WO2022198402A1 - Electrolyte, electrochemical device and electronic device - Google Patents

Electrolyte, electrochemical device and electronic device Download PDF

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Publication number
WO2022198402A1
WO2022198402A1 PCT/CN2021/082145 CN2021082145W WO2022198402A1 WO 2022198402 A1 WO2022198402 A1 WO 2022198402A1 CN 2021082145 W CN2021082145 W CN 2021082145W WO 2022198402 A1 WO2022198402 A1 WO 2022198402A1
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Prior art keywords
substituted
unsubstituted
electrolyte
formula
compound
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PCT/CN2021/082145
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French (fr)
Chinese (zh)
Inventor
许艳艳
徐春瑞
韩翔龙
唐超
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宁德新能源科技有限公司
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Priority to PCT/CN2021/082145 priority Critical patent/WO2022198402A1/en
Priority to CN202180006145.0A priority patent/CN114667624A/en
Publication of WO2022198402A1 publication Critical patent/WO2022198402A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to the field of electrochemistry, and in particular, to an electrolyte, an electrochemical device, and an electronic device.
  • the electrolyte is an important part of electrochemical devices (such as lithium-ion batteries), and plays a crucial role in the specific capacity, charge-discharge efficiency, cycle stability, rate performance, operating temperature range, and safety performance of electrochemical devices. .
  • electrochemical devices such as lithium-ion batteries
  • the purpose of the present application is to provide an electrolyte, an electrochemical device and an electronic device to solve the problems existing in the prior art.
  • An electrolyte solution is proposed in the embodiments of the present application, comprising: a compound of formula I;
  • R 1 is selected from substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted Substituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted C3 to C20 alicyclic hydrocarbyl, substituted or unsubstituted Any one of the C 2 to C 20 heterocyclyl groups, wherein, when substituted, the substituent includes halogen;
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 20
  • R 1 is selected from substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy , substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to Any one of C 10 aryl or heteroaryl, substituted or unsubstituted C 3 to C 10 alicyclic hydrocarbon group, substituted or unsubstituted C 2 to C 10 heterocyclic group;
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy alkenyl or heteroalkoxy, substituted or unsubstituted C
  • compounds of formula I include at least one of the following compounds:
  • the mass percentage content of the compound of formula I is 0.01% to 5% based on the mass of the electrolyte.
  • the electrolyte further includes a sulfur-oxygen double bond-containing compound, and the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-A) and formula (II-B);
  • R 21 , R 22 , R 23 and R 24 are each independently selected from substituted or unsubstituted C 1 to C 5 alkyl, substituted or Unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted Any one of C 6 to C 10 aryl, substituted or unsubstituted C 1 to C 6 heteroatom-containing groups, and, when substituted, the substituents include halogen and heteroatom-containing groups At least one, the heteroatom includes at least one of O, S, P, N, Si or B, wherein R 21 and R 22 can bond to form a ring structure, and R 23 and R 24 can bond combined to form a ring structure.
  • the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-1) to formula (II-20);
  • the mass percentage of the sulfur-oxygen double bond-containing compound is 0.01% to 5%.
  • the electrolyte further includes a polynitrile compound; the polynitrile compound includes at least one of the compounds represented by formula III;
  • the polynitrile compound includes at least one of the compounds represented by Formula III-1 to Formula III-18;
  • the mass percentage content of the polynitrile compound is 0.5% to 10% based on the mass of the electrolyte.
  • the electrolyte further includes a cyclic carbonate compound;
  • the cyclic carbonate compound includes at least one of the compounds represented by formula IV-A or IV-B;
  • R 41 and R 42 are each independently selected from any one of hydrogen, halogen, fluorine-substituted or unsubstituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl;
  • R 43 , R 44 are each independently selected from hydrogen, halogen and any one of fluorine-substituted C1 to C5 alkyl, C2 to C5 alkenyl, provided that at least one of R and R is selected from halogen , a fluorine-substituted C 1 to C 5 alkyl group or a C 2 to C 5 alkenyl group.
  • the cyclic carbonate compound includes at least one of the compounds represented by Formula IV-1 to Formula IV-7;
  • the mass percentage content of the cyclic carbonate compound is 0.01% to 5% based on the mass of the electrolyte.
  • the present application also proposes an electrochemical device, comprising: the above-mentioned electrolyte of the present application.
  • the present application also provides an electronic device, including the electrochemical device of the present application.
  • the embodiment of the present application provides an electrolyte, in which the compound of formula I can be preferentially oxidized and decomposed, forming a dense and stable CEI (cathode electrolyte interphase, positive electrode electrolyte interphase) film on the surface of the positive electrode, reducing the contact between the electrolyte and the positive electrode material. , thereby inhibiting the catalytic decomposition of the electrolyte and reducing the interface impedance. At the same time, it can be reduced to form a film on the surface of the negative electrode, reducing the reduction and decomposition of the electrolyte in the negative electrode.
  • CEI cathode electrolyte interphase, positive electrode electrolyte interphase
  • the compound of formula I can not only capture traces of water and hydrofluoric acid in the electrolyte, but also form a stable protective film on the positive electrode and negative electrode. During high temperature cycling and storage, it can effectively improve cycle stability and inhibit electrochemical Flatulence of the device.
  • the present application proposes a non-aqueous electrolyte that improves the high-temperature cycle performance of an electrochemical device, suppresses flatulence, and reduces impedance.
  • an electrolyte solution comprising: a compound of formula I;
  • R 1 is selected from substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted Substituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted C3 to C20 alicyclic hydrocarbyl, substituted or unsubstituted Any one of the C 2 to C 20 heterocyclyl groups, wherein, when substituted, the substituent includes halogen;
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 20
  • the electrolyte proposed in some embodiments of the present application can form stable interface protection on the surface of the positive electrode and the negative electrode of the electrochemical device, thereby significantly improving the cycle life and high temperature storage performance of the electrochemical device using the electrolyte.
  • the compound of formula I can be preferentially oxidized and decomposed, forming a dense and stable CEI film on the surface of the positive electrode, reducing the contact between the electrolyte and the positive electrode material, thereby inhibiting the catalytic decomposition of the electrolyte and reducing the interface impedance.
  • it can be reduced to form a film on the surface of the negative electrode, reducing the reduction and decomposition of the electrolyte in the negative electrode.
  • the compound of formula I can not only capture trace amounts of water and HF in the electrolyte, but also form a stable protective film on the positive and negative electrodes. During high-temperature cycling and storage, it can effectively improve cycle stability and inhibit electrochemical device degradation Flatulence.
  • R 1 is selected from substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy, or Heteroalkoxy, substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl, substituted or unsubstituted Any one of substituted C6 to C10 aryl or heteroaryl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted C2 to C10 heterocyclic group
  • R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy, substituted or unsubstit
  • the compound of formula I includes at least one of the following compounds:
  • the mass percentage content of the compound of formula I is 0.01% to 5% based on the mass of the electrolyte. In some embodiments, when the mass percentage of the compound of formula I is less than 0.01%, the improvement effect may not be obvious because the content is too small. When the mass percentage of the compound of formula I is greater than 5%, it may reduce the ions of the electrolyte. conductivity.
  • the electrolyte further includes a sulfur-oxygen double bond-containing compound, and the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-A) and formula (II-B);
  • R 21 , R 22 , R 23 and R 24 are each independently selected from substituted or unsubstituted C 1 to C 5 alkyl, substituted or Unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted Any one of C 6 to C 10 aryl, substituted or unsubstituted C 1 to C 6 heteroatom-containing groups, and, when substituted, the substituents include halogen and heteroatom-containing groups At least one, the heteroatom includes at least one of O, S, P, N, Si or B, wherein R 21 and R 22 can bond to form a ring structure, and R 23 and R 24 can bond combined to form a ring structure.
  • the above-mentioned sulfur-oxygen double bond compound is added to the electrolyte to improve the high-temperature cycle and storage performance of the electrochemical device using the electrolyte.
  • the sulfur-containing double bond compound can form an interface film rich in S element, which can further improve the thermal stability and mechanical stability of the interface film.
  • the reaction of the electrolyte at the negative electrode is alleviated, thereby further improving the cycle performance and high temperature storage performance.
  • the compound containing a sulfur-oxygen double bond includes at least one of the compounds represented by formula (II-1) to formula (II-20);
  • the mass percentage of the sulfur-oxygen double bond-containing compound is 0.01% to 5%. In some embodiments, if the mass percentage of the sulfur-oxygen double bond-containing compound is too low, the improvement effect is not obvious, and if the mass percentage is too high, the cost is increased.
  • the electrolyte further includes a polynitrile compound;
  • the polynitrile compound includes at least one of the compounds represented by formula III;
  • the introduction of the polynitrile compound can significantly improve both the thermal box performance and the electrical performance. This is because the polynitrile compound can well isolate the easily oxidizable components in the electrolyte from the surface of the positive electrode, which greatly reduces the oxidation of the positive electrode surface of the lithium-ion battery in the charged state to the electrolyte.
  • the above-mentioned polynitrile compound can form a synergistic effect with the compound of formula I in the electrolyte, and can form a more stable SEI film, thereby further improving the high temperature cycling, high temperature storage and hot box performance of the electrochemical device.
  • the polynitrile compound includes at least one of the compounds represented by formula III-1 to formula III-18;
  • the mass percentage content of the polynitrile compound is 0.5% to 10% based on the mass of the electrolyte. In some embodiments, if the mass content of the polynitrile compound is too low, the improvement effect may not be obvious, and if the mass content is too high, the ionic conductivity of the electrolyte may be affected.
  • the electrolyte further includes a cyclic carbonate compound;
  • the cyclic carbonate compound includes at least one of the compounds represented by formula IV-A or IV-B;
  • R 41 and R 42 are each independently selected from any one of hydrogen, halogen, fluorine-substituted or unsubstituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl;
  • R 43 , R 44 are each independently selected from hydrogen, halogen and any one of fluorine-substituted C1 to C5 alkyl, C2 to C5 alkenyl, provided that at least one of R and R is selected from halogen , a fluorine-substituted C 1 to C 5 alkyl group or a C 2 to C 5 alkenyl group.
  • the cyclic carbonic acid compound in the electrolyte can form a more stable SEI film, thereby further improving the high temperature cycling and high temperature storage performance of the electrochemical device.
  • the cyclic carbonate compound includes at least one of the compounds represented by Formula IV-1 to Formula IV-7;
  • the mass percentage content of the cyclic carbonate compound is 0.01% to 5% based on the mass of the electrolyte. In some embodiments, when the mass percentage of the cyclic carbonate compound is too low, the improvement effect is not obvious, and when the mass percentage is too high, the ionic conductivity of the electrolyte may decrease.
  • the electrolyte includes a cyclic ester and a chain ester, and the mass ratio of the cyclic ester and the chain ester is 1:9 to 7:3, wherein the cyclic ester is selected from ethylene carbonate (abbreviated as ethylene carbonate).
