WO2024197800A1 - 一种电化学装置和电子装置 - Google Patents

一种电化学装置和电子装置 Download PDF

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WO2024197800A1
WO2024197800A1 PCT/CN2023/085420 CN2023085420W WO2024197800A1 WO 2024197800 A1 WO2024197800 A1 WO 2024197800A1 CN 2023085420 W CN2023085420 W CN 2023085420W WO 2024197800 A1 WO2024197800 A1 WO 2024197800A1
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lithium
negative electrode
carbonate
electrolyte
electrochemical device
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French (fr)
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王翔
简俊华
唐超
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to CN202380012125.3A priority Critical patent/CN117461182A/zh
Priority to PCT/CN2023/085420 priority patent/WO2024197800A1/zh
Publication of WO2024197800A1 publication Critical patent/WO2024197800A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of electrochemical technology, and in particular to an electrochemical device and an electronic device.
  • the theoretical gram capacity of silicon material is 4200mAh/g, which is much higher than the theoretical gram capacity of graphite material 372mAh/g, but the volume of silicon material expands greatly during the charging and discharging process, and the electrolyte is continuously consumed and decomposed on the surface, resulting in serious cycle capacity decay.
  • the accumulation of by-products causes serious lithium precipitation during charging, making it difficult for silicon materials to be commercialized in lithium-ion batteries.
  • the methods currently used are to modify the structure of silicon materials or add fluoroethylene carbonate to the electrolyte to form interface protection. These methods improve the cycle stability of silicon negative electrodes to a certain extent, but the improvement effect and stability are limited, and they are basically unhelpful in improving the charge rate window. Therefore, how to improve the charge rate window on the basis of improving the cycle performance of lithium-ion batteries containing silicon negative electrodes is a technical problem that needs to be solved urgently by those skilled in the art.
  • the present application provides an electrochemical device and an electronic device to improve the cycle performance and charge rate window of the electrochemical device.
  • lithium-ion batteries are used as an example of electrochemical devices to explain this application, but the electrochemical devices of this application are not limited to lithium-ion batteries.
  • the specific technical solutions are as follows:
  • the present application provides an electrochemical device, comprising an electrolyte, a negative electrode plate, a separator and a positive electrode plate; the electrolyte comprises a compound of formula (I) and a polymerized monomer:
  • X1 , X2 , X3 , X4 , Y1 , Y2 , Y3 and Y4 are each independently selected from O, a C1 to C3 carbon chain or a single bond, X1 and Y1 are not O or a single bond at the same time, X2 and Y2 are not O or a single bond at the same time, X3 and Y3 are not O or a single bond at the same time, X4 and Y4 are not O or a single bond at the same time, at least one of X1 , X2 , Y1 and Y2 is O, and X3 , X4 , Y3 and Y4 are not O or a single bond at the same time.
  • Z1 and Z2 are each independently selected from halogen or C1 to C2 with a terminal polymerization functional group 4 carbon chains, the polymerized functional groups include carboxyl, hydroxyl, aldehyde, acyloxy, amino, alkenyl or alkynyl; the polymerized monomers include at least one of methyl acrylate, methyl methacrylate, vinylene carbonate, vinyl ethylene carbonate, ethylene, propylene, vinyl acetate, difluoroethylene, tetrafluoroethylene, hexafluoropropylene, acrylonitrile, ethylene glycol, ethylene glycol diacrylate, diethylene glycol diacrylate, ethylene oxide, dioxolane, 2,6-dimethylphenol, 3,4-ethylenedioxythiophene or 4,6-diamino-1,3-diphenol; based on the mass of the electrolyte, the mass percentage of the compound of formula (I) is m%, 0.
  • the compounds of formula (I) and the polymerized monomers can be cross-linked and polymerized to produce a regular structure similar to an organic molecular skeleton (COFs) on the positive electrode sheet and the negative electrode sheet.
  • This structure as a mesh skeleton of the SEI film, takes into account both rigidity and flexibility, can block the contact between the electrolyte and the negative electrode sheet, and inhibit the oxidative decomposition of the organic solvent in the electrolyte under high voltage.
  • the above-mentioned skeleton structure is combined with the electrolyte to make the electrochemical device have a lower impedance.
  • the electrochemical device can still improve the cycle performance under high-rate charging conditions. As a result, the cycle performance and charge rate window of the electrochemical device are improved.
  • the mass percentage of the polymerized monomer is controlled within the above preferred range, the cycle performance and charge rate window of the electrochemical device are better.
  • the compound of formula (I) includes at least one of the following compounds of formula (I-1) to formula (I-8):
  • the molar mass of the compound of formula (I) is M (I) g/mol
  • the molar mass of the polymerized monomer is M single g/mol
  • m, n, M (I) and M single satisfy: 2 ⁇ (n/M single )/(m/M (I) ) ⁇ 200.
  • the negative electrode material layer further includes an inorganic solid electrolyte, and the inorganic solid electrolyte includes any one of an inorganic oxide material or an inorganic sulfide material; based on the mass of the negative electrode material layer, the mass percentage of the inorganic solid electrolyte is ⁇ %, and 0.01 ⁇ 5.
  • the negative electrode material layer includes an inorganic solid electrolyte, and the mass percentage of the inorganic solid electrolyte in the negative electrode material layer is regulated within the above range, which is conducive to improving the cycle performance and charge rate window of the electrochemical device.
  • 0.5 ⁇ n/ ⁇ 100, and regulating the value of n/ ⁇ within the above range is beneficial to improving the cycle performance and charge rate window of the electrochemical device.
  • the crystalline structure of the inorganic oxide material includes at least one of NASICON type, LISICON type, perovskite type or garnet type;
  • the chemical formula of the NASICON type inorganic oxide material is Li 1+x M1 x D1 2-x (PO 4 ) 3 , wherein 0.01 ⁇ x ⁇ 0.5, M1 includes at least one of Al, Y, Ga, Cr, In, Fe, Se or La, and D1 includes at least one of Ti, Ge, Ta, Zr, Sn, Fe, V, and Hf;
  • the chemical formula of the LISICON type inorganic oxide material is Li 14 M2(D2O 4 ) 4 , wherein M2 includes at least one of Zr, Cr, Sn or Zn, and D2 includes at least one of Si, Ge, S or P;
  • the chemical formula of the perovskite type inorganic oxide material is Li 3y M3 2/3-y D3O 3 , wherein 0.01 ⁇ y ⁇ 0.5, M3 includes at least
  • the electrolyte further includes an initiator, and the initiator includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, or methyl ethyl ketone peroxide; based on the mass of the electrolyte, the mass percentage of the initiator is 0.001% to 2%.
  • the electrolyte includes the above-mentioned types of initiators and the mass percentage of the initiator in the electrolyte is regulated within the above range, which is conducive to improving the cycle performance and charge rate window of the electrochemical device.
  • the electrolyte further includes an additive containing an unsaturated bond
  • the additive containing an unsaturated bond includes at least one of fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, 1,3-propylene sultone, 1,3-propane sultone, 3-hexenedicyanide, fumaric anhydride or triallylmethoxysilane; based on the mass of the electrolyte, the mass percentage of the additive containing an unsaturated bond is 0.01% to 40%.
  • the electrolyte includes the above-mentioned type of additive containing an unsaturated bond, and the mass percentage of the additive containing an unsaturated bond is regulated within the above range, which is conducive to improving the cycle performance and charge rate window of the electrochemical device.
  • the silicon-containing negative electrode active material includes at least one of SiO w , a silicon-carbon compound, or a silicon single substance, and 0.5 ⁇ w ⁇ 1.5.
  • the electrolyte further includes an organic solvent
  • the organic solvent includes at least one of a carbonate, a carboxylate or an ether
  • the carbonate includes at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, dipropyl carbonate, methylpropyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, pentafluoropropyl ethylene carbonate, methyl trifluoroethyl carbonate, trifluoromethyl ethylene carbonate or di(2,2,2-trifluoroethyl) carbonate
  • the carboxylate includes at least one of propyl propionate, ethyl propionate, ethyl acetate, ethyl formate, methyl acetate, methyl propionate, propyl acetate, butyl butyrate, ethyl difluoroacetate, difluoroeth
  • the ether includes at least one of 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol formic acid ethyl ether, diethoxymethane, 1,3-dimethoxypropane, 1,1,3,3-tetraethoxypropane ether or 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether; based on the mass of the electrolyte, the mass percentage of carbonate is 20% to 80%, the mass percentage of carboxylic acid ester is 0% to 40%, and the mass percentage of ether is 0% to 60%.
  • the electrolyte also includes a lithium salt
  • the lithium salt includes at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetraphenylborate, lithium methanesulfonate, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(trifluoromethylsulfonyl)methyl lithium, lithium hexafluorosilicate, lithium dioxalatoborate or lithium difluorooxalatoborate; based on the mass of the electrolyte, the mass percentage of the lithium salt is 6% to 20%.
  • the second aspect of the present application provides an electronic device, which includes the electrochemical device described in any of the above embodiments. Therefore, the electronic device has good performance.
  • the present application provides an electrochemical device and an electronic device, wherein the electrochemical device comprises an electrolyte, a negative electrode sheet, The separator and the positive electrode plate; the electrolyte comprises a compound of formula (I) and a polymerized monomer, based on the mass of the electrolyte, the mass percentage of the compound of formula (I) is m%, 0.01 ⁇ m ⁇ 6, and the mass percentage of the polymerized monomer is n%, 0.5 ⁇ n ⁇ 10; the negative electrode plate comprises a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, and the negative electrode material layer comprises a silicon-containing negative electrode active material.
  • the electrochemical device obtained by the above arrangement has good cycle performance and a wide charging rate window.
  • lithium-ion batteries are used as an example of electrochemical devices to explain the present application, but the electrochemical devices of the present application are not limited to lithium-ion batteries.
  • the specific technical solutions are as follows:
  • the present application provides an electrochemical device, comprising an electrolyte, a negative electrode plate, a separator and a positive electrode plate; the electrolyte comprises a compound of formula (I) and a polymerized monomer:
  • X1 , X2 , X3 , X4 , Y1 , Y2 , Y3 and Y4 are each independently selected from O, a C1 to C3 carbon chain or a single bond, X1 and Y1 are not O or a single bond at the same time, X2 and Y2 are not O or a single bond at the same time, X3 and Y3 are not O or a single bond at the same time, X4 and Y4 are not O or a single bond at the same time, at least one of X1 , X2 , Y1 and Y2 is O, and at least one of X3 , X4 , Y3 and Y4 is O; Z1 and Z2 are each independently selected from halogen or a C1 to C3 carbon chain having a polymerizable functional group at the end; 4 carbon chains, the polymerized functional groups include carboxyl, hydroxyl, aldehyde, acyloxy
  • n is 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or any value between any two of the above numerical ranges.
