至42中额外添加了添加剂IV。
表4

其中，“-”表示未添加该物质。
通过引入添加剂IV可以进一步改善锂离子电池的低温容量保持率、循环阻抗增长率和厚度膨胀率。因为添加剂IV可以分解而在负极的表面上形成稳定的钝化膜，该钝化膜具有较好的的锂离子传输性能，并且在低温和高温条件下是稳定的，从而抑制气体的产生，并表现出改善的循环性能和膨胀性能。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解，本申请中所涉及的公开范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (15)

  1. 一种电解液，其特征在于，所述电解液包括添加剂I、添加剂II和添加剂III中的至少两种：
    所述添加剂I选自由如下式1a表示的化合物、式1b表示的化合物或二氟磷酸锂组成的组中的至少一种添加剂，
    所述添加剂II选自由氟磺酸锂、双氟磺酰亚胺和双三氟甲烷磺酰亚胺组成的组中的至少一种添加剂；
    所述添加剂III选自由二氟草酸硼酸锂、双草酸硼酸锂和四氟硼酸锂组成的组中的至少一种添加剂。
  2. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (1)所述添加剂I包括式1a表示的化合物，所述添加剂II包括氟磺酸锂；
    (2)所述添加剂I包括式1a表示的化合物，所述添加剂II包括双氟磺酰亚胺；
    (3)所述添加剂I包括式1a表示的化合物，所述添加剂II包括双三氟甲烷磺酰亚胺。
  3. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (4)所述添加剂I包括式1a表示的化合物，所述添加剂III包括二氟草酸硼酸锂；
    (5)所述添加剂I包括式1a表示的化合物，所述添加剂III包括双草酸硼酸锂；
    (6)所述添加剂I包括式1a表示的化合物，所述添加剂III包括四氟硼酸锂。
  4. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (7)所述添加剂I包括式1b表示的化合物，所述添加剂II包括氟磺酸锂；
    (8)所述添加剂I包括式1b表示的化合物，所述添加剂II包括双氟磺酰亚胺；
    (9)所述添加剂I包括式1b表示的化合物，所述添加剂II包括双三氟甲烷磺酰亚胺。
  5. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (10)所述添加剂I包括式1b表示的化合物，所述添加剂III包括二氟草酸硼酸锂；
    (11)所述添加剂I包括式1b表示的化合物，所述添加剂III包括双草酸硼酸锂；
    (12)所述添加剂I包括式1b表示的化合物，所述添加剂III包括四氟硼酸锂。
  6. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (13)所述添加剂I包括二氟磷酸锂，所述添加剂II包括氟磺酸锂；
    (14)所述添加剂I包括二氟磷酸锂，所述添加剂II包括双氟磺酰亚胺；
    (15)所述添加剂I包括二氟磷酸锂，所述添加剂II包括双三氟甲烷磺酰亚胺。
  7. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (16)所述添加剂I包括二氟磷酸锂，所述添加剂III包括二氟草酸硼酸锂；
    (17)所述添加剂I包括二氟磷酸锂，所述添加剂III包括双草酸硼酸锂；
    (18)所述添加剂I包括二氟磷酸锂，所述添加剂III包括四氟硼酸锂。
  8. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (1)所述电解液中的所述添加剂I的质量含量为a，0.01％≤a≤5％；
    (2)所述电解液中的所述添加剂II的质量含量为b，0.01％≤b≤5％；
    (3)所述电解液中的所述添加剂III的质量含量为c，0.01％≤c≤5％。
  9. 根据权利要求8所述的电解液，其特征在于，满足以下至少一项：
    (1)a为0.1％、0.2％、0.3％、1％、1.6％、2.5％、3％、3.2％或为其中任两个数值之间的范围；
    (2)b为0.05％、0.1％、0.2％、0.3％、1％、1.3％、2％或为其中任两个数值之间的范围；
    (3)c为0.05％、0.1％、0.2％或为其中任两个数值之间的范围。
  10. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (1)当所述电解液包括所述添加剂I和所述添加剂II时，0.1≤a/b≤50；
    (2)当所述电解液包括所述添加剂II和所述添加剂III时，0.1≤b/c≤50；
    (3)当所述电解液包括所述添加剂I和所述添加剂III时，0.1≤a/c≤50。
  11. 根据权利要求1所述的电解液，其特征在于，满足以下至少一项：
    (1)当所述电解液包括所述添加剂I和所述添加剂II时，0.1≤a/b≤40；
    (2)当所述电解液包括所述添加剂II和所述添加剂III时，0.1≤b/c≤40；
    (3)当所述电解液包括所述添加剂I和所述添加剂III时，0.5≤a/c≤45。
  12. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括有机溶剂，所述有机溶剂包括丙酸乙酯或丙酸丙酯中的至少一种，其中，所述电解液中的丙酸乙酯的质量含量为20％至60％，所述电解液中的丙酸丙酯的质量含量为32％至47％。
  13. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括式2所示的添加剂IV，
    其中，X1为CH或N，Ra为取代或未取代的C1-C20烷基；
    所述电解液中的所述添加剂IV的质量含量为0.01％至4％，优选1.2％至1.9％。
  14. 一种电化学装置，包括根据权利要求1至13中任一项所述的电解液。
  15. 一种电子装置，包括根据权利要求14所述的电化学装置。
PCT/CN2023/114966 2023-08-25 2023-08-25 电解液、电化学装置和电子装置 Pending WO2025043390A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202380010866.8A CN117397085A (zh) 2023-08-25 2023-08-25 电解液、电化学装置和电子装置
PCT/CN2023/114966 WO2025043390A1 (zh) 2023-08-25 2023-08-25 电解液、电化学装置和电子装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/114966 WO2025043390A1 (zh) 2023-08-25 2023-08-25 电解液、电化学装置和电子装置