  • EC propylene carbonate
  • PC propylene carbonate
  • BL ⁇ -butyrolactone
  • chain ester is selected from dimethyl carbonate (abbreviated as DMC), diethyl carbonate (abbreviated as BL) DEC), methyl ethyl carbonate (abbreviated as EMC), ethyl acetate (abbreviated as EA), methyl formate (abbreviated as MF), ethyl formate (abbreviated as MA), ethyl propionate (abbreviated as EP) , at least one of propyl propionate (abbreviated as PP), methyl butyrate (abbreviated as MB), fluoromethyl ethyl carbonate, fluoro ethyl propionate and the like.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC methyl ethyl carbonate
  • EA ethyl acetate
  • MF
  • the electrolyte contains a lithium salt
  • the lithium salt may be at least one of an organic lithium salt or an inorganic lithium salt.
  • the lithium salt contains fluorine, boron At least one of element or phosphorus element.
  • the lithium salt includes lithium hexafluorophosphate LiPF 6 , lithium bistrifluoromethanesulfonimide LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSI), lithium bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 ) (abbreviated as LiFSI), Lithium Bisoxalate Borate LiB(C 2 O 4 ) 2 (abbreviated as LiBOB) or Lithium Hexafluorocesium Oxide (LiCsF 6 ), Lithium Perchlorate LiClO 4 , Trifluoromethanesulfonate At least one of at least one of lithium oxides LiCF 3 SO 3 .
  • LiTFSI lithium bistrifluoromethanesulfonimide LiN(CF 3 SO 2 ) 2
  • LiFSI lithium bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 )
  • LiBOB Lithium Bis
  • the concentration of the lithium salt is 0.5 mol/L to 1.5 mol/L. If the concentration of lithium salt is too low, the ionic conductivity of the electrolyte will be low, which will affect the rate and cycle performance of the lithium-ion battery; if the concentration of lithium salt is too high, the viscosity of the electrolyte will be too large, which will also affect the rate performance of the lithium-ion battery.
  • the concentration of the lithium salt is 0.8 mol/L to 1.2 mol/L.
  • the present application also proposes an electrochemical device, comprising: a positive electrode, a negative electrode, a separator, and any one of the above-mentioned electrolytes.
  • the positive electrode of the above electrochemical device includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes a positive electrode material.
  • the positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li).
  • Examples of cathode materials capable of absorbing/releasing lithium (Li) may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, phosphoric acid Lithium iron, lithium titanate, and lithium-rich manganese-based materials.
  • the positive electrode material can be selected from one or more of the following materials: LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 1-y My O 2 , LiNi 1-y My O 2 , LiMn 2-y My O 4 , LiNi x Co y Mn z M 1-xyz O 2 , wherein M is selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti At least one of , and 0 ⁇ y ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, x+y+z ⁇ 1.
  • a conductive agent or a binder may be added to the positive electrode active material layer of the electrochemical device.
  • the positive electrode active material layer further includes a carbon material, and the carbon material may include conductive carbon black, graphite, graphene, At least one of carbon nanotubes, carbon fibers or carbon black.
  • the binder may include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-acrylate copolymer, styrene-butadiene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyamide At least one of acrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl acetate, polyethylene pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene .
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, and the negative electrode material may include, for example, carbon materials, metal alloys, lithium-containing oxides, and silicon-containing materials etc. made.
  • the carbon material is preferably graphite or a carbon material obtained by coating the surface of graphite with carbon that is amorphous compared to graphite.
  • the release membrane includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, or aramid.
  • the polyethylene includes at least one selected from high density polyethylene, low density polyethylene or ultra-high molecular weight polyethylene. Especially polyethylene and polypropylene, they have a good effect on preventing short circuits and can improve the stability of the battery through the shutdown effect.
  • the surface of the isolation membrane may further include a porous layer, the porous layer is disposed on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from aluminum oxide (Al 2 O 3 ), Silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium dioxide (HfO 2 ), tin oxide (SnO 2 ), ceria (CeO 2 ), nickel oxide (NiO), oxide Zinc (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 sulfuric acid at least one of barium.
  • the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyethylene At least one of alkanone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the porous layer on the surface of the separator can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the pole piece.
  • the present application also provides an electronic device, including the electrochemical device according to any one of the above.
  • the electronic device of the present application is not particularly limited, and it can be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, and large household batteries, etc.
  • Separator a polyethylene (PE) porous polymer film is used as the separator.
  • Preparation of lithium ion battery stack the positive pole piece, the separator and the negative pole piece in order, so that the separator is placed between the positive pole piece and the negative pole piece to play an isolation role, and then roll to obtain a bare cell ; After welding the tabs, place the bare cell in the outer packaging aluminum-plastic film, inject the above-prepared electrolyte into the dried bare cell, and go through the processes of vacuum packaging, standing, forming, shaping, and capacity testing. , to obtain a lithium-ion battery.
  • the test process of lithium-ion battery is as follows:
  • the lithium-ion battery was placed in a 45°C incubator for 30 minutes to allow the lithium-ion battery to reach a constant temperature.
  • the lithium-ion battery that has reached a constant temperature is charged at a constant current of 0.5C to a voltage of 4.2V, then charged at a constant voltage of 4.2V to a current of 0.05C, and then discharged at a constant current of 1C to a voltage of 3.0V. This is a charge-discharge cycle. . Taking the capacity of the first discharge as 100%, the charge-discharge cycle was repeated for 500 cycles, the test was stopped, and the cycle capacity retention rate was recorded as an index for evaluating the cycle performance of the lithium-ion battery.
  • Cycle capacity retention rate discharge capacity at the 500th cycle/discharge capacity at the first cycle.
  • Thickness swelling ratio (battery thickness after cycling - battery thickness before cycling)/battery thickness before cycling ⁇ 100%
  • the lithium-ion battery was charged to 4.2V at 0.5C at 25°C, and then charged to 0.05C under constant voltage at 4.2V, and the thickness of the battery was measured and recorded with a micrometer at this time as H 11 ; then the battery was placed at 60°C Store in an oven for 24 hours, and after 24 hours, test with a micrometer and record the thickness of the battery at this time, which is recorded as H 12 . .
  • Thickness expansion rate (%) of lithium ion battery after storage at 60°C for 24 hours (H 12 -H 11 )/H 11 ⁇ 100%
  • the lithium-ion battery was charged to 4.2V with a constant current of 0.5C and a constant voltage of 4.2V to a current of 0.05C.
  • the battery was placed in a high temperature box, heated to 140 °C with a temperature rise rate of 5 ⁇ 2 °C/min, and then kept for 1 h, and the voltage, temperature of the battery and changes in the temperature of the hot box were recorded. The test is passed if the battery does not catch fire, explode, or emit smoke. Test 10 batteries in each group, and record the number of batteries that pass the test.
  • the lithium-ion battery was charged to 4.2V at 0.5C at 25°C, and then charged to 0.05C under constant voltage at 4.2V. Test and record the thickness of the battery at this time with a micrometer as H 21 ; then place the battery at 85°C Store in an oven for 24 hours. After 24 hours, use a micrometer to test and record the thickness of the battery at this time, which is recorded as H 22 .
  • Thickness expansion rate (%) of lithium ion battery after storage at 85°C for 24 hours (H 22 -H 21 )/H 21 ⁇ 100%
  • Examples 1 to 19 and Comparative Examples 1 to 2 The additives used in Examples 1 to 19 and Comparative Examples 1 to 2, and the performance test results of lithium ion batteries are shown in Table 1.
  • the compound of formula I was added to the electrolyte. No additives were added to the solution, and phthalic anhydride was added to the electrolyte of Comparative Example 2.
  • Examples 4, 20 to 26 and Comparative Examples 1 and 3, and the performance test results of lithium ion batteries are shown in Table 2.
  • the electrolytes of Examples 20 to 26 were added with the compound of formula I and sulfur-containing oxygen. Double bond compound.
  • the 45°C cycle capacity retention rate and hot box throughput rate of Examples 27 to 32 are higher than those of Example 4, Comparative Example 1 and Comparative Example 4, and the storage thickness expansion rate at 85°C is lower than that of Example 4, Comparing Example 1 and Comparative Example 4, it can be seen that when the polynitrile compound is further added to the electrolyte, the 45 °C cycle capacity retention rate of the lithium-ion battery increases, the 85 °C storage thickness expansion rate decreases, and the hot box pass rate increases, It can be seen that the addition of polynitrile compounds improves the cycle performance, high temperature storage performance and safety performance of lithium-ion batteries, because the polynitrile compounds can form a synergistic effect with the compound of formula I in the electrolyte, which can form a more stable SEI film, and then Further improve the high temperature cycling, high temperature storage performance and hot box performance of Li-ion batteries.
  • Examples 4, 33 to 37 and Comparative Examples 1 and 5, and the performance test results of lithium ion batteries are shown in Table 4.
  • the compound of formula I and cyclic carbonic acid were added to the electrolyte. ester compound.

Abstract

The present application provides an electrolyte, an electrochemical device and an electronic device. An embodiment of the present application provides an electrolyte, comprising: a compound of formula (I); and the compound of formula I in the electrolyte can be preferentially oxidized and decomposed to form a dense and stable CEI film on the surface of a positive electrode, which reduces the contact between the electrolyte and the positive electrode material, such that the catalytic decomposition of the electrolyte is inhibited, the interface impedance is reduced, and the direct current impedance is improved. At the same time, a film can be formed on the surface of the negative electrode by means of reduction, thereby reducing the reduction decomposition of the electrolyte in the negative electrode. The compound of formula I can not only capture the trace amount of water and HF in the electrolyte, but also forms stable protective films on the positive electrode and the negative electrode, which can effectively improve the cycling stability and slow down the degassing in the cycling process during the continuous charging and discharging cycle.

Description

电解液、电化学装置和电子装置Electrolytes, Electrochemical Devices and Electronic Devices 技术领域technical field
本申请涉及电化学领域，尤其涉及一种电解液、电化学装置和电子装置。The present application relates to the field of electrochemistry, and in particular, to an electrolyte, an electrochemical device, and an electronic device.
背景技术Background technique
电解液是电化学装置(例如锂离子电池)的重要组成部分，对电化学装置的比容量、充放电效率、循环稳定性、倍率性能、工作温度范围以及安全性能等起到至关重要的作用。随着锂离子电池的广泛应用，人们对其在高温下的稳定性和安全性提出了更高的要求。The electrolyte is an important part of electrochemical devices (such as lithium-ion batteries), and plays a crucial role in the specific capacity, charge-discharge efficiency, cycle stability, rate performance, operating temperature range, and safety performance of electrochemical devices. . With the wide application of lithium-ion batteries, people have put forward higher requirements for their stability and safety at high temperatures.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本申请的目的在于提供一种电解液、电化学装置和电子装置，以解决现有技术中存在的问题。In view of this, the purpose of the present application is to provide an electrolyte, an electrochemical device and an electronic device to solve the problems existing in the prior art.