  • the inventors have found through extensive research that the compound of formula (I) and the polymerized monomer have the function of cross-linking polymerization, and can form a two-dimensional network or three-dimensional cage-shaped organic polymer, or the polymerized monomer undergoes polymerization to form the main chain segment and the monomer and oligomer of the functional chain segment of the organic polymer, which are attached to the surface of the silicon-containing negative electrode active material.
  • the oxygen in the cyclic ether bond of the compound of formula (I) easily forms a hydrogen bond with the hydroxyl group on the surface of the silicon-containing negative electrode active material, and has affinity with the interface of the silicon-containing negative electrode active material.
  • the mass percentage of the compound of formula (I) is less than 0.01%, and/or the mass percentage of the polymerized monomer is less than 0.5%, and the amount of organic polymer generated is insufficient, which easily causes poor contact between the inorganic solid electrolyte and the negative electrode active material particles, thereby increasing the impedance of the negative electrode plate and the polarization of the electrochemical device; the mass percentage of the compound of formula (I) is greater than 6%, and/or the mass percentage of the polymerized monomer is greater than 10%, and the amount of organic polymer generated is too much, which easily causes the lithium ion desolvation energy barrier to rise, thereby the negative electrode plate impedance will also be too large, charging lithium deposition, in addition, it will also cause a large number of residual monomers, continuous reaction and consumption of lithium ions during the charge and discharge process, and rapid capacity decay of the electrochemical device.
  • the compounds of formula (I) and the polymerized monomers can be cross-linked and polymerized to produce a regular structure similar to a covalent organic framework (COFs) on the positive electrode and the negative electrode.
  • COFs covalent organic framework
  • the structure as a mesh skeleton of the SEI film, takes into account both rigidity and flexibility, can block the contact between the electrolyte and the negative electrode, and inhibit the oxidative decomposition of the organic solvent in the electrolyte at a high voltage (greater than or equal to 4.25V).
  • the above-mentioned skeleton structure is combined with the electrolyte to make the electrochemical device have a lower impedance, so that even if the silicon-containing negative electrode active material expands in volume during the charge and discharge process of the electrochemical device, the electrochemical device can still improve the cycle performance under high rate (greater than or equal to 0.5C) charging conditions. As a result, the cycle performance and charge rate window of the electrochemical device are improved.
  • negative electrode material layer disposed on at least one surface of the negative electrode current collector means that the negative electrode material layer can be disposed on one surface of the negative electrode current collector or on both surfaces of the negative electrode current collector, and the above-mentioned “surface” refers to the entire area or a portion of the surface of the negative electrode current collector.
  • m is 0.05, 0.5, 1, 1.5, 2, 2.5, 3 or any value between any two of the above numerical ranges.
  • n is 1, 2, 3, 4, 5, 6, or any number between any two of the above ranges.
  • the compound of formula (I) includes at least one of the following compounds of formula (I-1) to formula (I-8):
  • the molar mass of the compound of formula (I) is M (I) g/mol
  • the molar mass of the polymerized monomer is M single g/mol
  • m, n, M (I) and M single satisfy: 2 ⁇ (n/M single )/(m/M (I) ) ⁇ 200.
  • the value of (n/M single )/(m/M (I) ) is 2, 3, 10, 20, 30, 50, 100, 150, 200 or any value between any two of the above numerical ranges.
  • the compound of formula (I) and the polymerized monomer can realize directional control of the organic polymer repeating unit composition and design of the organic polymer type.
  • the compound of formula (I) and the polymerized monomer have a polymer structure formed by cross-linking polymerization, which has more suitable rigidity and flexibility, is beneficial to blocking the contact between the electrolyte and the negative electrode plate, inhibits the oxidative decomposition of the organic solvent in the electrolyte under high voltage, and is beneficial to reducing the impedance of the electrochemical device, thereby improving the cycle performance and charge rate window of the electrochemical device.
  • (n/M single )/(m/M (I) ) can also be understood as ⁇ (n/M single )/ ⁇ (m/M (I) ).
  • the negative electrode material layer also includes an inorganic solid electrolyte, and the inorganic solid electrolyte includes any one of an inorganic oxide material or an inorganic sulfide material; based on the mass of the negative electrode material layer, the mass percentage of the inorganic solid electrolyte is ⁇ %, and 0.01 ⁇ 5.
  • the value of ⁇ is 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or any value between any two of the above numerical ranges.
  • the negative electrode material layer includes an inorganic solid electrolyte, and the silicon-containing negative electrode active material is partially or completely coated by the inorganic solid electrolyte.
  • the inorganic solid electrolyte has good electrical conductivity and mechanical stability, and can improve the charging performance and cycle stability of the negative electrode plate.
  • the silicon-containing negative electrode active material coated with the inorganic solid electrolyte works synergistically with the electrolyte containing the compound of formula (I) and the polymerized monomer in the present application.
  • the electrolyte is polymerized in situ to form a negative electrode SEI film, which complements the inorganic solid electrolyte, improves the interface compatibility between the electrolyte and the negative electrode plate, and can improve the cycle performance and rate performance of the high energy density silicon-based negative electrode.
  • the mass percentage of the inorganic solid electrolyte in the negative electrode material layer is controlled within the above range, matching the content of the compound of formula (I) and the polymerized monomer, which can stabilize the interface between the negative electrode plate and the electrolyte, and widen the charge rate window of the electrochemical device of the silicon-based negative electrode to 0.5C and above, thereby improving the cycle performance and charge rate window of the electrochemical device.
  • 0.5 ⁇ n/ ⁇ 100 In some embodiments of the present application, 0.5 ⁇ n/ ⁇ 100.
  • the value of n/ ⁇ is 0.5, 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 or any value between any two of the above numerical ranges.
  • the inorganic solid electrolyte has the function of a fast ion conductor, and the value of n/ ⁇ is regulated within the above range.
  • the contact interface between the inorganic solid electrolyte and the silicon-containing negative electrode active material has good density, and the SEI film generated by the in-situ polymerization of the polymerized monomer has a good protective effect on the silicon-containing negative electrode active material, so that the possibility of the silicon-containing negative electrode active material breaking and decomposing during the charge and discharge cycle of the electrochemical device is reduced, and the electrolyte has a suitable degree of polymerization, and there are enough liquid components remaining after the polymerized monomers are polymerized, so that the electrochemical device has a lower impedance. As a result, the cycle performance and charge rate window of the electrochemical device are improved.
  • ⁇ is 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or any value between any two of the above numerical ranges. Controlling the mass percentage of the inorganic solid electrolyte in the negative electrode material layer within the above preferred range is conducive to further improving the cycle performance and charge rate window of the electrochemical device.
  • n/ ⁇ 30 Preferably, 1 ⁇ n/ ⁇ 30.
  • the value of n/ ⁇ is 1, 5, 10, 15, 20, 25, 30, or any value between any two of the above ranges. Regulating the value of n/ ⁇ within the above preferred range is beneficial to further improve the cycle performance and charge rate window of the electrochemical device.
  • 0.1 ⁇ 5, 1 ⁇ n/ ⁇ 30 Preferably, 0.1 ⁇ 5, 1 ⁇ n/ ⁇ 30. Controlling the mass percentage of the inorganic solid electrolyte in the negative electrode material layer and the value of n/ ⁇ within the above preferred ranges is beneficial to further improving the cycle performance and charge rate window of the electrochemical device.
  • the crystalline structure of the inorganic oxide material includes NASICON type, LISICON type
  • the chemical formula of the NASICON type inorganic oxide material is Li 1+x M1 x D1 2-x (PO 4 ) 3 , wherein 0.01 ⁇ x ⁇ 0.5, M1 includes at least one of Al, Y, Ga, Cr, In, Fe, Se or La, and D1 includes at least one of Ti, Ge, Ta, Zr, Sn, Fe, V and Hf;
  • the chemical formula of the LISICON type inorganic oxide material is Li 14 M2(D2O 4 ) 4 , wherein M2 includes at least one of Zr, Cr, Sn or Zn, and D2 includes at least one of Si, Ge, S or P;
  • the chemical formula of the perovskite type inorganic oxide material is Li 3y M3 2/3-y D3O 3 , wherein 0.01 ⁇ y ⁇ 0.5, M3 includes at least one of La, Al, Mg, Fe or Ta, and D3
  • the electrolyte includes the above-mentioned type of initiator and the mass percentage of the initiator in the electrolyte is regulated within the above-mentioned range.
  • the initiator can further enhance the polymerization effect of the compound of formula (I) and the polymerized monomer, as well as the polymerization effect of the polymerized monomer itself, so as to form an organic polymer that is better attached to the surface of the silicon-containing negative electrode active material and/or the surface of the inorganic solid electrolyte to block the contact between the electrolyte and the negative electrode plate, inhibit the oxidative decomposition of the organic solvent in the electrolyte under high voltage, reduce the impedance of the electrochemical device, and thus improve the cycle performance and charge rate window of the electrochemical device.
  • the compound of formula (I) and the polymerized monomer, or the polymerized monomer can also be induced to undergo polymerization reaction under any of the initiation modes of electrical initiation (current catalytic polymerization reaction), photoinitiation (ultraviolet light catalytic polymerization reaction) or thermal initiation (high temperature catalytic polymerization reaction) to form an organic polymer, or monomers and oligomers of the main chain segment and functional segment of the organic polymer, which are attached to the surface of the silicon-containing negative electrode active material and the surface of the inorganic solid electrolyte.
  • electrical initiation current catalytic polymerization reaction
  • photoinitiation ultraviolet light catalytic polymerization reaction
  • thermal initiation high temperature catalytic polymerization reaction
  • the cross-linking polymerization of the compound of formula (I) and the polymerized monomer to form an organic polymer, and the polymerization of the polymerized monomer to form an organic polymer are all generated in the electrochemical device process stage.
  • the polymerization is initiated by heat, or in the formation stage, the polymerization is initiated by electricity.
  • the electrolyte further comprises an additive containing an unsaturated bond.