Publications (1)

Publication Number Publication Date
WO2025043390A1 true WO2025043390A1 (zh) 2025-03-06

Family

ID=89463566

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/114966 Pending WO2025043390A1 (zh) 2023-08-25 2023-08-25 电解液、电化学装置和电子装置

Country Status (2)

Country Link
CN (1) CN117397085A (zh)
WO (1) WO2025043390A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099171A (zh) * 2016-07-13 2016-11-09 东莞市凯欣电池材料有限公司 一种锂离子动力电池电解液及锂离子动力电池
CN109891654A (zh) * 2017-07-03 2019-06-14 株式会社Lg化学 电解质添加剂和包括该添加剂的用于锂二次电池的非水电解质溶液
CN110350244A (zh) * 2018-04-05 2019-10-18 三星Sdi株式会社 用于可再充电的锂电池的电解质和包括其的可再充电的锂电池
US20210328266A1 (en) * 2018-12-17 2021-10-21 Lg Energy Solution, Ltd. Electrolyte Solution For Lithium Secondary Battery and Lithium Secondary Battery Including the Same
CN113809399A (zh) * 2021-09-16 2021-12-17 宁德新能源科技有限公司 一种电解液、包含该电解液的电化学装置和电子装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106099171A (zh) * 2016-07-13 2016-11-09 东莞市凯欣电池材料有限公司 一种锂离子动力电池电解液及锂离子动力电池
CN109891654A (zh) * 2017-07-03 2019-06-14 株式会社Lg化学 电解质添加剂和包括该添加剂的用于锂二次电池的非水电解质溶液
CN110350244A (zh) * 2018-04-05 2019-10-18 三星Sdi株式会社 用于可再充电的锂电池的电解质和包括其的可再充电的锂电池
US20210328266A1 (en) * 2018-12-17 2021-10-21 Lg Energy Solution, Ltd. Electrolyte Solution For Lithium Secondary Battery and Lithium Secondary Battery Including the Same
CN113809399A (zh) * 2021-09-16 2021-12-17 宁德新能源科技有限公司 一种电解液、包含该电解液的电化学装置和电子装置

Also Published As

Publication number Publication date
CN117397085A (zh) 2024-01-12

Similar Documents

Publication Publication Date Title
CN115799466B (zh) 电化学装置和电子装置
CN109728340B (zh) 锂离子电池
KR102612376B1 (ko) 전해액, 전기화학장치 및 전자장치
CN113841281B (zh) 电解液、电化学装置和电子装置
CN111048831A (zh) 用于二次电池的电解液以及包含电解液的锂二次电池
WO2022052019A1 (zh) 电化学装置和电子装置
WO2022205661A1 (zh) 电化学装置和电子装置
WO2025001892A1 (zh) 一种电极组件、电化学装置及用电装置
WO2023236198A1 (zh) 电解液和电化学装置
WO2025180096A1 (zh) 一种二次电池以及电子装置
CN115548442A (zh) 一种锂离子电池电解液及其锂离子电池
WO2025152661A1 (zh) 二次电池及电子装置
WO2025200762A1 (zh) 一种二次电池以及电子装置
WO2025118888A1 (zh) 电解液添加剂、电解液和电池
WO2025194630A1 (zh) 一种电解液及其应用
CN115298875B (zh) 电解液、电化学装置及电子装置
WO2022133641A1 (zh) 电解液、电化学装置和电子装置
CN113078359B (zh) 电解液、电化学装置和电子装置
CN114667624B (zh) 电解液、电化学装置和电子装置
CN113892207B (zh) 电解液、电化学装置及电子装置
CN112670580B (zh) 电解液、电化学装置及电子装置
WO2025043390A1 (zh) 电解液、电化学装置和电子装置
CN113659200B (zh) 一种改善锂电池高温性能的电解液添加剂、电解液及电化学装置
WO2026067429A1 (zh) 电解液添加剂、电解液和锂离子电池
CN117239241A (zh) 一种电解液及锂离子电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23949985

Country of ref document: EP

Kind code of ref document: A1

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112026004418

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2023949985

Country of ref document: EP