本申请实施例中提出一种电解液，包括：式I化合物；An electrolyte solution is proposed in the embodiments of the present application, comprising: a compound of formula I;
Figure PCTCN2021082145-appb-000001
Figure PCTCN2021082145-appb-000001
其中，A选自-C(＝O)-或-S(＝O) 2-；R 1选自经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素；R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代 或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素；当含杂原子时，杂原子包括O、N、P、S、Si或B中的至少一种；n选自1或2；m选自0或1；m+n＝2。 Wherein, A is selected from -C(=O)- or -S(=O) 2 -; R 1 is selected from substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted Substituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted C3 to C20 alicyclic hydrocarbyl, substituted or unsubstituted Any one of the C 2 to C 20 heterocyclyl groups, wherein, when substituted, the substituent includes halogen; R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkene alkynyl or heteroalkenyl, substituted or unsubstituted C2 to C20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted Any of a substituted C3 to C20 alicyclic hydrocarbon group, a substituted or unsubstituted C2 to C20 heterocyclic group, wherein, when substituted, the substituent includes halogen; when a heteroatom is contained , the heteroatom includes at least one of O, N, P, S, Si or B; n is selected from 1 or 2; m is selected from 0 or 1; m+n=2.
一些实施例中，R 1选自经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种；R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种。 In some embodiments, R 1 is selected from substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy , substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to Any one of C 10 aryl or heteroaryl, substituted or unsubstituted C 3 to C 10 alicyclic hydrocarbon group, substituted or unsubstituted C 2 to C 10 heterocyclic group; R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy alkenyl or heteroalkoxy, substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl, substituted or of unsubstituted C6 to C10 aryl or heteroaryl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted C2 to C10 heterocyclic group any kind.
一些实施例中，式I化合物包括如下所示化合物中的至少一种：In some embodiments, compounds of formula I include at least one of the following compounds:
Figure PCTCN2021082145-appb-000002
Figure PCTCN2021082145-appb-000002
Figure PCTCN2021082145-appb-000003
Figure PCTCN2021082145-appb-000003
一些实施例中，基于电解液的质量，式I化合物的质量百分含量为0.01％至5％。一些实施例中，电解液还包括含硫氧双键化合物，含硫氧双键化合物包括式(II-A)和式(II-B)表示的化合物中的至少一种；In some embodiments, the mass percentage content of the compound of formula I is 0.01% to 5% based on the mass of the electrolyte. In some embodiments, the electrolyte further includes a sulfur-oxygen double bond-containing compound, and the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-A) and formula (II-B);
Figure PCTCN2021082145-appb-000004
Figure PCTCN2021082145-appb-000004
在式(II-A)和式(II-B)中，R 21、R 22、R 23和R 24各自独立地选自经取代或未经取代的C 1至C 5烷基、经取代或未经取代的C 2至C 10烯基、经取代或未经取代的C 2至C 10炔基、经取代或未经取代的C 3至C 10脂环烃基、经取代或未经取代的C 6至C 10芳基、经取代或未经取代的C 1至C 6含杂原子基团中的任意一种，并且，当经取代时，取代基包括卤素和含杂原子基团中的至 少一种，杂原子包括O、S、P、N、Si或B中的至少一种，其中，R 21和R 22之间可以键合而形成环结构，R 23和R 24之间可以键合而形成环结构。 In formula (II-A) and formula (II-B), R 21 , R 22 , R 23 and R 24 are each independently selected from substituted or unsubstituted C 1 to C 5 alkyl, substituted or Unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted Any one of C 6 to C 10 aryl, substituted or unsubstituted C 1 to C 6 heteroatom-containing groups, and, when substituted, the substituents include halogen and heteroatom-containing groups At least one, the heteroatom includes at least one of O, S, P, N, Si or B, wherein R 21 and R 22 can bond to form a ring structure, and R 23 and R 24 can bond combined to form a ring structure.
一些实施例中，含硫氧双键化合物包括式(II-1)至式(II-20)表示的化合物中的至少一种；In some embodiments, the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-1) to formula (II-20);
Figure PCTCN2021082145-appb-000005
Figure PCTCN2021082145-appb-000005
一些实施例中，基于电解液的质量，含硫氧双键化合物的质量百分含量为0.01％至5％。一些实施例中，电解液还包括多腈化合物；多腈化合物包括式III表示的化合物中的至少一种；In some embodiments, based on the mass of the electrolyte, the mass percentage of the sulfur-oxygen double bond-containing compound is 0.01% to 5%. In some embodiments, the electrolyte further includes a polynitrile compound; the polynitrile compound includes at least one of the compounds represented by formula III;
Figure PCTCN2021082145-appb-000006
Figure PCTCN2021082145-appb-000006
在式III中，R 31、R 32、R 33、R 34各自独立地选自氢、经取代或未经取代的C 1至C 10烷基、经取代或未经取代的-(CH 2) a-CN、经取代或未经取代的-(CH 2) b-O-(CH 2) c-CN、经取代或未经取代的-(CH 2) d-CH＝CH-(CH 2) k-CN、经取 代或未经取代的
Figure PCTCN2021082145-appb-000007
经取代或未经取代的
Figure PCTCN2021082145-appb-000008
经取代或未经取代的烷氧基羰基中的任意一种，其中，a、b、c、d、e、f、g、h、i、j、k各自独立地选自0至10的整数，并且，当经取代时，取代基包括卤素中的至少一种；x选自0至3的整数，并且，当n选自1至3的整数时，R 31、R 32、R 33、R 34中的至少两个为含有氰基的基团，当n选自0时，R 32和R 34均至少含有氰基基团。 In Formula III, R 31 , R 32 , R 33 , R 34 are each independently selected from hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted -(CH 2 ) a -CN, substituted or unsubstituted-( CH2 ) b -O-( CH2 ) c -CN, substituted or unsubstituted-( CH2 ) d -CH=CH-( CH2 ) k -CN, substituted or unsubstituted
Figure PCTCN2021082145-appb-000007
substituted or unsubstituted
Figure PCTCN2021082145-appb-000008
Any of a substituted or unsubstituted alkoxycarbonyl group, wherein a, b, c, d, e, f, g, h, i, j, k are each independently an integer from 0 to 10 , and, when substituted, the substituent includes at least one of halogen; x is selected from an integer from 0 to 3, and when n is selected from an integer from 1 to 3, R 31 , R 32 , R 33 , R At least two of 34 are groups containing a cyano group, and when n is selected from 0, both R 32 and R 34 contain at least a cyano group.
一些实施例中，多腈化合物包括式III-1至式III-18表示的化合物中的至少一种；In some embodiments, the polynitrile compound includes at least one of the compounds represented by Formula III-1 to Formula III-18;
Figure PCTCN2021082145-appb-000009
Figure PCTCN2021082145-appb-000009
Figure PCTCN2021082145-appb-000010
Figure PCTCN2021082145-appb-000010
一些实施例中，基于电解液的质量，多腈化合物的质量百分含量为0.5％至10％。In some embodiments, the mass percentage content of the polynitrile compound is 0.5% to 10% based on the mass of the electrolyte.
一些实施例中，电解液还包括环状碳酸酯化合物；环状碳酸酯化合物包括式Ⅳ-A或Ⅳ-B表示的化合物中的至少一种；In some embodiments, the electrolyte further includes a cyclic carbonate compound; the cyclic carbonate compound includes at least one of the compounds represented by formula IV-A or IV-B;
Figure PCTCN2021082145-appb-000011
Figure PCTCN2021082145-appb-000011
R 41和R 42各自独立地选自氢、卤素、经氟取代或未经氟取代的C 1至C 5的烷基、C 2至C 5的烯基中的任意一种；R 43、R 44各自独立地选自氢、卤素和经氟取代的C 1至C 5烷基、C 2至C 5的烯基中的任意一种，条件是R 43和R 44中的至少一个选自卤素、经氟取代的C 1至C 5的烷基或C 2至C 5的烯基。 R 41 and R 42 are each independently selected from any one of hydrogen, halogen, fluorine-substituted or unsubstituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl; R 43 , R 44 are each independently selected from hydrogen, halogen and any one of fluorine-substituted C1 to C5 alkyl, C2 to C5 alkenyl, provided that at least one of R and R is selected from halogen , a fluorine-substituted C 1 to C 5 alkyl group or a C 2 to C 5 alkenyl group.
一些实施例中，环状碳酸酯化合物包括式Ⅳ-1至式Ⅳ-7表示的化合物中的至少一种；In some embodiments, the cyclic carbonate compound includes at least one of the compounds represented by Formula IV-1 to Formula IV-7;
Figure PCTCN2021082145-appb-000012
Figure PCTCN2021082145-appb-000012
一些实施例中，基于电解液的质量，环状碳酸酯化合物的质量百分含量为0.01％至5％。In some embodiments, the mass percentage content of the cyclic carbonate compound is 0.01% to 5% based on the mass of the electrolyte.
本申请还提出一种电化学装置，包括：本申请上述的电解液。The present application also proposes an electrochemical device, comprising: the above-mentioned electrolyte of the present application.
本申请还提出一种电子装置，包括本申请的电化学装置。The present application also provides an electronic device, including the electrochemical device of the present application.
本申请实施例提供了一种电解液，电解液中的式I化合物能够优先氧化分解，在正极表面形成致密稳定的CEI(cathode electrolyte interphase，正极电解质界相)膜，减少电解液与正极材料接触，从而抑制电解液催化分解，降低界面阻抗。同时，能够在负极表面还原成膜，减少电解液在负极的还原分解。该式I化合物既可捕获电解液中的痕量水及氢氟酸，同时在正极、负极形成稳定的保护膜，在高温循环和存储过程中，可以有效地提升循环稳定性、并抑制电化学装置的胀气。The embodiment of the present application provides an electrolyte, in which the compound of formula I can be preferentially oxidized and decomposed, forming a dense and stable CEI (cathode electrolyte interphase, positive electrode electrolyte interphase) film on the surface of the positive electrode, reducing the contact between the electrolyte and the positive electrode material. , thereby inhibiting the catalytic decomposition of the electrolyte and reducing the interface impedance. At the same time, it can be reduced to form a film on the surface of the negative electrode, reducing the reduction and decomposition of the electrolyte in the negative electrode. The compound of formula I can not only capture traces of water and hydrofluoric acid in the electrolyte, but also form a stable protective film on the positive electrode and negative electrode. During high temperature cycling and storage, it can effectively improve cycle stability and inhibit electrochemical Flatulence of the device.
具体实施方式Detailed ways
下面将更详细地描述本申请的实施例。虽然显示了本申请的某些实施例，然而应当理解的是，本申请可以通过各种形式来实现，而且不应该被解释为限于这里阐述的实施例，相反提供这些实施例是为了更加透彻和完整地理解本申请。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。以下将对本申请实施例提供的方案进行详细描述。Embodiments of the present application will be described in more detail below. While certain embodiments of the present application have been shown, it should be understood that the present application may be embodied in various forms and should not be construed as limited to the embodiments set forth herein, but rather are provided for the purpose of greater thoroughness and clarity. understand this application completely. The following examples may enable those skilled in the art to more fully understand the present application, but do not limit the present application in any way. The solutions provided by the embodiments of the present application will be described in detail below.