  • the additive includes at least one of fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, 1,3-propylene sultone, 1,3-propane sultone, 3-hexenedicyanide, fumaric anhydride or triallylmethoxysilane; based on the mass of the electrolyte, the mass percentage of the additive containing an unsaturated bond is 0.01% to 40%.
  • the mass percentage of the additive containing an unsaturated bond is 0.01%, 0.05%, 1%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or any value between any two of the above numerical ranges.
  • the electrolyte includes the above-mentioned type of additive containing unsaturated bonds, and the mass percentage of the additive containing unsaturated bonds is controlled within the above-mentioned range.
  • the unsaturated bond additive copolymerizes with the polymerization monomer, and the formed copolymer also has the function of adjusting the physical properties and electrochemical properties of the above-mentioned organic polymer, and can also improve the ionic conductivity, oxidation resistance or reduction resistance window of the copolymer to produce a synergistic effect, which can further improve the cycle performance and charge rate window of the electrochemical device.
  • the above-mentioned "unsaturated bond” refers to a double bond, a triple bond, or a ring formed by bonding of elements such as carbon, nitrogen, oxygen, sulfur, or phosphorus.
  • the silicon-containing negative electrode active material includes at least one of SiO w , silicon-carbon compound or silicon element, 0.5 ⁇ w ⁇ 1.5; the silicon-carbon compound includes silicon element, carbon element and oxygen element, and the mass ratio of silicon element, carbon element and oxygen element is 1:1:1 to 6:3:0.
  • the electrolyte further comprises an organic solvent, the organic solvent comprising at least one of carbonate, carboxylate or ether; in one embodiment, the organic solvent comprises carbonate; in one embodiment, the organic solvent comprises carboxylate; in one embodiment, the organic solvent comprises ether; in one embodiment, the organic solvent comprises carbonate and carboxylate; in one embodiment, the organic solvent comprises carbonate and ether; in one embodiment, the organic solvent comprises carboxylate and ether; in one embodiment, the organic solvent comprises carbonate, carboxylate and ether.
  • the carbonate ester includes at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate (DEC), propylene carbonate (also known as propylene carbonate, abbreviated as PC), ethylene carbonate (EC), dipropyl carbonate, methylpropyl carbonate, fluoroethylene carbonate, difluoroethylene carbonate, pentafluoropropylethylene carbonate, methyl trifluoroethyl carbonate, trifluoromethylethylene carbonate or di(2,2,2-trifluoroethyl) carbonate, and the carboxylic acid ester includes propyl propionate, ethyl propionate, ethyl acetate, ethyl formate, methyl acetate, methyl propionate, propyl acetate, butyl butyrate, At least one of ethyl difluoroacetate, difluoroethyl acetate, ethyl trifluoroacetate,
  • the mass percentage of carbonate is 20% to 80%
  • the mass percentage of carboxylic acid ester is 0% to 40%
  • the mass percentage of ether is 0% to 60%.
  • the mass percentage of carbonate is 20%, 30%, 40%, 50%, 60%, 70%, 80% or any two of the above numerical ranges.
  • the mass percentage of carboxylate is 0%, 10%, 20%, 30%, 40% or any value between any two of the above numerical ranges
  • the mass percentage of ether is 0%, 10%, 20%, 30%, 40%, 50%, 60% or any value between any two of the above numerical ranges.
  • the selection of the above-mentioned organic solvents and the regulation of the mass percentages of carbonate, carboxylate and ether in the electrolyte within the above-mentioned ranges are conducive to the electrolyte having good wettability for the positive electrode active material and the negative electrode active material, improving the transmission speed of lithium ions, and making the electrolyte have good stability, reducing the occurrence of risks such as decomposition and gas production of the electrolyte, thereby improving the cycle performance and rate performance of the electrochemical device.
  • the electrolyte further includes a lithium salt
  • the lithium salt includes lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ), lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ), lithium methanesulfonate (LiCH 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiCF 3 SO 3 (LiTA)), lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 (LiTFSI)), tris(trifluoromethylsulfonyl)methyl lithium (LiC(SO 2 CF 3 ) 3 ), lithium hex
  • the mass percentage of the lithium salt is 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20% or any value between any two of the above ranges. Selecting the above types of lithium salts and regulating their mass percentage in the electrolyte within the above range is conducive to accelerating the transmission of lithium ions and improving the cycle performance of the electrochemical device.
  • the negative electrode current collector may include copper foil, copper alloy foil, nickel foil, stainless steel foil, titanium foil, nickel foam or copper foam, etc.
  • the negative electrode active material layer of the present application contains a negative electrode active material.
  • the thickness of the negative electrode current collector and the negative electrode active material layer there is no particular restriction on the thickness of the negative electrode current collector and the negative electrode active material layer, as long as the purpose of the present application can be achieved.
  • the thickness of the negative electrode current collector is 6 ⁇ m to 10 ⁇ m, and the thickness of the negative electrode active material layer is 30 ⁇ m to 130 ⁇ m.
  • the negative electrode active material layer may also include at least one of a conductive agent, a stabilizer, and a binder.
  • the present application has no particular restrictions on the types of conductive agents, stabilizers and binders in the negative electrode active material layer, as long as the purpose of the present application can be achieved.
  • the present application has no particular restrictions on the mass ratio of negative electrode active materials, conductive agents, stabilizers and binders in the negative electrode active material layer, as long as the purpose of the present application can be achieved.
  • the mass ratio of the negative electrode active material, the conductive agent, the binder and the stabilizer in the negative electrode active material layer is (75-95):(0.01-8):(0.01-20):(0.01-10).
  • the present application has no special restrictions on the positive electrode plate, as long as the purpose of the present application can be achieved.
  • the positive electrode plate includes a positive current collector and a positive active material layer.
  • the present application has no special restrictions on the positive current collector, as long as the purpose of the present application can be achieved.
  • the positive current collector may include aluminum foil, aluminum alloy foil or a composite current collector, etc.
  • the positive active material layer of the present application includes positive active materials.
  • the present application has no special restrictions on the type of positive active materials, as long as the purpose of the present application can be achieved.
  • the positive active material may include lithium nickel cobalt manganese oxide (NCM811, NCM622, NCM523, NCM111, Ni88), lithium nickel cobalt aluminum oxide, lithium iron phosphate, lithium-rich manganese-based materials, lithium cobalt oxide (LiCoO 2 ), At least one of lithium manganate, lithium iron manganese phosphate or lithium titanate.
  • the positive active material may also contain non-metallic elements, for example, non-metallic elements include at least one of fluorine, phosphorus, boron, chlorine, silicon or sulfur, which can further improve the stability of the positive active material.
  • the thickness of the positive current collector and the positive active material layer there is no particular restriction on the thickness of the positive current collector and the positive active material layer, as long as the purpose of the present application can be achieved.
  • the thickness of the positive current collector is 5 ⁇ m to 20 ⁇ m, preferably 6 ⁇ m to 18 ⁇ m.
  • the thickness of the single-sided positive active material layer is 30 ⁇ m to 120 ⁇ m.
  • the positive active material layer may be arranged on one surface in the thickness direction of the positive current collector, or on two surfaces in the thickness direction of the positive current collector.
  • the positive active material layer may also include a conductive agent and a binder.
  • the present application does not particularly limit the types of conductive agents and binders in the positive active material layer, as long as the purpose of the present application can be achieved.
  • the present application has no particular restrictions on the mass ratio of the positive electrode active material, the conductive agent, and the binder in the positive electrode active material layer. Those skilled in the art can select according to actual needs as long as the purpose of the present application can be achieved.
  • the mass ratio of the positive electrode active material, the conductive agent, and the binder in the positive electrode active material layer is (97.5-97.9): (0.9-1.7): (1.0-2.0).
  • the material of the diaphragm may include but is not limited to polyethylene (PE), polypropylene (PP)-based polyolefin (PO), polyester (such as polyethylene terephthalate (PET)), cellulose, polyimide (PI), polyamide (PA), spandex or aramid at least one;
  • the type of diaphragm may include but is not limited to woven membrane, non-woven membrane (non-woven fabric), microporous membrane, composite membrane, diaphragm paper, rolled membrane or spinning membrane at least one.
  • the diaphragm may include a substrate layer and a surface treatment layer.
  • the substrate layer may be a non-woven fabric, a membrane or a composite membrane with a porous structure, and the material of the substrate layer may include at least one of polyethylene, polypropylene, polyethylene terephthalate or polyimide.
  • a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene non-woven fabric, a polyethylene non-woven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane may be used.
  • a surface treatment layer is provided on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by a mixed polymer and an inorganic substance.
  • the inorganic layer includes inorganic particles and a binder, and the inorganic particles are not particularly limited, for example, they can be selected from at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the binder is not particularly limited, for example, it can be selected from at least one of polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylic acid salt, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the polymer layer contains a polymer, and the material of the polymer includes at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylic acid salt, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene) etc.
  • the electrochemical device of the present application may also include a packaging bag, which is not particularly limited in the present application and may be any packaging bag known in the art as long as it can achieve the purpose of the present application, such as an aluminum-plastic film or a steel shell.
  • a packaging bag which is not particularly limited in the present application and may be any packaging bag known in the art as long as it can achieve the purpose of the present application, such as an aluminum-plastic film or a steel shell.
  • the present application does not particularly limit the type of electrochemical device, which may include any device that undergoes an electrochemical reaction.
  • the electrochemical device may include, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery (lithium ion battery), a sodium ion secondary battery (sodium ion battery), a lithium polymer secondary battery, and a lithium ion polymer secondary battery.
  • the preparation method of the electrochemical device includes but is not limited to the following steps: stacking the positive electrode sheet, the separator and the negative electrode sheet in order, and winding, folding and other operations as needed to obtain an electrode assembly with a wound structure, placing the electrode assembly in a packaging bag, injecting an electrolyte into the packaging bag and sealing it to obtain an electrochemical device; or stacking the positive electrode sheet, the separator and the negative electrode sheet in order, and then fixing the four corners of the entire stacked structure to obtain an electrode assembly with a stacked structure, placing the electrode assembly in a packaging bag, injecting an electrolyte into the packaging bag and sealing it to obtain an electrochemical device.
  • the second aspect of the present application provides an electronic device, which includes the electrochemical device described in any of the above embodiments. Therefore, the electronic device has good performance.
  • the electronic devices of the present application are not particularly limited, and may include but are not limited to: laptop computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, head-mounted stereo headphones, video recorders, LCD televisions, portable cleaners, portable CD players, mini CDs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • the lithium-ion battery (state of charge 0%, working voltage 2.5V) was disassembled to obtain the negative electrode plate.