本申请提出了一种提高电化学装置的高温循环性能、抑制胀气且兼顾降低阻抗的非水电解液。The present application proposes a non-aqueous electrolyte that improves the high-temperature cycle performance of an electrochemical device, suppresses flatulence, and reduces impedance.
本申请一些实施例中提出一种电解液，包括：式I化合物；In some embodiments of the present application, an electrolyte solution is proposed, comprising: a compound of formula I;
Figure PCTCN2021082145-appb-000013
Figure PCTCN2021082145-appb-000013
其中，A选自-C(＝O)-或-S(＝O) 2-；R 1选自经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素；R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素；当含杂原子时，杂原子包括O、N、P、S、Si或B中的至少一种；n选自1或2；m选自0或1；m+n＝2。 Wherein, A is selected from -C(=O)- or -S(=O) 2 -; R 1 is selected from substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted Substituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted C3 to C20 alicyclic hydrocarbyl, substituted or unsubstituted Any one of the C 2 to C 20 heterocyclyl groups, wherein, when substituted, the substituent includes halogen; R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkene alkynyl or heteroalkenyl, substituted or unsubstituted C2 to C20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted Any of a substituted C3 to C20 alicyclic hydrocarbon group, a substituted or unsubstituted C2 to C20 heterocyclic group, wherein, when substituted, the substituent includes halogen; when a heteroatom is contained , the heteroatom includes at least one of O, N, P, S, Si or B; n is selected from 1 or 2; m is selected from 0 or 1; m+n=2.
本申请一些实施例中提出的电解液能够在电化学装置的正极表面和负极表面形成稳定的界面保护，从而显著改善采用该电解液的电化学装置的循环寿命和高温存储性能。在电化学装置首次充电时，式I化合物能够优先氧化分解，在正极表面形成致密稳定的CEI膜，减少电解液与正极材料接触，从而抑制电解液催化分解，降低界面阻抗。同时，能够在负极表面还原成膜，减少电解液在负极的还原分解。该式I化合物既可捕获电解液中的痕量水及HF，同时在正极、负极形成稳定的保护膜，在高温循环和存储过程中，可以有效地提升循环稳定性、并抑制电化学装置的胀气。The electrolyte proposed in some embodiments of the present application can form stable interface protection on the surface of the positive electrode and the negative electrode of the electrochemical device, thereby significantly improving the cycle life and high temperature storage performance of the electrochemical device using the electrolyte. When the electrochemical device is charged for the first time, the compound of formula I can be preferentially oxidized and decomposed, forming a dense and stable CEI film on the surface of the positive electrode, reducing the contact between the electrolyte and the positive electrode material, thereby inhibiting the catalytic decomposition of the electrolyte and reducing the interface impedance. At the same time, it can be reduced to form a film on the surface of the negative electrode, reducing the reduction and decomposition of the electrolyte in the negative electrode. The compound of formula I can not only capture trace amounts of water and HF in the electrolyte, but also form a stable protective film on the positive and negative electrodes. During high-temperature cycling and storage, it can effectively improve cycle stability and inhibit electrochemical device degradation Flatulence.
在本申请的一些实施例中，R 1选自经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种； R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种。 In some embodiments of the present application, R 1 is selected from substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy, or Heteroalkoxy, substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl, substituted or unsubstituted Any one of substituted C6 to C10 aryl or heteroaryl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted C2 to C10 heterocyclic group R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy, substituted or unsubstituted C2 to C10 alkenyl or heteroalkenyl, substituted or unsubstituted C2 to C10 alkynyl or heteroalkynyl , substituted or unsubstituted C 6 to C 10 aryl or heteroaryl, substituted or unsubstituted C 3 to C 10 alicyclic hydrocarbon groups, substituted or unsubstituted C 2 to C 10 hetero any of the ring groups.
在本申请一些实施例中，式I化合物包括如下所示化合物中的至少一种：In some embodiments of the present application, the compound of formula I includes at least one of the following compounds:
Figure PCTCN2021082145-appb-000014
Figure PCTCN2021082145-appb-000014
Figure PCTCN2021082145-appb-000015
Figure PCTCN2021082145-appb-000015
在本申请的一些实施例中，基于电解液的质量，式I化合物的质量百分含量为0.01％至5％。一些实施例中，当式I化合物的质量百分含量低于0.01％时，可能因为含量太少导致改善效果不明显，当式I化合物的质量百分含量大于5％可能会降低电解液的离子电导率。In some embodiments of the present application, the mass percentage content of the compound of formula I is 0.01% to 5% based on the mass of the electrolyte. In some embodiments, when the mass percentage of the compound of formula I is less than 0.01%, the improvement effect may not be obvious because the content is too small. When the mass percentage of the compound of formula I is greater than 5%, it may reduce the ions of the electrolyte. conductivity.
在本申请的一些实施例中，电解液还包括含硫氧双键化合物，含硫氧双键化合物包括式(II-A)和式(II-B)表示的化合物中的至少一种；In some embodiments of the present application, the electrolyte further includes a sulfur-oxygen double bond-containing compound, and the sulfur-oxygen double bond-containing compound includes at least one of the compounds represented by formula (II-A) and formula (II-B);
Figure PCTCN2021082145-appb-000016
Figure PCTCN2021082145-appb-000016
在式(II-A)和式(II-B)中，R 21、R 22、R 23和R 24各自独立地选自经取代或未经取代的C 1至C 5烷基、经取代或未经取代的C 2至C 10烯基、经取代或未经取代的C 2至C 10炔基、经取代或未经取代的C 3至C 10脂环烃基、经取代或未经取代的C 6至C 10芳基、经取代或未经取代的C 1至C 6含杂原子基团中的任意一种，并且，当经取代时，取代基包括卤素和含杂原子基团中的至少一种，杂原子包括O、S、P、N、Si或B中的至少一种，其中，R 21和R 22之间可以键合而形成环结构，R 23和R 24之间可以键合而形成环结构。一些实施例中，电解液中加入上述的含硫氧双键化合物，提升了采用该电解液的电化学装置高温循环和存储性能。这主要是因为含硫双键化合物可以形成富含S元素的界面膜，可以进一步提升界面膜的热稳定性和机械稳定性，其可在负极成膜修饰SEI，形成更优异的界面保护膜，缓解电解液在负极的反应，从而进一步改善循环性能和高温存储性能。 In formula (II-A) and formula (II-B), R 21 , R 22 , R 23 and R 24 are each independently selected from substituted or unsubstituted C 1 to C 5 alkyl, substituted or Unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted Any one of C 6 to C 10 aryl, substituted or unsubstituted C 1 to C 6 heteroatom-containing groups, and, when substituted, the substituents include halogen and heteroatom-containing groups At least one, the heteroatom includes at least one of O, S, P, N, Si or B, wherein R 21 and R 22 can bond to form a ring structure, and R 23 and R 24 can bond combined to form a ring structure. In some embodiments, the above-mentioned sulfur-oxygen double bond compound is added to the electrolyte to improve the high-temperature cycle and storage performance of the electrochemical device using the electrolyte. This is mainly because the sulfur-containing double bond compound can form an interface film rich in S element, which can further improve the thermal stability and mechanical stability of the interface film. The reaction of the electrolyte at the negative electrode is alleviated, thereby further improving the cycle performance and high temperature storage performance.
在本申请的一些实施例中，含硫氧双键的化合物包括式(II-1)至式(II-20)表示的化合物中的至少一种；In some embodiments of the present application, the compound containing a sulfur-oxygen double bond includes at least one of the compounds represented by formula (II-1) to formula (II-20);
Figure PCTCN2021082145-appb-000017
Figure PCTCN2021082145-appb-000017
在本申请的一些实施例中，基于电解液的质量，含硫氧双键化合物的质量百分含量为0.01％至5％。一些实施例中，含硫氧双键化合物的质量百分含量过低导致改善效果不明显，质量百分含量过高增加成本。In some embodiments of the present application, based on the mass of the electrolyte, the mass percentage of the sulfur-oxygen double bond-containing compound is 0.01% to 5%. In some embodiments, if the mass percentage of the sulfur-oxygen double bond-containing compound is too low, the improvement effect is not obvious, and if the mass percentage is too high, the cost is increased.
在本申请的一些实施例中，电解液还包括多腈化合物；多腈化合物包括式III表示的化合物中的至少一种；In some embodiments of the present application, the electrolyte further includes a polynitrile compound; the polynitrile compound includes at least one of the compounds represented by formula III;
Figure PCTCN2021082145-appb-000018
Figure PCTCN2021082145-appb-000018
在式III中，R 31、R 32、R 33、R 34各自独立地选自氢、经取代或未经取代的C 1至C 10烷基、经取代或未经取代的-(CH 2) a-CN、经取代或未经取代的-(CH 2) b-O-(CH 2) c-CN、经取代或未经取代的-(CH 2) d-CH＝CH-(CH 2) k-CN、经取 代或未经取代的
Figure PCTCN2021082145-appb-000019
经取代或未经取代的
Figure PCTCN2021082145-appb-000020
经取代或未经取代的烷氧基羰基中的任意一种，其中，a、b、c、d、e、f、g、h、i、j、k各自独立地选自0至10的整数，并且，当经取代时，取代基包括卤素中的至少一种；x选自0至3的整数，并且，当n选自1至3的整数时，R 31、R 32、R 33、R 34中的至少两个为含有氰基的基团，当n选自0时，R 32和R 34均至少含有氰基基团。一些实施例中，多腈化合物的引入能够使热箱性能及电性能均得到明显提升。这是由于，多腈化合物可以很好地将电解液中易氧化组分与正极表面隔开，大大降低了充电态的锂离子电池的正极表面对电解液的氧化作用。上述多腈化合物能够与电解液中的式I化合物形成协同作用，可形成更加稳定的SEI膜，进而进一步改善电化学装置的高温循环、高温存储以及热箱性能。 In Formula III, R 31 , R 32 , R 33 , R 34 are each independently selected from hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted -(CH 2 ) a -CN, substituted or unsubstituted-( CH2 ) b -O-( CH2 ) c -CN, substituted or unsubstituted-( CH2 ) d -CH=CH-( CH2 ) k -CN, substituted or unsubstituted
Figure PCTCN2021082145-appb-000019
substituted or unsubstituted
Figure PCTCN2021082145-appb-000020
Any of a substituted or unsubstituted alkoxycarbonyl group, wherein a, b, c, d, e, f, g, h, i, j, k are each independently an integer from 0 to 10 , and, when substituted, the substituent includes at least one of halogen; x is selected from an integer from 0 to 3, and when n is selected from an integer from 1 to 3, R 31 , R 32 , R 33 , R At least two of 34 are groups containing a cyano group, and when n is selected from 0, both R 32 and R 34 contain at least a cyano group. In some embodiments, the introduction of the polynitrile compound can significantly improve both the thermal box performance and the electrical performance. This is because the polynitrile compound can well isolate the easily oxidizable components in the electrolyte from the surface of the positive electrode, which greatly reduces the oxidation of the positive electrode surface of the lithium-ion battery in the charged state to the electrolyte. The above-mentioned polynitrile compound can form a synergistic effect with the compound of formula I in the electrolyte, and can form a more stable SEI film, thereby further improving the high temperature cycling, high temperature storage and hot box performance of the electrochemical device.
本申请的一些实施例中，多腈化合物包括式III-1至式III-18表示的化合物中的至少一种；In some embodiments of the present application, the polynitrile compound includes at least one of the compounds represented by formula III-1 to formula III-18;
Figure PCTCN2021082145-appb-000021
Figure PCTCN2021082145-appb-000021
Figure PCTCN2021082145-appb-000022
Figure PCTCN2021082145-appb-000022
一些实施例中，基于电解液的质量，多腈化合物的质量百分含量为0.5％至10％。一些实施例中，多腈化合物的质量含量过少可能改善效果不明显，质量含量过高可能对电解液的离子电导率造成影响。In some embodiments, the mass percentage content of the polynitrile compound is 0.5% to 10% based on the mass of the electrolyte. In some embodiments, if the mass content of the polynitrile compound is too low, the improvement effect may not be obvious, and if the mass content is too high, the ionic conductivity of the electrolyte may be affected.
一些实施例中，电解液还包括环状碳酸酯化合物；环状碳酸酯化合物包括式Ⅳ-A或Ⅳ-B表示的化合物中的至少一种；In some embodiments, the electrolyte further includes a cyclic carbonate compound; the cyclic carbonate compound includes at least one of the compounds represented by formula IV-A or IV-B;
Figure PCTCN2021082145-appb-000023
Figure PCTCN2021082145-appb-000023
R 41和R 42各自独立地选自氢、卤素、经氟取代或未经氟取代的C 1至C 5的烷基、C 2至C 5的烯基中的任意一种；R 43、R 44各自独立地选自氢、卤素和经氟取代的C 1至C 5烷基、C 2至C 5的烯基中的任意一种，条件是R 43和R 44中的至少一个选自卤素、经氟取代的C 1至C 5的烷基或C 2至C 5的烯基。一些实施例中，电解液中的环状碳酸化合物可形成更加稳定的SEI膜，进而进一步改 善电化学装置的高温循环和高温存储性能。 R 41 and R 42 are each independently selected from any one of hydrogen, halogen, fluorine-substituted or unsubstituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl; R 43 , R 44 are each independently selected from hydrogen, halogen and any one of fluorine-substituted C1 to C5 alkyl, C2 to C5 alkenyl, provided that at least one of R and R is selected from halogen , a fluorine-substituted C 1 to C 5 alkyl group or a C 2 to C 5 alkenyl group. In some embodiments, the cyclic carbonic acid compound in the electrolyte can form a more stable SEI film, thereby further improving the high temperature cycling and high temperature storage performance of the electrochemical device.
一些实施例中，环状碳酸酯化合物包括式Ⅳ-1至式Ⅳ-7表示的化合物中的至少一种；In some embodiments, the cyclic carbonate compound includes at least one of the compounds represented by Formula IV-1 to Formula IV-7;
Figure PCTCN2021082145-appb-000024
Figure PCTCN2021082145-appb-000024
在本申请的一些实施例中，基于电解液的质量，环状碳酸酯化合物的质量百分含量为0.01％至5％。一些实施例中，环状碳酸酯化合物的质量百分含量过低时改善效果不明显，质量百分含量过高时，可能导致电解液的离子电导率下降。In some embodiments of the present application, the mass percentage content of the cyclic carbonate compound is 0.01% to 5% based on the mass of the electrolyte. In some embodiments, when the mass percentage of the cyclic carbonate compound is too low, the improvement effect is not obvious, and when the mass percentage is too high, the ionic conductivity of the electrolyte may decrease.
在本申请的一些实施例中，电解液包括环状酯和链状酯，环状酯和链状酯的质量比为1:9至7:3，其中环状酯选自碳酸乙烯酯(简写为EC)、碳酸丙烯酯(简写为PC)、γ-丁内酯(简写为BL)中的至少一种；链状酯选自碳酸二甲酯(简写为DMC)、碳酸二乙酯(简写为DEC)、碳酸甲乙酯(简写为EMC)、乙酸乙酯(简写为EA)、甲酸甲酯(简写为MF)、甲酸乙酯(简写为MA)、丙酸乙酯(简写为EP)、丙酸丙酯(简写为PP)、丁酸甲酯(简写为MB)、氟代碳酸甲乙酯、氟代丙酸乙酯等中的至少一种。In some embodiments of the present application, the electrolyte includes a cyclic ester and a chain ester, and the mass ratio of the cyclic ester and the chain ester is 1:9 to 7:3, wherein the cyclic ester is selected from ethylene carbonate (abbreviated as ethylene carbonate). EC), propylene carbonate (abbreviated as PC), at least one of γ-butyrolactone (abbreviated as BL); chain ester is selected from dimethyl carbonate (abbreviated as DMC), diethyl carbonate (abbreviated as BL) DEC), methyl ethyl carbonate (abbreviated as EMC), ethyl acetate (abbreviated as EA), methyl formate (abbreviated as MF), ethyl formate (abbreviated as MA), ethyl propionate (abbreviated as EP) , at least one of propyl propionate (abbreviated as PP), methyl butyrate (abbreviated as MB), fluoromethyl ethyl carbonate, fluoro ethyl propionate and the like.
在本申请的一些实施例中，电解液中含有锂盐，锂盐可以是有机锂盐或无机锂盐中的至少一种，在本申请的一些实施例中，锂盐中含有氟元素、硼元素或磷元素中的至少一种。在一些实施例中，锂盐包括六氟磷酸锂LiPF 6、双三氟甲烷磺酰亚胺锂LiN(CF 3SO 2) 2(简写为LiTFSI)、双(氟磺酰)亚胺锂Li(N(SO 2F) 2)(简写为LiFSI)、双草酸硼酸锂LiB(C 2O 4) 2(简写为LiBOB)或六氟铯酸锂(LiCsF 6)、高氯酸锂LiClO 4、三氟甲磺酸锂LiCF 3SO 3中的至少一种的至少一种。 In some embodiments of the present application, the electrolyte contains a lithium salt, and the lithium salt may be at least one of an organic lithium salt or an inorganic lithium salt. In some embodiments of the present application, the lithium salt contains fluorine, boron At least one of element or phosphorus element. In some embodiments, the lithium salt includes lithium hexafluorophosphate LiPF 6 , lithium bistrifluoromethanesulfonimide LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSI), lithium bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 ) (abbreviated as LiFSI), Lithium Bisoxalate Borate LiB(C 2 O 4 ) 2 (abbreviated as LiBOB) or Lithium Hexafluorocesium Oxide (LiCsF 6 ), Lithium Perchlorate LiClO 4 , Trifluoromethanesulfonate At least one of at least one of lithium oxides LiCF 3 SO 3 .
在本申请的一些实施例中锂盐的浓度为0.5mol/L至1.5mol/L。锂盐浓度过低，电解液的离子电导率低，会影响锂离子电池的倍率和循环性能；锂盐浓度过高，电解液粘度过大，同样影响锂离子电池的倍率性能。可选的，锂盐的浓度为0.8mol/L至1.2mol/L。In some embodiments of the present application, the concentration of the lithium salt is 0.5 mol/L to 1.5 mol/L. If the concentration of lithium salt is too low, the ionic conductivity of the electrolyte will be low, which will affect the rate and cycle performance of the lithium-ion battery; if the concentration of lithium salt is too high, the viscosity of the electrolyte will be too large, which will also affect the rate performance of the lithium-ion battery. Optionally, the concentration of the lithium salt is 0.8 mol/L to 1.2 mol/L.
本申请的还提出一种电化学装置，包括：正极、负极、隔离膜和上述中任一的电解液。上述电化学装置的正极包括正极集流体和设置在所述正极集流体上的正极活性物质层，正极活性物质层包括正极材料。在一些实施方案中，正极材料包括够吸收和释放锂(Li)的正极材料。能够吸收/释放锂(Li)的正极材料的例子可以包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂、锰酸锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、磷酸铁锂、钛酸锂和富锂锰基材料。正极材料可选自下列材料中的一种或多种：LiCoO 2、LiNiO 2、LiMn 2O 4、LiCo 1-yM yO 2、LiNi 1-yM yO 2、LiMn 2-yM yO 4、LiNi xCo yMn zM 1-x-y-zO 2，其中M选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V、Ti中的至少一种，且0≤y≤1,0≤x≤1,0≤z≤1,x+y+z≤1。 The present application also proposes an electrochemical device, comprising: a positive electrode, a negative electrode, a separator, and any one of the above-mentioned electrolytes. The positive electrode of the above electrochemical device includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes a positive electrode material. In some embodiments, the positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li). Examples of cathode materials capable of absorbing/releasing lithium (Li) may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, phosphoric acid Lithium iron, lithium titanate, and lithium-rich manganese-based materials. The positive electrode material can be selected from one or more of the following materials: LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 1-y My O 2 , LiNi 1-y My O 2 , LiMn 2-y My O 4 , LiNi x Co y Mn z M 1-xyz O 2 , wherein M is selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti At least one of , and 0≤y≤1, 0≤x≤1, 0≤z≤1, x+y+z≤1.
电化学装置的正极活性物质层中可以加有导电剂或粘结剂，在本申请的一些实施例中，正极活性物质层还包括碳材料，碳材料可以包括导电炭黑、石墨、石墨烯、碳纳米管、碳纤维或炭黑中的至少一种。粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、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、羧甲基纤维素纳、聚醋酸乙烯酯、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。A conductive agent or a binder may be added to the positive electrode active material layer of the electrochemical device. In some embodiments of the present application, the positive electrode active material layer further includes a carbon material, and the carbon material may include conductive carbon black, graphite, graphene, At least one of carbon nanotubes, carbon fibers or carbon black. The binder may include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-acrylate copolymer, styrene-butadiene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyamide At least one of acrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl acetate, polyethylene pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene .
在一些实施例中，负极包括负极集流体和位于负极集流体上的负极活性物质层，负极活性物质层包括负极材料，负极材料例如可以包括碳材料、金属合金、含锂氧化物及含硅材料等制成。其中，碳材料优选石墨或与石墨相比非晶质的碳包覆在石墨表面而得的碳材料。In some embodiments, the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, and the negative electrode material may include, for example, carbon materials, metal alloys, lithium-containing oxides, and silicon-containing materials etc. made. Among them, the carbon material is preferably graphite or a carbon material obtained by coating the surface of graphite with carbon that is amorphous compared to graphite.