  • the negative electrode plate was cleaned with dimethyl carbonate (DMC), X-ray diffraction (XRD) was used to test the structural type of the inorganic solid electrolyte in the negative electrode material layer on the surface of the negative electrode plate, and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) was used to test the composition of the inorganic solid electrolyte.
  • DMC dimethyl carbonate
  • XRD X-ray diffraction
  • SEM-EDS scanning electron microscopy-energy dispersive spectroscopy
  • the lithium ion battery (charge state of 0%, working voltage 2.5V) was disassembled to obtain an electrolyte, and the mass percentage of the organic solvent, the compound of formula (I), the polymerization monomer, the initiator, and the unsaturated bond additive in the electrolyte was tested by gas chromatography-mass spectrometry (GCMS), and the mass percentage of the lithium salt was tested by ion chromatography-mass spectrometry.
  • GCMS gas chromatography-mass spectrometry
  • the mass percentage of LiPF6 is 8%
  • the mass percentage of LiFSI is 6%
  • the rest is organic solvent.
  • the sum of the mass percentages of the organic solvent, lithium salt, the compound of formula (I) and the polymerized monomer is 100%.
  • the negative electrode active material SiO, the conductive agent conductive carbon black (Super P), the binder styrene butadiene rubber (SBR, solid content 45wt%), and the stabilizer sodium carboxymethyl cellulose (CMC-Na, weight average molecular weight of about 400000) were mixed in a mass ratio of 86:2:2:10, and then deionized water was added as a solvent, and stirred under the action of a vacuum mixer until the solid content was 53wt% and the system was uniform.
  • the negative electrode slurry was evenly coated on one surface of the negative electrode current collector copper foil with a thickness of 8 ⁇ m, and dried at 85°C to obtain a negative electrode sheet with a single-sided coating of the negative electrode active material layer (thickness 130 ⁇ m). After that, the above steps were repeated on the other surface of the copper foil to obtain a negative electrode sheet with a double-sided coating of the negative electrode active material layer. After cold pressing, cutting, and slitting, it was dried under vacuum conditions at 120°C for 12h to obtain a negative electrode sheet with a specification of 76mm ⁇ 851mm for standby use.
  • the positive electrode active material Ni88 Li[Ni 0.88 Co 0.02 Mn 0.1 ]O 2
  • the binder polyvinylidene fluoride (PVDF) was added as a solvent.
  • the mixture was stirred in a vacuum mixer until the solid content was 75wt% and the system was uniform.
  • the positive electrode slurry was evenly coated on one surface of a positive electrode current collector aluminum foil with a thickness of 10 ⁇ m, and dried at 85°C for 4h to obtain a positive electrode sheet with a single-sided coating of a positive electrode active material layer (thickness 110 ⁇ m).
  • the above steps were repeated on the other surface of the aluminum foil to obtain a positive electrode sheet with a double-sided coating of a positive electrode active material layer.
  • the positive electrode sheet was dried at 85°C in a vacuum oven. After drying for 4 h under air conditions, a positive electrode sheet with a specification of 74 mm ⁇ 867 mm was obtained for standby use.
  • a polyethylene film with a thickness of 7 ⁇ m was used.
  • the negative electrode sheet, separator and positive electrode sheet prepared above are stacked and wound in sequence to obtain an electrode assembly with a wound structure.
  • the electrode assembly is placed in an aluminum-plastic film packaging bag, and the electrolyte is injected after drying.
  • the lithium-ion battery is obtained through vacuum packaging, high-temperature standing, formation, degassing, trimming and other processes.
  • the high-temperature standing temperature is 60°C and the standing time is 14h.
  • the upper limit voltage of the formation is 4.15V
  • the formation temperature is 70°C
  • the formation standing time is 2h.
  • Example 1-1 Except for adjusting the relevant preparation parameters according to Table 1, the rest is the same as Example 1-1.
  • Example 1-4 Except for adjusting the relevant preparation parameters according to Table 1, the rest is the same as Example 1-4.
  • Example 1-8 Except for adjusting the relevant preparation parameters according to Table 1, the rest is the same as Example 1-8.
  • Example 1-4 Except for adjusting the relevant preparation parameters according to Table 1, the rest is the same as Example 1-4.
  • the negative electrode active material SiO, the inorganic solid electrolyte Li 7 La 3 Zr 2 O 12 (garnet-type inorganic oxide material), the conductive agent conductive carbon black (Super P), the binder styrene butadiene rubber (SBR, solid content 45wt%), and the stabilizer sodium carboxymethyl cellulose (CMC-Na, weight average molecular weight of about 400000) were mixed in a mass ratio of 85:1:2:2:10, and then deionized water was added as a solvent, and stirred in a vacuum mixer until the solid content was 53wt% and the system was uniform.
  • the slurry was evenly coated on one surface of a negative electrode current collector copper foil with a thickness of 8 ⁇ m, and dried at 85°C to obtain a negative electrode sheet with a negative electrode active material layer (thickness 130 ⁇ m) coated on one side. After that, the above steps were repeated on the other surface of the copper foil to obtain a negative electrode sheet with a negative electrode active material layer coated on both sides. After cold pressing, cutting, and slitting, it was dried under vacuum conditions at 120°C for 12 hours to obtain a negative electrode sheet with a specification of 76 mm ⁇ 851 mm for standby use.
  • Example 2-1 Except for adjusting the relevant preparation parameters according to Table 2, the rest is the same as Example 2-1.
  • Example 2-1 Except for adjusting the relevant preparation parameters according to Table 2, the rest is the same as Example 2-1.
  • Example 2-1 The rest is the same as Example 2-1 except that Li 7 La 3 Zr 2 O 12 is replaced by Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 in ⁇ Preparation of Negative Electrode Sheet>.
  • Example 3-2 to Example 3-6
  • Example 3-1 Except that the mass percentage of the initiator is adjusted to y% according to Table 3, the mass percentage of the organic solvent is reduced accordingly, and the mass percentage of the compound of formula (I), lithium salt and polymerization monomer remain unchanged, the rest is the same as Example 3-1.
  • Example 3-5 Except for adjusting the relevant preparation parameters according to Table 3, the rest is the same as Example 3-5.
  • Example 3-14 Except for adjusting the relevant preparation parameters according to Table 3, the rest is the same as Example 3-14.
  • Example 1-1 Except for adjusting the relevant preparation parameters according to Table 1, the rest is the same as Example 1-1.
  • Examples 1-1 to 1-20 and Comparative Examples 1 to 9 that the lithium ion batteries in which the compound of formula (I) of the present application and the polymerized monomer are simultaneously added to the electrolyte, and the mass percentage of the compound of formula (I) and the polymerized monomer is within the range of the present application, have higher cycle numbers at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium ion batteries of the embodiments have higher cycle performance and a wider charge rate window, and their cycle performance and charge rate window are improved.
  • the electrolyte of Comparative Example 1 did not contain the compound of formula (I) and the polymerized monomer of the present application; the electrolytes of Comparative Examples 2 and 3 contained the polymerized monomer of the present application, but did not contain the compound of formula (I) of the present application; the electrolytes of Comparative Examples 4 to 6 contained the compound of formula (I) of the present application, but did not contain the polymerized monomer of the present application; the electrolytes of Comparative Examples 7 and 8 contained both the compound of formula (I) of the present application and the polymerized monomer, but the mass percentage of the polymerized monomer was not within the scope of the present application; the electrolyte of Comparative Example 9 contained both the compound of formula (I) of the present application and the polymerized monomer of the present application.
  • the lithium ion batteries of Comparative Examples 1 to Comparative Examples 9 have lower cycle numbers at charge rates of 0.2C, 0.5C and 1C, or have lower cycle numbers at charge rates of 0.5C and 1C, or have lower cycle numbers at a high charge rate of 1C, indicating that the cycle performance of the lithium ion battery or the cycle performance at a high rate is poor, the charge rate window of the lithium ion battery is small, and the cycle performance and charge rate window of the lithium ion battery are not improved.
  • the mass percentage content m% of the compound of formula (I) generally also affects the cycle performance and charge rate window of the lithium ion battery. From Examples 1-1 to 1-7 and Comparative Example 9, it can be seen that the mass percentage content m% of the compound of formula (I) is selected.
  • the lithium-ion battery within the scope of the present application has a high number of cycles at charging rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charging rate window.
  • the type of compound of formula (I) also generally affects the cycle performance and charge rate window of the lithium ion battery. It can be seen from Examples 1-4, 1-8 to 1-13 that the lithium ion battery using the type of compound of formula (I) within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium ion battery has good cycle performance and a wide charge rate window.
  • the mass percentage content n% of the polymerized monomers also generally affects the cycle performance and charge rate window of the lithium-ion battery. From Examples 1-14 to 1-18, Comparative Examples 7 and 8, it can be seen that the lithium-ion battery with the mass percentage content n% of the polymerized monomers within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charge rate window.
  • the type of polymerized monomers also generally affects the cycle performance and charge rate window of lithium-ion batteries. It can be seen from Examples 1-8, 1-16, 1-19 and 1-20 that lithium-ion batteries using polymerized monomers within the scope of the present application have a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion batteries have good cycle performance and a wide charge rate window.
  • the value of (n/M single )/(m/M (I) ) also generally affects the cycle performance and charge rate window of the lithium ion battery. From Examples 1-1 to 1-25, it can be seen that the lithium ion battery with the value of (n/M single )/(m/M (I) ) within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium ion battery has good cycle performance and a wide charge rate window.
  • the mass percentage ⁇ % of the inorganic solid electrolyte usually also affects the cycle performance and charge rate window of the lithium ion battery. It can be seen from Examples 1-19 and 2-1 to 2-7 that the lithium ion battery using the inorganic solid electrolyte with a mass percentage ⁇ % within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium ion battery has good cycle performance and a wide charge rate window.
  • n/ ⁇ also generally affects the cycle performance and charge rate window of the lithium-ion battery. It can be seen from Examples 1-19 and 2-1 to 2-7 that the lithium-ion battery with the value of n/ ⁇ within the range of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charge rate window.
  • the type of inorganic solid electrolyte usually also affects the cycle performance and charge rate window of the lithium-ion battery. From Examples 1-3 and 2-14, 1-19, 2-1, 2-8 to 2-13, 1-20 and 2-15, it can be seen that the lithium-ion battery using the inorganic solid electrolyte within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charge rate window.