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稳定性。在一些实施例中，隔离膜表面还可包括多孔层，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和粘结剂，无机颗粒选自氧化铝(Al 2O 3)、氧化硅(SiO 2)、氧化镁(MgO)、氧化钛(TiO 2)、 二氧化铪(HfO 2)、氧化锡(SnO 2)、二氧化铈(CeO 2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO 2)、氧化钇(Y 2O 3)、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。粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、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。 In some embodiments, the release membrane includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, or aramid. For example, the polyethylene includes at least one selected from high density polyethylene, low density polyethylene or ultra-high molecular weight polyethylene. Especially polyethylene and polypropylene, they have a good effect on preventing short circuits and can improve the stability of the battery through the shutdown effect. In some embodiments, the surface of the isolation membrane may further include a porous layer, the porous layer is disposed on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from aluminum oxide (Al 2 O 3 ), Silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium dioxide (HfO 2 ), tin oxide (SnO 2 ), ceria (CeO 2 ), nickel oxide (NiO), oxide Zinc (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 sulfuric acid at least one of barium. The binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyethylene At least one of alkanone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene. The porous layer on the surface of the separator can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the pole piece.
本申请还提出一种电子装置，包括上述中任一项的电化学装置。本申请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、照相机和家庭用大型蓄电池等。The present application also provides an electronic device, including the electrochemical device according to any one of the above. The electronic device of the present application is not particularly limited, and it can be used in any electronic device known in the prior art. In some embodiments, electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, and large household batteries, etc.
为了更好的说明本申请实施例中提出的电解液的有益效果，以下将结合实施例以及对比例进行说明，实施例以及对比例的区别仅在于所采用的电解液不同，在实施例以及对比例中将对采用不同电解液的锂离子电池进行性能测试，以说明电解液对锂离子电池性能的影响。In order to better illustrate the beneficial effects of the electrolytes proposed in the embodiments of the present application, the following will be described in conjunction with the examples and comparative examples. The difference between the examples and the comparative examples is only in the electrolytes used. The performance test of lithium-ion batteries with different electrolytes will be carried out in the ratio to illustrate the effect of electrolytes on the performance of lithium-ion batteries.
锂离子电池的制备Preparation of Lithium Ion Batteries
1)正极的制备：将锰酸锂LiMn 2O 4、Super P、聚偏二氟乙烯(PVDF)按照重量比96:2:2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72wt％；将正极浆料均匀涂覆于13μm的铝箔上；将铝箔在85℃下烘干，然后经过冷压、裁片、分切后，在85℃的真空条件下干燥4h，得到正极极片。 1) Preparation of positive electrode: Lithium manganate LiMn 2 O 4 , Super P, and polyvinylidene fluoride (PVDF) were mixed in a weight ratio of 96:2:2, N-methylpyrrolidone (NMP) was added, and the mixture was placed in a vacuum mixer. Under the action of stirring evenly, a positive electrode slurry was obtained, wherein the solid content of the positive electrode slurry was 72 wt%; the positive electrode slurry was uniformly coated on a 13 μm aluminum foil; the aluminum foil was dried at 85°C, and then subjected to cold pressing and cutting , After cutting, it was dried under vacuum condition of 85℃ for 4h to obtain the positive pole piece.
2)负极的制备：将人造石墨、Super P、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按照重量比96.4:1.5:0.5:1.6进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料，其中负极浆料的固含量为54wt％；将负极浆料均匀涂覆在负极集流体铜箔上；将铜箔在85℃下烘干，然后经过冷压、裁片、分切后，在120℃的真空条件下干燥12h，得到负极极片。2) Preparation of negative electrode: artificial graphite, Super P, sodium carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) were mixed according to the weight ratio of 96.4:1.5:0.5:1.6, and deionized water was added. A negative electrode slurry is obtained under the action of the negative electrode slurry, wherein the solid content of the negative electrode slurry is 54wt%; the negative electrode slurry is uniformly coated on the negative electrode current collector copper foil; the copper foil is dried at 85°C, and then subjected to cold pressing and cutting , After cutting, it was dried under vacuum condition of 120℃ for 12h to obtain the negative pole piece.
3)电解液的制备：在干燥的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照质量比为EC:EMC:DEC＝3:5:2进行混合，接着加入添加剂，溶解并充分搅拌后加入锂盐LiPF 6，混合均匀后获得电解液。其中，LiPF 6的浓度为1mol/L。各个实施例的区别在于电解液中所用到的添加剂不同，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含量。 3) Preparation of electrolyte: in a dry argon atmosphere glove box, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are in a mass ratio of EC:EMC:DEC= Mixing at 3:5:2, then adding additives, dissolving and fully stirring, adding lithium salt LiPF 6 , and mixing uniformly to obtain an electrolyte. Among them, the concentration of LiPF 6 is 1 mol/L. The difference between each embodiment is that the additives used in the electrolyte are different. The specific types of additives and their mass percentages in the electrolyte are shown in Tables 1 to 4 below. The content of the additives is calculated based on the total mass of the electrolyte. mass percentage.
4)隔离膜：以聚乙烯(PE)多孔聚合物薄膜作为隔离膜。4) Separator: a polyethylene (PE) porous polymer film is used as the separator.
5)锂离子电池的制备：将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正极极片、负极极片之间起到隔离的作用，然后卷绕得到裸电芯；焊接极耳后将裸电芯置于外包装铝塑膜中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形、容量测试等工序，获得锂离子电池。5) Preparation of lithium ion battery: stack the positive pole piece, the separator and the negative pole piece in order, so that the separator is placed between the positive pole piece and the negative pole piece to play an isolation role, and then roll to obtain a bare cell ; After welding the tabs, place the bare cell in the outer packaging aluminum-plastic film, inject the above-prepared electrolyte into the dried bare cell, and go through the processes of vacuum packaging, standing, forming, shaping, and capacity testing. , to obtain a lithium-ion battery.
锂离子电池的测试过程如下：The test process of lithium-ion battery is as follows:
(1)锂离子电池循环性能测试(1) Lithium-ion battery cycle performance test
将锂离子电池置于45℃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以0.5C恒流充电至电压为4.2V，然后以4.2V恒压充电至电流为0.05C，接着以1C恒流放电至电压为3.0V，此为一个充放电循环。以首次放电的容量为100％，反复进行充放电循环500圈，停止测试，记录循环容量保持率，作为评价锂离子电池循环性能的指标。The lithium-ion battery was placed in a 45°C incubator for 30 minutes to allow the lithium-ion battery to reach a constant temperature. The lithium-ion battery that has reached a constant temperature is charged at a constant current of 0.5C to a voltage of 4.2V, then charged at a constant voltage of 4.2V to a current of 0.05C, and then discharged at a constant current of 1C to a voltage of 3.0V. This is a charge-discharge cycle. . Taking the capacity of the first discharge as 100%, the charge-discharge cycle was repeated for 500 cycles, the test was stopped, and the cycle capacity retention rate was recorded as an index for evaluating the cycle performance of the lithium-ion battery.
循环容量保持率＝第500圈循环的放电容量/首次循环的放电容量。Cycle capacity retention rate=discharge capacity at the 500th cycle/discharge capacity at the first cycle.
测量电池的厚度，按下式计算电池的厚度膨胀率：Measure the thickness of the battery, and calculate the thickness expansion rate of the battery as follows:
厚度膨胀率＝(循环后的电池厚度-循环前的电池厚度)/循环前的电池厚度×100％Thickness swelling ratio = (battery thickness after cycling - battery thickness before cycling)/battery thickness before cycling × 100%
(2)60℃存储厚度膨胀率测试(2) 60℃ storage thickness expansion rate test
将锂离子电池在25℃下以0.5C充电至4.2V，之后在4.2V下恒压充电至0.05C，用千分尺测试并记录此时电池的厚度记为H 11；之后将电池放置到60℃烘箱当中存储24小时，24小时结束后用千分尺测试并记录此时电池的厚度，记为H 12。。 The lithium-ion battery was charged to 4.2V at 0.5C at 25°C, and then charged to 0.05C under constant voltage at 4.2V, and the thickness of the battery was measured and recorded with a micrometer at this time as H 11 ; then the battery was placed at 60°C Store in an oven for 24 hours, and after 24 hours, test with a micrometer and record the thickness of the battery at this time, which is recorded as H 12 . .
锂离子电池60℃存储24小时后的厚度膨胀率(％)＝(H 12-H 11)/H 11×100％ Thickness expansion rate (%) of lithium ion battery after storage at 60°C for 24 hours = (H 12 -H 11 )/H 11 ×100%
(3)140℃热箱通过率测试(3) 140℃ hot box pass rate test
在25℃下，将锂离子电池以0.5C恒流充电至4.2V，4.2V恒压充电至电流为0.05C。将电池放置在高温箱中，用5±2℃/分钟的温升速率加热到140℃，然后保持1h，记录电池的电压、温度以及热箱温度的变化。电池不起火、不爆炸、不冒烟即为通过测试。每组测试10个电池，记录通过测试电池个数。At 25°C, the lithium-ion battery was charged to 4.2V with a constant current of 0.5C and a constant voltage of 4.2V to a current of 0.05C. The battery was placed in a high temperature box, heated to 140 °C with a temperature rise rate of 5 ± 2 °C/min, and then kept for 1 h, and the voltage, temperature of the battery and changes in the temperature of the hot box were recorded. The test is passed if the battery does not catch fire, explode, or emit smoke. Test 10 batteries in each group, and record the number of batteries that pass the test.
(4)85℃存储厚度膨胀率测试(4) 85℃ storage thickness expansion rate test
将锂离子电池在25℃下以0.5C充电至4.2V，之后在4.2V下恒压充电至0.05C，用千分尺测试并记录此时电池的厚度记为H 21；之后将电池放置到85℃烘箱当中存储24小时，24小时结束后用千分尺测试并记录此时电池的厚度，记为H 22。 The lithium-ion battery was charged to 4.2V at 0.5C at 25°C, and then charged to 0.05C under constant voltage at 4.2V. Test and record the thickness of the battery at this time with a micrometer as H 21 ; then place the battery at 85°C Store in an oven for 24 hours. After 24 hours, use a micrometer to test and record the thickness of the battery at this time, which is recorded as H 22 .
锂离子电池85℃存储24小时后的厚度膨胀率(％)＝(H 22-H 21)/H 21×100％ Thickness expansion rate (%) of lithium ion battery after storage at 85°C for 24 hours = (H 22 -H 21 )/H 21 ×100%
实施例1至19以及对比例1至2中使用的添加剂，以及锂离子电池的性能测试结果如表1所示，实施例1至19在电解液中加入了式I化合物，对比例1的电解液中没有添加添加剂，对比例2的电解液中添加了邻苯二甲酸酐。The additives used in Examples 1 to 19 and Comparative Examples 1 to 2, and the performance test results of lithium ion batteries are shown in Table 1. In Examples 1 to 19, the compound of formula I was added to the electrolyte. No additives were added to the solution, and phthalic anhydride was added to the electrolyte of Comparative Example 2.