  • Example 2-1 and Example 3-1 to Example 3-7 it can be seen from Example 2-1 and Example 3-1 to Example 3-7 that when an initiator is further added to the electrolyte so that the polymerization monomers in the electrolyte are polymerized using the initiator, the cycle performance and charge rate window of the lithium-ion battery are further improved.
  • the mass percentage of the initiator y% usually also affects the cycle performance and charge rate window of the lithium-ion battery. From Examples 2-1, 3-1 to 3-6, it can be seen that the lithium-ion battery with the mass percentage of the initiator y% within the scope of the present application has a higher number of cycles at the charge rates of 0.2C, 0.5C and 1C, indicating that Lithium-ion batteries have good cycle performance and a wide charge rate window.
  • the type of initiator usually also affects the cycle performance and charge rate window of the lithium-ion battery. It can be seen from Examples 3-5 and 3-7 that the lithium-ion battery using the type of initiator within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charge rate window.
  • Example 2-1 and Example 3-8 to Example 3-11 that by further adding an additive containing an unsaturated bond to the electrolyte, the cycle performance and charge rate window of the lithium-ion battery can be further improved.
  • the mass percentage h% of the additive containing unsaturated bonds also generally affects the cycle performance and charge rate window of the lithium-ion battery. It can be seen from Examples 2-1, 3-8 to 3-12 that the lithium-ion battery with the mass percentage h% of the additive containing unsaturated bonds within the scope of the present application has a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion battery has good cycle performance and a wide charge rate window.
  • the type of additive containing unsaturated bonds also generally affects the cycle performance and charge rate window of lithium-ion batteries. It can be seen from Examples 3-8 and 3-13 that lithium-ion batteries using additives containing unsaturated bonds within the scope of the present application have a high number of cycles at charge rates of 0.2C, 0.5C and 1C, indicating that the lithium-ion batteries have good cycle performance and a wide charge rate window.

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Abstract

一种电化学装置和电子装置，其中，电化学装置包括电解液、负极极片、隔膜和正极极片；电解液包括式(I)化合物和聚合单体，基于电解液的质量，式(I)化合物的质量百分含量为m％，0.01≤m≤6，聚合单体的质量百分含量为n％，0.5≤n≤10；负极极片包括负极集流体以及设置于负极集流体至少一个表面上的负极材料层，负极材料层包括含硅负极活性材料。

Description

一种电化学装置和电子装置 技术领域
本申请涉及电化学技术领域，特别是涉及一种电化学装置和电子装置。
背景技术
随着电化学装置(如锂离子电池)在手机、笔记本电脑等领域的广泛应用，目前电子数码产品对锂离子电池的能量密度要求越来越高，而现有的负极活性材料石墨很难满足能量密度要求。硅材料的理论克容量为4200mAh/g，远高于石墨材料的理论克容量372mAh/g，但硅材料在充放电过程中体积膨胀大，电解液在表面持续消耗分解，造成循环容量衰减严重，副产物累积造成充电时严重的锂析出，使硅材料目前在锂离子电池中难以商用化。
对于上述问题，目前采用较多的办法是对硅材料进行结构改性，或电解液中加入氟代碳酸乙烯酯形成界面保护。这些方法在一定程度上提高了硅负极的循环稳定性，但改善效果和稳定性有限，并且对充电倍率窗口的提高基本无帮助。因此，如何在提高含硅负极锂离子电池的循环性能的基础上，提高其充电倍率窗口，是本领域技术人员亟待解决的技术问题。
发明内容
本申请提供了一种电化学装置和电子装置，以提高电化学装置的循环性能和充电倍率窗口。
需要说明的是，本申请的发明内容中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。具体技术方案如下：
本申请第一方面提供了一种电化学装置，包括电解液、负极极片、隔膜和正极极片；电解液包括式(I)化合物和聚合单体：
其中，X1、X2、X3、X4、Y1、Y2、Y3和Y4各自独立地选自O、C1至C3碳链或单键，X1和Y1不同时为O或单键，X2和Y2不同时为O或单键，X3和Y3不同时为O或单键，X4和Y4不同时为O或单键，X1、X2、Y1和Y2中的至少一个为O，X3、X4、Y3和Y4中 的至少一个为O；Z1和Z2各自独立地选自卤素或末端具有聚合功能基团的C1至C4碳链，聚合功能基团包括羧基、羟基、醛基、酰氧基、氨基、烯基或炔基；聚合单体包括丙烯酸甲酯、甲基丙烯酸甲酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、乙烯、丙烯、醋酸乙烯酯、二氟乙烯、四氟乙烯、六氟丙烯、丙烯腈、乙二醇、乙二醇双丙烯酸酯、二乙二醇双丙烯酸酯、环氧乙烷、二氧戊烷、2,6-二甲基苯酚、3,4-乙烯二氧噻吩或4,6-二氨基-1,3-间二苯酚中的至少一种；基于电解液的质量，式(I)化合物的质量百分含量为m％，0.01≤m≤6，聚合单体的质量百分含量为n％，0.5≤n≤10；负极极片包括负极集流体以及设置于负极集流体至少一个表面上的负极材料层，负极材料层包括含硅负极活性材料。通过选用上述种类的式(I)化合物和聚合单体，并且将式(I)化合物的质量百分含量和聚合单体的质量百分含量调控在上述范围内，式(I)化合物和聚合单体能够经交联聚合，在正极极片和负极极片上产生类似有机分子骨架(COFs)的规则结构，该结构作为SEI膜的网状骨架，兼顾刚性和柔性，能够阻隔电解液和负极极片的接触，抑制高电压下电解液中的有机溶剂氧化分解。并且，上述骨架结构结合电解液，使电化学装置具有较低的阻抗，这样，即使含硅负极活性材料在电化学装置充放电过程中发生体积膨胀，电化学装置在大倍率充电条件下依然能够改善循环性能。由此，电化学装置的循环性能和充电倍率窗口得到提高。
优选地，0.05≤m≤4。将式(I)化合物的质量百分含量调控在上述优选范围内，电化学装置的循环性能和充电倍率窗口更优。
优选地，1≤n≤6。将聚合单体的质量百分含量调控在上述优选范围内，电化学装置的循环性能和充电倍率窗口更优。
例如，式(I)化合物包括以下式(I-1)化合物至式(I-8)化合物中的至少一个：

在本申请的一些实施方案中，式(I)化合物的摩尔质量为M(I)g/mol，聚合单体的摩尔质量为M单g/mol，m、n、M(I)和M单之间满足：2≤(n/M单)/(m/M(I))≤200。优选地，3≤(n/M单)/(m/M(I))≤30。将(n/M单)/(m/M(I))的值调控在上述范围内，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，负极材料层还包括无机固态电解质，无机固态电解质包括无机氧化物材料或无机硫化物材料中的任一种；基于负极材料层的质量，无机固态电解质的质量百分含量为θ％，0.01≤θ≤5。负极材料层包括无机固态电解质，且将无机固态电解质在负极材料层中的质量百分含量调控在上述范围内，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，0.5≤n/θ≤100，将n/θ的值调控在上述范围内，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
优选地，0.1≤θ≤5。
优选地，1≤n/θ≤30。
优选地，0.1≤θ≤5，1≤n/θ≤30。
在本申请的一些实施方案中，无机氧化物材料的晶型结构包括NASICON型、LISICON型、钙钛矿型或石榴石型中的至少一种；NASICON型无机氧化物材料的化学式为Li1+xM1xD12-x(PO4)3，其中，0.01≤x≤0.5，M1包括Al、Y、Ga、Cr、In、Fe、Se或La中的至少一种，D1包括Ti、Ge、Ta、Zr、Sn、Fe、V、Hf中的至少一种；LISICON型无机氧化物材料的化学式为Li14M2(D2O4)4，其中，M2包括Zr、Cr、Sn或Zn中的至少一种，D2包括Si、Ge、S或P中的至少一种；钙钛矿型无机氧化物材料的化学式为Li3yM32/3-yD3O3，其中，0.01≤y≤0.5，M3包括La、Al、Mg、Fe或Ta中的至少一种，D3包括Ti、Nb、Sr或Pr中的至少一种；石榴石型无机氧化物材料的化学式为LiZM43D42O12，其中，6≤z≤7，M4包括La、Ca、Sr、Ba或K中的至少一种，D4包括Zr、Ta、Nb或Hf中的至少一种；无机硫化物材料包括锂锗磷硫、锂磷硫、锂磷硫氯、锂锡磷硫、锂硅磷硫、锂锗硅磷硫、锂铝磷硫、锂锗硫或锂硅硫中的至少一种。选用上述无机固态电解质，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，电解液还包括引发剂，引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯或过氧化甲乙酮中的至少一种；基于电解液的质量，引发剂的质量百分含量为0.001％至2％。电解液中包括上述种类的引发剂且将引发剂在电解液中的质量百分含量调控在上述范围内，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，电解液还包括含不饱和键的添加剂，含不饱和键的添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙烯磺酸内酯、1,3-丙烷磺酸内酯、3-己烯二氰、反丁烯二酸酐或三烯丙基甲氧基硅烷中的至少一种；基于电解液的质量，含不饱和键的添加剂的质量百分含量为0.01％至40％。电解液中包括上述种类的含不饱和键的添加剂，且将含不饱和键的添加剂的质量百分含量调控在上述范围内，有利于使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，含硅负极活性材料包括SiOw、硅碳化合物或硅单质中的至少一种，0.5≤w≤1.5。
在本申请的一些实施方案中，电解液还包括有机溶剂，有机溶剂包括碳酸酯、羧酸酯或醚中的至少一种；碳酸酯包括碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸丙烯酯、碳酸乙烯酯、碳酸二丙酯、碳酸甲丙酯、氟代碳酸乙烯酯、二氟代碳酸乙烯酯、五氟丙基碳酸乙烯酯、甲基三氟乙基碳酸酯、三氟甲基碳酸乙烯酯或二(2,2,2-三氟乙基)碳酸酯中的至少一种，羧酸酯包括丙酸丙酯、丙酸乙酯、乙酸乙酯、甲酸乙酯、乙酸甲酯、丙酸甲酯、乙酸丙酯、丁酸丁酯、二氟乙酸乙酯、乙酸二氟乙酯、三氟乙酸乙酯、乙酸三氟乙酯或三氟丙酸甲酯中的至少一种，醚包括1,3-二氧六环、1,4-二氧六环、1,3-二氧戊环、4-甲基-1,3-二氧戊环、二乙醚、乙二醇二乙醚、二乙二醇二甲醚、三甘醇二甲醚、乙二醇甲酸乙醚、二乙氧基甲烷、1,3-二甲氧基丙烷、1,1,3,3-四乙氧基丙烷醚或1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚中的至少一种；基于电解液的质量，碳酸酯的质量百分含量为20％至80％，羧酸酯的质量百分含量为0％至40％，醚的质量百分含量为0％至60％。
在本申请的一些实施方案中，电解液还包括锂盐，锂盐包括六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、四苯基硼酸锂、甲基磺酸锂、双氟磺酰亚胺锂、三氟甲磺酸锂、双三氟甲磺酰亚胺锂、三(三氟甲基磺酰)甲基锂、六氟硅酸锂、二草酸硼酸锂或二氟草酸硼酸锂中的至少一种；基于电解液的质量，锂盐的质量百分含量为6％至20％。
本申请第二方面提供了一种电子装置，其包括前述任一实施方案所述的电化学装置。因此，电子装置具有良好的使用性能。
本申请提供了一种电化学装置和电子装置，其中，电化学装置包括电解液、负极极片、 隔膜和正极极片；电解液包括式(I)化合物和聚合单体，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m％，0.01≤m≤6，所述聚合单体的质量百分含量为n％，0.5≤n≤10；负极极片包括负极集流体以及设置于负极集流体至少一个表面上的负极材料层，负极材料层包括含硅负极活性材料。通过上述设置得到的电化学装置，具有良好的循环性能和较宽的充电倍率窗口。
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下举实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本申请保护的范围。
需要说明的是，本申请的具体实施方式中，以锂离子电池作为电化学装置的例子来解释本申请，但是本申请的电化学装置并不仅限于锂离子电池。具体技术方案如下：
本申请第一方面提供了一种电化学装置，包括电解液、负极极片、隔膜和正极极片；电解液包括式(I)化合物和聚合单体：
其中，X1、X2、X3、X4、Y1、Y2、Y3和Y4各自独立地选自O、C1至C3碳链或单键，X1和Y1不同时为O或单键，X2和Y2不同时为O或单键，X3和Y3不同时为O或单键，X4和Y4不同时为O或单键，X1、X2、Y1和Y2中的至少一个为O，X3、X4、Y3和Y4中的至少一个为O；Z1和Z2各自独立地选自卤素或末端具有聚合功能基团的C1至C4碳链，聚合功能基团包括羧基、羟基、醛基、酰氧基、氨基、烯基或炔基；聚合单体包括丙烯酸甲酯、甲基丙烯酸甲酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、乙烯、丙烯、醋酸乙烯酯、二氟乙烯、四氟乙烯、六氟丙烯、丙烯腈、乙二醇、乙二醇双丙烯酸酯、二乙二醇双丙烯酸酯、环氧乙烷、二氧戊烷、2,6-二甲基苯酚、3,4-乙烯二氧噻吩或4,6-二氨基-1,3-间二苯酚中的至少一种；基于电解液的质量，式(I)化合物的质量百分含量为m％，0.01≤m≤6，聚合单体的质量百分含量为n％，0.5≤n≤10；负极极片包括负极集流体以及设置于负极集流体至少一个表面上的负极材料层，负极材料层包括含硅负极活性材料。例如，m为0.01、 0.5、1、1.5、2、2.5、3、3.5、4、4.5、5、5.5、6或上述任两个数值范围间的任一数值。n为0.5、1、2、3、4、5、6、7、8、9、10或上述任两个数值范围间的任一数值。
发明人经大量研究发现，式(I)化合物和聚合单体具有交联聚合的功能，可以形成二维网状或三维笼状有机聚合物，或者聚合单体发生聚合形成有机聚合物的主链段及功能链段的单体和低聚物，附着在含硅负极活性材料表面。式(I)化合物上环醚键中的氧，一方面容易和含硅负极活性材料表面的羟基形成氢键，亲和含硅负极活性材料界面，在微量水、HF(可以是锂盐分解产生)存在的情况下起到捕水缚酸(HF)的功能，维持固体电解质界面(SEI)膜的稳定性；另一方面正极极片中的正极活性材料表面有残碱(如LiOH、Li2CO3)存在时，部分环醚结构可以发生开环反应，促进式(I)化合物和聚合单体的聚合效果，电化学装置充放电过程中能够抑制正极活性材料中的过渡金属溶出。式(I)化合物的质量百分含量小于0.01％，和/或聚合单体的质量百分含量小于0.5％，有机聚合物生成量不足，容易造成无机固态电解质与负极活性材料颗粒接触不良，从而使负极极片阻抗增加、电化学装置的极化增大；式(I)化合物的质量百分含量大于6％，和/或聚合单体的质量百分含量大于10％，有机聚合物生成量过多，容易造成锂离子脱溶剂化能垒上升，从而负极极片阻抗也会过大、充电析锂，此外还会造成残留单体较多，在充放电过程中持续反应消耗锂离子、电化学装置容量衰减较快。通过选用上述种类的式(I)化合物和聚合单体，并且将式(I)化合物的质量百分含量和聚合单体的质量百分含量调控在上述范围内，式(I)化合物和聚合单体能够经交联聚合，在正极极片和负极极片上产生类似共价有机分子骨架(Covalent organic frameworks,COFs)的规则结构，该结构作为SEI膜的网状骨架，兼顾刚性和柔性，能够阻隔电解液和负极极片的接触，抑制高电压(大于或等于4.25V)下电解液中的有机溶剂氧化分解。并且，上述骨架结构结合电解液，使电化学装置具有较低的阻抗，这样，即使含硅负极活性材料在电化学装置充放电过程中发生体积膨胀，电化学装置在大倍率(大于或等于0.5C)充电条件下依然能够改善循环性能。由此，电化学装置的循环性能和充电倍率窗口得到提高。
本领域技术人员应当理解，上述“设置于负极集流体至少一个表面上的负极材料层”是指负极材料层可以设置于负极集流体的一个表面上，也可以设置于负极集流体的两个表面上，上述的“表面”为负极集流体表面的全部区域或部分区域。
优选地，0.05≤m≤4。例如，m为0.05、0.5、1、1.5、2、2.5、3或上述任两个数值范围间的任一数值。将式(I)化合物的质量百分含量调控在上述优选范围内，电化学装置的循环性能和充电倍率窗口更优。
优选地，1≤n≤6。例如，n为1、2、3、4、5、6或上述任两个数值范围间的任一数 值。将聚合单体的质量百分含量调控在上述优选范围内，电化学装置的循环性能和充电倍率窗口更优。
例如，式(I)化合物包括以下式(I-1)化合物至式(I-8)化合物中的至少一个：
在本申请的一些实施方案中，式(I)化合物的摩尔质量为M(I)g/mol，聚合单体的摩尔质量为M单g/mol，m、n、M(I)和M单之间满足：2≤(n/M单)/(m/M(I))≤200。优选地，3≤(n/M单)/(m/M(I))≤30。例如，(n/M单)/(m/M(I))的值为2、3、10、20、30、50、100、150、200或上述任两个数值范围间的任一数值。将(n/M单)/(m/M(I))的值调控在上述范围内，式(I)化合物和聚合单体可以实现定向控制有机聚合物重复单元构成、设计有机聚合物类型，式(I)化合物和聚合单体具有交联聚合所形成的聚合物结构，具有更合适的刚性和柔性，有利于阻隔电解液和负极极片的接触，抑制高电压下电解液中的有机溶剂氧化分解，并且，有利于降低电化学装置的阻抗，从而使电化学装置的循环性能和充电倍率窗口得到提高。
需要说明的是，电解液中选用两种以上聚合单体和/或两种以上式(I)化合物时，(n/M单)/(m/M(I))也可以理解为∑(n/M单)/∑(m/M(I))。
在本申请的一些实施方案中，负极材料层还包括无机固态电解质，无机固态电解质包括无机氧化物材料或无机硫化物材料中的任一种；基于负极材料层的质量，无机固态电解质的质量百分含量为θ％，0.01≤θ≤5。例如，θ的值为0.01、0.1、0.5、1、1.5、2、2.5、3、3.5、4、4.5、5或上述任两个数值范围间的任一数值。负极材料层包括无机固态电解质，含硅负极活性材料被无机固态电解质部分或全部包覆，无机固态电解质具有良好的电导率和机械稳定性，可以提高负极极片的充电性能和循环稳定性。无机固态电解质包覆的含硅负极活性材料与本申请包含有式(I)化合物和聚合单体的电解液协同作用，电解液原位聚合生成负极SEI膜，与无机固态电解质相辅相成，提升了电解液与负极极片之间的界面相容性，能够改善高能量密度的硅基负极的循环性能和倍率性能。将无机固态电解质在负极材料层中的质量百分含量调控在上述范围内，与式(I)化合物和聚合单体的含量相匹配，能够稳定负极极片与电解液的界面，将硅基负极的电化学装置的充电倍率窗口拓宽至0.5C及以上，从而使电化学装置的循环性能和充电倍率窗口得到提高。