表1Table 1
Figure PCTCN2021082145-appb-000025
Figure PCTCN2021082145-appb-000025
Figure PCTCN2021082145-appb-000026
Figure PCTCN2021082145-appb-000026
如表1所示，实施例1至19的45℃循环后的容量保持率均高于对比例1和2，且45℃循环后的厚度膨胀率和60℃存储厚度膨胀率均小于对比例1和对比例2，由此可见，相比于在电解液中没有使用添加剂的对比例1，以及使用邻苯二甲酸作为添加剂的对比例2，使用式I化合物能够更好的提高高温循环和高温存储性能，这主要是因为式I化合物可以吸附电解液中的痕量水及HF，增加了电解液的稳定性；同时易于氧化并在正极形成致密的保护膜，减少电解液对正极的破坏；且在首次充放电时优先在负极还原成膜，成膜致密，抑制了电解液在负极的分解反应。As shown in Table 1, the capacity retention rates of Examples 1 to 19 after cycling at 45°C are all higher than those of Comparative Examples 1 and 2, and the thickness expansion rate after cycling at 45°C and the thickness expansion rate after storage at 60°C are both smaller than those of Comparative Example 1 With Comparative Example 2, it can be seen that compared to Comparative Example 1 without using additives in the electrolyte, and Comparative Example 2 using phthalic acid as an additive, the use of the compound of formula I can better improve high temperature cycling and high temperature. Storage performance, this is mainly because the compound of formula I can adsorb trace water and HF in the electrolyte, which increases the stability of the electrolyte; at the same time, it is easy to oxidize and form a dense protective film on the positive electrode, reducing the damage of the electrolyte to the positive electrode; In addition, during the first charge and discharge, the film is preferentially reduced to form a film on the negative electrode, and the film is densely formed, which inhibits the decomposition reaction of the electrolyte solution on the negative electrode.
从实施例1至12可以看出，随着式I化合物的增加，锂离子电池的高温循环性能和高温存储性能先升高后降低，当式I化合物的质量百分含量为1％时性能最佳，这主要是因为该添加量既能有效地稳定电解液，又能够同时在正负极形成优异的界面保护，式I化合物含量过高导致成膜阻抗较大，进而导致电池阻抗增加，会降低电池性能；式I化合物质量含量过低时不足以形成好的界面保护，达不到明显改善电池性能的效果。It can be seen from Examples 1 to 12 that with the increase of the compound of formula I, the high temperature cycle performance and high temperature storage performance of the lithium ion battery first increased and then decreased, and when the mass percentage of the compound of formula I was 1%, the performance was the highest This is mainly because the addition amount can not only effectively stabilize the electrolyte, but also form excellent interface protection at the positive and negative electrodes at the same time. The excessive content of the compound of formula I leads to a large film-forming resistance, which in turn leads to an increase in the battery resistance, which will cause Reduce the battery performance; when the mass content of the compound of formula I is too low, it is insufficient to form good interface protection, and the effect of significantly improving the battery performance cannot be achieved.
从实施例4、16至19可以看出，使用单一类型的式I化合物和使用多种式I化合物均能达到相似的改善效果。As can be seen from Examples 4, 16 to 19, similar improvements can be achieved with a single type of compound of formula I and with multiple compounds of formula I.
实施例4、20至26以及对比例1和3中使用的添加剂，以及锂离子电池的性能测试结果如表2所示，实施例20至26的电解液中加入了式I化合物和含硫氧双键化合物。The additives used in Examples 4, 20 to 26 and Comparative Examples 1 and 3, and the performance test results of lithium ion batteries are shown in Table 2. The electrolytes of Examples 20 to 26 were added with the compound of formula I and sulfur-containing oxygen. Double bond compound.
表2Table 2
Figure PCTCN2021082145-appb-000027
Figure PCTCN2021082145-appb-000027
如表2所示，对比实施例20至26、实施例4以及对比例1和3的数据 可以看出，实施例20至26的45℃循环容量保持率高于实施例4、对比例1和对比例3，且45℃循环厚度膨胀率、60℃存储厚度膨胀率低于实施例4、对比例1和对比例3，由此可见，在含式I化合物电解液中加入含硫氧双键化合物可以继续提升电池的高温循环性能和高温存储性能。这主要是因为含硫双键化合物可以形成富含S元素的界面膜，可以进一步提升界面膜的热稳定性和机械稳定性。因此，联合使用式I化合物和含硫氧双键化合物可以进一步改善锂离子电池的循环性能和高温存储性能。As shown in Table 2, from the data of Comparative Examples 20 to 26, Example 4, and Comparative Examples 1 and 3, it can be seen that the 45°C cycle capacity retention rates of Examples 20 to 26 are higher than those of Example 4, Comparative Examples 1 and 3. Comparative example 3, and the cycle thickness expansion rate at 45°C and the storage thickness expansion rate at 60°C are lower than those in Example 4, Comparative Example 1 and Comparative Example 3. It can be seen that adding a sulfur-oxygen double bond to the electrolyte containing the compound of formula I Compounds can continue to improve the high-temperature cycling performance and high-temperature storage performance of batteries. This is mainly because the sulfur-containing double bond compound can form an interfacial film rich in S element, which can further improve the thermal and mechanical stability of the interfacial film. Therefore, the combined use of the compound of formula I and the sulfur-oxygen double bond-containing compound can further improve the cycle performance and high-temperature storage performance of lithium-ion batteries.
实施例4、27至32以及对比例1和4中使用的添加剂，以及锂离子电池的性能测试结果如表3所示，实施例27至32在电解液中加入了式I化合物和多腈化合物。The additives used in Examples 4, 27 to 32 and Comparative Examples 1 and 4, and the performance test results of lithium ion batteries are shown in Table 3. In Examples 27 to 32, compounds of formula I and polynitrile compounds were added to the electrolyte. .
表3table 3
Figure PCTCN2021082145-appb-000028
Figure PCTCN2021082145-appb-000028
如表3所示，实施例27至32的45℃循环容量保持率和热箱通过率高于实施例4、对比例1和对比例4，且85℃存储厚度膨胀率低于实施例4、对比例1和对比例4，由此可见，当向电解液中进一步加入多腈化合物后，锂离子电池的45℃循环容量保持率提升、85℃存储厚度膨胀率下降且热箱通过率提高，可见多腈化合物的加入提高了锂离子电池的循环性能、高温存储性能和安全性能，这是因为多腈化合物能够与电解液中的式I化合物形成协同作用，可形成更加稳定的SEI膜，进而进一步改善锂离子电池高温循环、高温存储性能和热箱性能。As shown in Table 3, the 45°C cycle capacity retention rate and hot box throughput rate of Examples 27 to 32 are higher than those of Example 4, Comparative Example 1 and Comparative Example 4, and the storage thickness expansion rate at 85°C is lower than that of Example 4, Comparing Example 1 and Comparative Example 4, it can be seen that when the polynitrile compound is further added to the electrolyte, the 45 ℃ cycle capacity retention rate of the lithium-ion battery increases, the 85 ℃ storage thickness expansion rate decreases, and the hot box pass rate increases, It can be seen that the addition of polynitrile compounds improves the cycle performance, high temperature storage performance and safety performance of lithium-ion batteries, because the polynitrile compounds can form a synergistic effect with the compound of formula I in the electrolyte, which can form a more stable SEI film, and then Further improve the high temperature cycling, high temperature storage performance and hot box performance of Li-ion batteries.
实施例4、33至37以及对比例1和5中使用的添加剂，以及锂离子电池的性能测试结果如表4所示，实施例33至37在电解液中加入了式I化合物和环状碳酸酯化合物。The additives used in Examples 4, 33 to 37 and Comparative Examples 1 and 5, and the performance test results of lithium ion batteries are shown in Table 4. In Examples 33 to 37, the compound of formula I and cyclic carbonic acid were added to the electrolyte. ester compound.
表4Table 4
Figure PCTCN2021082145-appb-000029
Figure PCTCN2021082145-appb-000029
如表4所示，实施例33至37的45℃循环容量保持率高于实施例4、对比例1和对比例5，且45℃循环厚度膨胀率和60℃存储厚度膨胀率低于实施例4、对比例1和对比例5，由此可见，当向电解液中进一步加入本申请所述的环状碳酸酯化合物时，可形成更加稳定的SEI膜，从而进一步改善锂离子电池高温循环和高温存储性能，并且无论是使用单一种类的环状碳酸酯化合物还是使用多种环状碳酸酯化合物均能达到相似的效果。As shown in Table 4, the 45°C cycle capacity retention rates of Examples 33 to 37 are higher than those of Example 4, Comparative Example 1 and Comparative Example 5, and the 45°C cycle thickness expansion ratio and the 60°C storage thickness expansion ratio are lower than those of Examples 4. Comparative Example 1 and Comparative Example 5, it can be seen that when the cyclic carbonate compound described in this application is further added to the electrolyte, a more stable SEI film can be formed, thereby further improving the high temperature cycle and the lithium ion battery. High temperature storage performance, and similar effects can be achieved whether a single species of cyclic carbonate compound or multiple cyclic carbonate compounds are used.
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，同时也应涵盖在不脱离上述公开构思的情况下，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(但不限于)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。The above description is only a preferred embodiment of the present application and an illustration of the applied technical principles. Those skilled in the art should understand that the scope of disclosure involved in this application is not limited to the technical solutions formed by the specific combination of the above-mentioned technical features, and should also cover, without departing from the above-mentioned disclosed concept, the technical solutions made of the above-mentioned technical features or Other technical solutions formed by any combination of its equivalent features. For example, a technical solution is formed by replacing the above-mentioned features with the technical features disclosed in this application (but not limited to) with similar functions.
尽管已经采用特定于结构特征和/或方法逻辑动作的语言描述了本主题，但是应当理解所附权利要求书中所限定的主题未必局限于上面描述的特定特征或动作。相反，上面所描述的特定特征和动作仅仅是实现权利要求书的示例形式。Although the subject matter has been described in language specific to structural features and/or logical acts of method, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are merely example forms of implementing the claims.

Claims (15)

  1. 一种电解液，其特征在于，包括：式I化合物；An electrolyte, comprising: a compound of formula I;
    Figure PCTCN2021082145-appb-100001
    Figure PCTCN2021082145-appb-100001
    其中，A选自-C(＝O)-或-S(＝O) 2-；R 1选自经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素；R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 20的烷基或杂烷基、经取代或未经取代的C 1至C 20的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 20的烯基或杂烯基、经取代或未经取代的C 2至C 20的炔基或杂炔基、经取代或未经取代C 6至C 20的芳基或杂芳基、经取代或未经取代的C 3至C 20的脂环烃基、经取代或未经取代的C 2至C 20杂环基中的任意一种，其中，当经取代时，取代基包括卤素； Wherein, A is selected from -C(=O)- or -S(=O) 2 -; R 1 is selected from substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted Substituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted C3 to C20 alicyclic hydrocarbyl, substituted or unsubstituted Any one of the C 2 to C 20 heterocyclyl groups, wherein, when substituted, the substituent includes halogen; R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 20 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 20 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 20 alkene alkynyl or heteroalkenyl, substituted or unsubstituted C2 to C20 alkynyl or heteroalkynyl, substituted or unsubstituted C6 to C20 aryl or heteroaryl, substituted or unsubstituted Any of a substituted C3 to C20 alicyclic hydrocarbon group, a substituted or unsubstituted C2 to C20 heterocyclic group, wherein, when substituted, the substituent includes a halogen;
    当含杂原子时，杂原子包括O、N、P、S、Si或B中的至少一种；When containing heteroatoms, the heteroatoms include at least one of O, N, P, S, Si or B;
    n选自1或2；m选自0或1；m+n＝2。n is selected from 1 or 2; m is selected from 0 or 1; m+n=2.