在本申请的一些实施方案中，0.5≤n/θ≤100。例如，n/θ的值为0.5、1、5、10、15、20、25、30、40、50、60、70、80、90、100或上述任两个数值范围间的任一数值。无机固态电解质具有快离子导体的功能，将n/θ的值调控在上述范围内，无机固态电解质与含硅负极活性材料之间的接触界面致密性较好，聚合单体原位聚合生成的SEI膜对含硅负极活性材料具有良好的保护效果，使含硅负极活性材料在电化学装置充放电循环过程中破裂、分解的可能性减小，并且，电解液具有合适的聚合度，聚合单体发生聚合后剩余有足够的液态组分，使电化学装置具有较低的阻抗。由此，电化学装置的循环性能和充电倍率窗口得到提高。
优选地，0.1≤θ≤5。例如，θ的值为0.1、0.5、1、1.5、2、2.5、3、3.5、4、4.5、5或上述任两个数值范围间的任一数值。将无机固态电解质在负极材料层中的质量百分含量调控在上述优选范围内，有利于使电化学装置的循环性能和充电倍率窗口得到进一步提高。
优选地，1≤n/θ≤30。例如，n/θ的值为1、5、10、15、20、25、30或上述任两个数值范围间的任一数值。将n/θ的值调控在上述优选范围内，有利于使电化学装置的循环性能和充电倍率窗口得到进一步提高。
优选地，0.1≤θ≤5，1≤n/θ≤30。将无机固态电解质在负极材料层中的质量百分含量和n/θ的值同时调控在上述优选范围内，有利于使电化学装置的循环性能和充电倍率窗口得到进一步提高。
在本申请的一些实施方案中，无机氧化物材料的晶型结构包括NASICON型、LISICON 型、钙钛矿型或石榴石型中的至少一种；NASICON型无机氧化物材料的化学式为Li1+xM1xD12-x(PO4)3，其中，0.01≤x≤0.5，M1包括Al、Y、Ga、Cr、In、Fe、Se或La中的至少一种，D1包括Ti、Ge、Ta、Zr、Sn、Fe、V、Hf中的至少一种；LISICON型无机氧化物材料的化学式为Li14M2(D2O4)4，其中，M2包括Zr、Cr、Sn或Zn中的至少一种，D2包括Si、Ge、S或P中的至少一种；钙钛矿型无机氧化物材料的化学式为Li3yM32/3-yD3O3，其中，0.01≤y≤0.5，M3包括La、Al、Mg、Fe或Ta中的至少一种，D3包括Ti、Nb、Sr或Pr中的至少一种；石榴石型无机氧化物材料的化学式为LiZM43D42O12，其中，6≤z≤7，M4包括La、Ca、Sr、Ba或K中的至少一种，D4包括Zr、Ta、Nb或Hf中的至少一种；无机硫化物材料包括锂锗磷硫、锂磷硫(Li2S-P2S5)、锂磷硫氯(Li6PS5Cl)、锂锡磷硫、锂硅磷硫、锂锗硅磷硫、锂铝磷硫、锂锗硫或锂硅硫中的至少一种。上述无机固态电解质具有良好的电导率，有利于改善负极极片和电解液的界面阻抗，与本申请提供的电解液相匹配，式(I)化合物和聚合单体聚合形成的有机聚合物可以降低无机固态电解质与含硅负极活性材料接触的可能性，降低负极极片的阻抗，协同提高SEI膜的稳定性以及负极极片和电解液之间的界面相容性，改善电化学装置的循环性能和充电倍率窗口。
在本申请的一些实施方案中，电解液还包括引发剂，引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯或过氧化甲乙酮中的至少一种；基于电解液的质量，引发剂的质量百分含量为0.001％至2％。例如，引发剂的质量百分含量为0.001％、0.01％、0.05％、0.1％、0.4％、0.6％、0.8％、1.0％、1.2％、1.4％、1.6％、1.8％、2.0％或上述任两个数值范围间的任一数值。电解液中包括上述种类的引发剂且将引发剂在电解液中的质量百分含量调控在上述范围内，引发剂能够进一步提升式(I)化合物和聚合单体的聚合效果，以及聚合单体自身的聚合效果，形成有机聚合物更好地附着在含硅负极活性材料表面和和/或无机固态电解质表面，以阻隔电解液和负极极片的接触，抑制高电压下电解液中的有机溶剂氧化分解，降低电化学装置的阻抗，从而提高电化学装置的循环性能和充电倍率窗口。
在本申请的一些实施方案中，式(I)化合物和聚合单体，或者聚合单体还可以在电引发(电流催化聚合反应)、光引发(紫外光催化聚合反应)或热引发(高温催化聚合反应)中的任一种引发方式下经引发发生聚合反应，形成有机聚合物，或者有机聚合物的主链段及功能链段的单体和低聚物，附着在含硅负极活性材料表面、无机固态电解质表面。在本申请中，式(I)化合物和聚合单体交联聚合形成有机聚合物，以及聚合单体发生聚合形成有机聚合物均是在电化学装置制程阶段生成。例如，注液阶段在电解液中加入单体后通过热引发聚合、或化成阶段通过电引发聚合。
在本申请的一些实施方案中，电解液还包括含不饱和键的添加剂，含不饱和键的添加 剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙烯磺酸内酯、1,3-丙烷磺酸内酯、3-己烯二氰、反丁烯二酸酐或三烯丙基甲氧基硅烷中的至少一种；基于电解液的质量，含不饱和键的添加剂的质量百分含量为0.01％至40％。例如，含不饱和键的添加剂的质量百分含量为0.01％、0.05％、1％、10％、15％、20％、25％、30％、35％、40％或上述任两个数值范围间的任一数值。电解液中包括上述种类的含不饱和键的添加剂，且将含不饱和键的添加剂的质量百分含量调控在上述范围内，不饱和键的添加剂与聚合单体发生共聚反应，形成的共聚物也具有调节前述有机聚合物物理性质、电化学性质的作用，也能提高共聚物的离子电导率、耐氧化或耐还原窗口，以产生协同效果，能够进一步提高电化学装置的循环性能和充电倍率窗口。
在本申请中，上述“不饱和键”是指由碳、氮、氧、硫、磷等元素键连成的双键、三键、环。
在本申请的一些实施方案中，含硅负极活性材料包括SiOw、硅碳化合物或硅单质中的至少一种，0.5≤w≤1.5；硅碳化合物包括硅元素、碳元素和氧元素，硅元素、碳元素和氧元素的质量比为1:1:1至6:3:0。选用上述种类的含硅负极活性材料，有利于在提高电化学装置的循环性能和倍率窗口的情况下，提高电化学装置的能量密度。
在本申请的一些实施方案中，电解液还包括有机溶剂，有机溶剂包括碳酸酯、羧酸酯或醚的至少一种；在一种实施方案中，有机溶剂包括碳酸酯；在一种实施方案中，有机溶剂包括羧酸酯；在一种实施方案中，有机溶剂包括醚；在一种实施方案中，有机溶剂包括碳酸酯和羧酸酯；在一种实施方案中，有机溶剂包括碳酸酯和醚；在一种实施方案中，有机溶剂包括羧酸酯和醚；在一种实施方案中，有机溶剂包括碳酸酯、羧酸酯和醚。碳酸酯包括碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯(DEC)、碳酸丙烯酯(也称碳酸亚丙酯，简写PC)、碳酸乙烯酯(EC)、碳酸二丙酯、碳酸甲丙酯、氟代碳酸乙烯酯、二氟代碳酸乙烯酯、五氟丙基碳酸乙烯酯、甲基三氟乙基碳酸酯、三氟甲基碳酸乙烯酯或二(2,2,2-三氟乙基)碳酸酯中的至少一种，羧酸酯包括丙酸丙酯、丙酸乙酯、乙酸乙酯、甲酸乙酯、乙酸甲酯、丙酸甲酯、乙酸丙酯、丁酸丁酯、二氟乙酸乙酯、乙酸二氟乙酯、三氟乙酸乙酯、乙酸三氟乙酯或三氟丙酸甲酯中的至少一种，醚包括1,3-二氧六环、1,4-二氧六环、1,3-二氧戊环、4-甲基-1,3-二氧戊环、二乙醚、乙二醇二乙醚、二乙二醇二甲醚、三甘醇二甲醚、乙二醇甲酸乙醚、二乙氧基甲烷、1,3二甲氧基丙烷、1,1,3,3-四乙氧基丙烷醚或1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚中的至少一种。基于电解液的质量，碳酸酯的质量百分含量为20％至80％，羧酸酯的质量百分含量为0％至40％，醚的质量百分含量为0％至60％。例如，碳酸酯的质量百分含量为20％、30％、40％、50％、60％、70％、80％或上述任两个数值范围间 的任一数值，羧酸酯的质量百分含量为0％、10％、20％、30％、40％或上述任两个数值范围间的任一数值，醚的质量百分含量为0％、10％、20％、30％、40％、50％、60％或上述任两个数值范围间的任一数值。选用上述种类的有机溶剂，且将碳酸酯、羧酸酯和醚在电解液中的质量百分含量调控在上述范围内，有利于使电解液对正极活性材料和负极活性材料具有良好的浸润性，提高锂离子的传输速度，且使电解液具有良好的稳定性，减少电解液分解产气等风险的发生，从而提高电化学装置的循环性能和倍率性能。
在本申请的一些实施方案中，电解液还包括锂盐，锂盐包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、六氟砷酸锂(LiAsF6)、高氯酸锂(LiClO4)、四苯基硼酸锂(LiB(C6H5)4)、甲基磺酸锂(LiCH3SO3)、双氟磺酰亚胺锂(LiFSI)、三氟甲磺酸锂(LiCF3SO3(LiTA))、双三氟甲磺酰亚胺锂(LiN(SO2CF3)2(LiTFSI))、三(三氟甲基磺酰)甲基锂(LiC(SO2CF3)3)、六氟硅酸锂(LiSiF6)、二草酸硼酸锂(LiBOB)或二氟草酸硼酸锂(LiDFOB)中的至少一种；基于电解液的质量，锂盐的质量百分含量为6％至20％。例如，锂盐的质量百分含量为6％、8％、10％、12％、14％、16％、18％、20％或上述任两个数值范围间的任一数值。选用上述种类的锂盐且将其在电解液中的质量百分含量调控在上述范围内，有利于加快锂离子的传输，提升电化学装置的循环性能。
本申请对负极集流体没有特别限制，只要能够实现本申请目的即可。例如，负极集流体可以包含铜箔、铜合金箔、镍箔、不锈钢箔、钛箔、泡沫镍或泡沫铜等。本申请的负极活性材料层包含负极活性材料。在本申请中，对负极集流体、负极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，负极集流体的厚度为6μm至10μm，负极活性材料层的厚度为30μm至130μm。任选地，负极活性材料层还可以包括导电剂、稳定剂、粘结剂中的至少一种。本申请对负极活性材料层中的导电剂、稳定剂和粘结剂的种类没有特别限制，只要能够实现本申请目的即可。本申请对负极活性材料层中负极活性材料、导电剂、稳定剂和粘结剂的质量比没有特别限制，只要能够实现本申请目的即可。例如，负极活性材料层中负极活性材料、导电剂、粘结剂和稳定剂的质量比为(75～95):(0.01～8):(0.01～20):(0.01～10)。