  2. 根据权利要求1所述的电解液，其特征在于，所述R 1选自经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种；所述R 2、R 3和R 4各自独立地选自氢、卤素、经取代或未经取代的C 1至C 10的烷基或杂烷基、经取代或未经取代的C 1至C 10的烷氧基或杂烷氧基、经取代或未经取代的C 2至C 10的烯基或杂烯基、经取代或未经取代的C 2至C 10的炔基或杂炔基、经取代或未经取代C 6至C 10的芳基 或杂芳基、经取代或未经取代的C 3至C 10的脂环烃基、经取代或未经取代的C 2至C 10杂环基中的任意一种。 The electrolyte according to claim 1, wherein the R 1 is selected from substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 10 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 10 alkynyl or heteroalkyne base, substituted or unsubstituted C6 to C10 aryl or heteroaryl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted C2 to C10 Any one of heterocyclyl; said R 2 , R 3 and R 4 are each independently selected from hydrogen, halogen, substituted or unsubstituted C 1 to C 10 alkyl or heteroalkyl, substituted or unsubstituted C 1 to C 10 alkoxy or heteroalkoxy, substituted or unsubstituted C 2 to C 10 alkenyl or heteroalkenyl, substituted or unsubstituted C 2 to C 10 alkynyl or heteroalkynyl, substituted or unsubstituted C 6 to C 10 aryl or heteroaryl, substituted or unsubstituted C 3 to C 10 alicyclic hydrocarbyl, substituted or unsubstituted Any of substituted C 2 to C 10 heterocyclyl.
  3. 根据权利要求1所述的电解液，所述式I化合物包括如下所示化合物中的至少一种：The electrolyte according to claim 1, the compound of formula I comprises at least one of the following compounds:
    Figure PCTCN2021082145-appb-100002
    Figure PCTCN2021082145-appb-100002
    Figure PCTCN2021082145-appb-100003
    Figure PCTCN2021082145-appb-100003
  4. 根据权利要求1所述的电解液，其特征在于，基于所述电解液的质量，所述式I化合物的质量百分含量为0.01％至5％。The electrolyte solution according to claim 1, characterized in that, based on the mass of the electrolyte solution, the mass percentage content of the compound of formula I is 0.01% to 5%.
  5. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括含硫氧双键化合物，所述含硫氧双键化合物包括式(II-A)和式(II-B)表示的化合物中的至少一种；The electrolyte solution according to claim 1, characterized in that, the electrolyte solution further comprises a sulfur-oxygen double bond-containing compound, and the sulfur-oxygen double bond-containing compound comprises formulas (II-A) and (II-B) represented by formula (II-A) and formula (II-B). at least one of the compounds;
    Figure PCTCN2021082145-appb-100004
    Figure PCTCN2021082145-appb-100004
    在式(II-A)和式(II-B)中，R 21、R 22、R 23和R 24各自独立地选自经取代或未经取代的C 1至C 5烷基、经取代或未经取代的C 2至C 10烯基、经取代或未经取代的C 2至C 10炔基、经取代或未经取代的C 3至C 10脂环烃基、经取代或未经取代的C 6至C 10芳基、经取代或未经取代的C 1至C 6含杂原子基团中的任意一种，并且，当经取代时，取代基包括卤素和含杂原子基团中的至少一种，所述杂原子包括O、S、P、N、Si或B中的至少一种，其中，R 21和R 22之间可以键合而形成环结构，R 23和R 24之间可以键合而形成环结构。 In formula (II-A) and formula (II-B), R 21 , R 22 , R 23 and R 24 are each independently selected from substituted or unsubstituted C 1 to C 5 alkyl, substituted or Unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C10 alicyclic hydrocarbon group, substituted or unsubstituted Any one of C 6 to C 10 aryl, substituted or unsubstituted C 1 to C 6 heteroatom-containing groups, and, when substituted, the substituents include halogen and heteroatom-containing groups At least one, the heteroatom includes at least one of O, S, P, N, Si or B, wherein R 21 and R 22 can be bonded to form a ring structure, and between R 23 and R 24 Can be bonded to form a ring structure.
  6. 根据权利要求5所述的电解液，其特征在于，所述含硫氧双键化合物包括式(II-1)至式(II-20)表示的化合物中的至少一种；The electrolyte according to claim 5, wherein the sulfur-oxygen double bond-containing compound comprises at least one of the compounds represented by formula (II-1) to formula (II-20);
    Figure PCTCN2021082145-appb-100005
    Figure PCTCN2021082145-appb-100005
  7. 根据权利要求5所述的电解液，其特征在于，基于所述电解液的质量，所述含硫氧双键化合物的质量百分含量为0.01％至5％。The electrolyte solution according to claim 5, characterized in that, based on the mass of the electrolyte solution, the mass percentage of the sulfur-oxygen double bond-containing compound is 0.01% to 5%.
  8. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括多腈化合物；所述多腈化合物包括式III表示的化合物中的至少一种；The electrolyte according to claim 1, characterized in that, the electrolyte further comprises a polynitrile compound; the polynitrile compound comprises at least one of the compounds represented by formula III;
    Figure PCTCN2021082145-appb-100006
    Figure PCTCN2021082145-appb-100006
    在式III中，In formula III,
    R 31、R 32、R 33、R 34各自独立地选自氢、经取代或未经取代的C 1至C 10烷基、经取代或未经取代的-(CH 2) a-CN、经取代或未经取代的-(CH 2) b-O-(CH 2) c-CN、经取代或未经取代的-(CH 2) d-CH＝CH-(CH 2) k-CN、经取 代或未经取代的
    Figure PCTCN2021082145-appb-100007
    经取代或未经取代的
    Figure PCTCN2021082145-appb-100008
    经取代或未经取代的烷氧基羰基中的任意一种，其中，a、b、c、d、e、f、g、h、i、j、k各自独立地选自0至10的整数，并且，当经取代时，取代基包括卤素中的至少一种；     R 31 , R 32 , R 33 , R 34 are each independently selected from hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted -(CH 2 ) a -CN, Substituted or unsubstituted -(CH 2 ) b -O-(CH 2 ) c -CN, substituted or unsubstituted -(CH 2 ) d -CH=CH-(CH 2 ) k -CN, substituted or unsubstituted substituted or unsubstituted
    Figure PCTCN2021082145-appb-100007
    substituted or unsubstituted
    Figure PCTCN2021082145-appb-100008
    Any of a substituted or unsubstituted alkoxycarbonyl group, wherein a, b, c, d, e, f, g, h, i, j, k are each independently an integer from 0 to 10 , and, when substituted, the substituent includes at least one of halogen;
    x选自0至3的整数，并且，当n选自1至3的整数时，R 31、R 32、R 33、R 34中的至少两个为含有氰基的基团，当n选自0时，R 32和R 34均至少含有氰基基团。 x is selected from an integer of 0 to 3, and, when n is selected from an integer of 1 to 3, at least two of R 31 , R 32 , R 33 , R 34 are groups containing a cyano group, and when n is selected from When 0, both R 32 and R 34 contain at least a cyano group.
  9. 根据权利要求8所述的电解液，其特征在于，所述多腈化合物包括式III-1至式III-18表示的化合物中的至少一种；The electrolyte according to claim 8, wherein the polynitrile compound comprises at least one of the compounds represented by formula III-1 to formula III-18;
    Figure PCTCN2021082145-appb-100009
    Figure PCTCN2021082145-appb-100009
    Figure PCTCN2021082145-appb-100010
    Figure PCTCN2021082145-appb-100010
  10. 根据权利要求8所述的电解液，其特征在于，基于所述电解液的质量，所述多腈化合物的质量百分含量为0.5％至10％。The electrolyte according to claim 8, wherein, based on the mass of the electrolyte, the mass percentage of the polynitrile compound is 0.5% to 10%.
  11. 根据权利要求1所述的电解液，其特征在于，所述电解液还包括环状碳酸酯化合物；所述环状碳酸酯化合物包括式Ⅳ-A或Ⅳ-B表示的化合物中的至少一种；The electrolyte according to claim 1, wherein the electrolyte further comprises a cyclic carbonate compound; the cyclic carbonate compound comprises at least one of compounds represented by formula IV-A or IV-B ;
    Figure PCTCN2021082145-appb-100011
    Figure PCTCN2021082145-appb-100011
    R 41和R 42各自独立地选自氢、卤素、经氟取代或未经氟取代的C 1至C 5的烷基、C 2至C 5的烯基中的任意一种； R 41 and R 42 are each independently selected from any one of hydrogen, halogen, fluorine-substituted or unsubstituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl;
    R 43、R 44各自独立地选自氢、卤素和经氟取代的C 1至C 5烷基、C 2至C 5的烯基中的任意一种，条件是R 43和R 44中的至少一个选自卤素、经氟取代的C 1至C 5的烷基或C 2至C 5的烯基。 R 43 , R 44 are each independently selected from any one of hydrogen, halogen and fluorine-substituted C 1 to C 5 alkyl, C 2 to C 5 alkenyl, provided that at least one of R 43 and R 44 One is selected from halogen, fluorine substituted C1 to C5 alkyl or C2 to C5 alkenyl.
  12. 根据权利要求11所述电解液，其特征在于，所环状碳酸酯化合物包括式Ⅳ-1至式Ⅳ-7表示的化合物中的至少一种；The electrolyte according to claim 11, wherein the cyclic carbonate compound comprises at least one of the compounds represented by formula IV-1 to formula IV-7;
    Figure PCTCN2021082145-appb-100012
    Figure PCTCN2021082145-appb-100012
  13. 根据权利要求11所述的电解液，其特征在于，基于所述电解液的质量，所述环状碳酸酯化合物的质量百分含量为0.01％至5％。The electrolyte solution according to claim 11, wherein, based on the mass of the electrolyte solution, the mass percentage content of the cyclic carbonate compound is 0.01% to 5%.
  14. 一种电化学装置，其特征在于，包括如权利要求1至13中任一项所述的电解液。An electrochemical device, characterized by comprising the electrolyte according to any one of claims 1 to 13.
  15. 一种电子装置，其特征在于，包括如权利要求14所述的电化学装置。An electronic device, characterized by comprising the electrochemical device as claimed in claim 14 .
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