本申请对正极极片没有特别限制，只要能够实现本申请目的即可。例如，正极极片包含正极集流体和正极活性材料层。本申请对正极集流体没有特别限制，只要能够实现本申请目的即可。例如，正极集流体可以包含铝箔、铝合金箔或复合集流体等。本申请的正极活性材料层包含正极活性材料。本申请对正极活性材料的种类没有特别限制，只要能够实现本申请目的即可。例如，正极活性材料可以包含镍钴锰酸锂(NCM811、NCM622、NCM523、NCM111、Ni88)、镍钴铝酸锂、磷酸铁锂、富锂锰基材料、钴酸锂(LiCoO2)、 锰酸锂、磷酸锰铁锂或钛酸锂等中的至少一种。在本申请中，正极活性材料还可以包含非金属元素，例如非金属元素包括氟、磷、硼、氯、硅或硫中的至少一种，这些元素能进一步提高正极活性材料的稳定性。在本申请中，对正极集流体和正极活性材料层的厚度没有特别限制，只要能够实现本申请目的即可。例如，正极集流体的厚度为5μm至20μm，优选为6μm至18μm。单面正极活性材料层的厚度为30μm至120μm。在本申请中，正极活性材料层可以设置于正极集流体厚度方向上的一个表面上，也可以设置于正极集流体厚度方向上的两个表面上。任选地，正极活性材料层还可以包括导电剂和粘结剂。本申请对正极活性材料层中的导电剂和粘结剂的种类没有特别限制，只要能够实现本申请目的即可。本申请对正极活性材料层中正极活性材料、导电剂、粘结剂的质量比没有特别限制，本领域技术人员可以根据实际需要选择，只要能够实现本申请目的即可。例如，正极活性材料层中正极活性材料、导电剂和粘结剂的质量比为(97.5～97.9):(0.9～1.7):(1.0～2.0)。
本申请对隔膜没有特别限制，只要能够实现本申请目的即可。例如，隔膜的材料可以包括但不限于聚乙烯(PE)、聚丙烯(PP)为主的聚烯烃(PO)、聚酯(例如聚对苯二甲酸二乙酯(PET))、纤维素、聚酰亚胺(PI)、聚酰胺(PA)、氨纶或芳纶中的至少一种；隔膜的类型可以包括但不限于织造膜、非织造膜(无纺布)、微孔膜、复合膜、隔膜纸、碾压膜或纺丝膜中的至少一种。例如，隔膜可以包括基材层和表面处理层。基材层可以为具有多孔结构的无纺布、膜或复合膜，基材层的材料可以包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺等中的至少一种。任选地，可以使用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。任选地，基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。例如，无机物层包括无机颗粒和粘结剂，所述无机颗粒没有特别限制，例如可以选自氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡等中的至少一种。所述粘结剂没有特别限制，例如可以选自聚偏氟乙烯、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、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。聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)等中的至少一种。
本申请的电化学装置还可以包括包装袋，本申请对包装袋没有特别限制，可以为本领域公知的包装袋，只要能够实现本申请目的即可。例如，铝塑膜或钢壳。
本申请对电化学装置的种类没有特别限制，其可以包括发生电化学反应的任何装置。例如，电化学装置可以包括但不限于：锂金属二次电池、锂离子二次电池(锂离子电池)、钠离子二次电池(钠离子电池)、锂聚合物二次电池、锂离子聚合物二次电池。
本申请对电化学装置的制备方法没有特别限制，可以选用本领域公知的制备方法，只要能够实现本申请目的即可。例如，电化学装置的制备方法包括但不限于如下步骤：将正极极片、隔膜和负极极片按顺序堆叠，并根据需要将其卷绕、折叠等操作得到卷绕结构的电极组件，将电极组件放入包装袋内，将电解液注入包装袋并封口，得到电化学装置；或者，将正极极片、隔膜和负极极片按顺序堆叠，然后将整个叠片结构的四个角固定好得到叠片结构的电极组件，将电极组件放入包装袋内，将电解液注入包装袋并封口，得到电化学装置。
本申请第二方面提供了一种电子装置，其包括前述任一实施方案所述的电化学装置。因此，电子装置具有良好的使用性能。
本申请的电子装置没有特别限制，其可以包括但不限于：笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。
测试方法和设备：
无机固态电解质、电解液成分及含量测试：
将锂离子电池(荷电状态为0％，工作电压2.5V)拆解得到负极极片，用碳酸二甲酯(DMC)清洗负极极片后，采用X射线衍射(XRD)测试负极极片表面的负极材料层中无机固态电解质的结构类型，扫描电子显微镜-能谱(SEM-EDS)测试无机固态电解质的组成。
将锂离子电池(荷电状态为0％，工作电压2.5V)拆解得到电解液，采用气相色谱质谱联用仪(GCMS)测试电解液中有机溶剂、式(I)化合物、聚合单体、引发剂、不饱和键的添加剂的质量百分含量，采用离子色谱-质谱联用测试锂盐的质量百分含量。
不同充电倍率的循环圈数测试：
将锂离子电池置于25℃常温环境中，静置30分钟，分别以0.2C、0.5C、1C恒流充电至电压为4.25V，恒压充电至0.05C，再以0.5C恒流放电至2.5V，按照上述流程进行充放电循环。记录首次放电容量、每圈循环后的放电容量、累计循环圈数分别为C1、C1'、ε，并利用如下公式计算循环容量保持率：η＝(C1'/C1)×100％，当η＝70％时，取当前累计循环圈数ε计为循环寿命。以循环圈数评价锂离子电池的循环性能，当循环圈数越大，则循环性能越好，反之，则循环性能越差。
实施例1-1
<电解液的制备>
在含水量小于10ppm的氩气气氛手套箱中，将有机溶剂按照EC:PC:DEC＝1:2:7的质量含量比例混合均匀后，加入锂盐LiPF6、LiFSI溶解并混合均匀，得到基础电解液。在基础电解液中加入式(I)化合物式(I-4)、聚合单体环氧乙烷和乙二醇双丙烯酸酯，混合均匀后得到电解液。
基于电解液的质量，LiPF6的质量百分含量为8％，LiFSI的质量百分含量为6％，式(I)化合物的质量百分含量m％＝0.01％，聚合单体的质量百分含量n％＝0.52％(环氧乙烷和乙二醇双丙烯酸酯分别为0.35％和0.17％)，其余为有机溶剂，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
<负极极片的制备>
将负极活性材料SiO、导电剂导电炭黑(Super P)、粘结剂丁苯橡胶(SBR，固含量45wt％)、稳定剂羧甲基纤维素钠(CMC-Na，重均分子量约400000)按照质量比86:2:2:10进行混合，然后加入去离子水作为溶剂，在真空搅拌机作用下搅拌至固含量为53wt％且体系均匀的负极浆料。将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔的一个表面上，85℃条件下烘干，得到单面涂布负极活性材料层(厚度130μm)的负极极片。之后，在该铜箔的另一个表面上重复以上步骤，得到双面涂布负极活性材料层的负极极片。经冷压，裁片，分切后，在120℃的真空条件下干燥12h得到规格为76mm×851mm的负极极片待用。
<正极极片的制备>
将正极活性材料Ni88(Li[Ni0.88Co0.02Mn0.1]O2)、导电剂导电炭黑(Super P)、粘结剂聚偏二氟乙烯(PVDF)按照质量比97:2:1进行混合，加入N-甲基吡咯烷酮(NMP)作为溶剂，在真空搅拌机作用下搅拌至固含量为75wt％且体系均匀的正极浆料。将正极浆料均匀涂覆在厚度为10μm的正极集流体铝箔的一个表面上，85℃条件下干燥4h，得到单面涂布正极活性材料层(厚度110μm)的正极极片。之后，在该铝箔的另一个表面上重复以上步骤，即得到双面涂布正极活性材料层的正极极片。经冷压，裁片，分切后，在85℃的真 空条件下干燥4h得到规格为74mm×867mm正极极片待用。
<隔膜>
采用厚度为7μm的聚乙烯薄膜。
<锂离子电池的制备>
将上述制备得到的负极极片、隔膜以及正极极片按顺序堆叠卷绕得到卷绕结构的电极组件。将电极组件置于铝塑膜包装袋中，干燥后注入电解液，经过真空封装、高温静置、化成、脱气、切边等工序得到锂离子电池。高温静置温度为60℃，静置时间为14h。化成上限电压为4.15V，化成温度为70℃，化成静置时间为2h。
实施例1-2至实施例1-7
除了按照表1调整相关制备参数以外，其余与实施例1-1相同。
实施例1-2至实施例1-7，式(I)化合物的质量百分含量发生变化时，有机溶剂的质量含量随之发生变化，其余组分的质量百分含量不变，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
实施例1-8至实施例1-13
除了按照表1调整相关制备参数以外，其余与实施例1-4相同。
实施例1-14至实施例1-20
除了按照表1调整相关制备参数以外，其余与实施例1-8相同。
实施例1-14至实施例1-20中，聚合单体的质量百分含量发生变化时，有机溶剂的质量含量随之发生变化，其余组分的质量百分含量不变，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
实施例1-21至实施例1-25
除了按照表1调整相关制备参数以外，其余与实施例1-4相同。
实施例1-21至实施例1-25中，式(I)化合物的质量百分含量和/或聚合单体的质量百分含量发生变化时，有机溶剂的质量含量随之发生变化，其余组分的质量百分含量不变，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
实施例2-1
<负极极片的制备>
将负极活性材料SiO、无机固态电解质Li7La3Zr2O12(石榴石型无机氧化物材料)、导电剂导电炭黑(Super P)、粘结剂丁苯橡胶(SBR，固含量45wt％)、稳定剂羧甲基纤维素钠(CMC-Na，重均分子量约400000)按照质量比85:1:2:2:10进行混合，然后加入去离子水作为溶剂，在真空搅拌机作用下搅拌至固含量为53wt％且体系均匀的负极浆料。将负极 浆料均匀涂覆在厚度为8μm的负极集流体铜箔的一个表面上，85℃条件下烘干，得到单面涂布负极活性材料层(厚度130μm)的负极极片。之后，在该铜箔的另一个表面上重复以上步骤，得到双面涂布负极活性材料层的负极极片。经冷压，裁片，分切后，在120℃的真空条件下干燥12h得到规格为76mm×851mm的负极极片待用。
其余与实施例1-19相同。
实施例2-2至实施例2-7
除了按照表2调整相关制备参数以外，其余与实施例2-1相同。
实施例2-2至实施例2-7中，无机固态电解质的质量百分含量θ发生变化时，负极活性材料的质量百分含量随之变化，其余组分含量不变，负极活性材料、无机固态电解质、导电剂、粘结剂和稳定剂的质量百分含量之和为100％；聚合单体的质量百分含量发生变化时，有机溶剂的质量含量随之发生变化，其余组分的质量百分含量不变，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
实施例2-8至实施例2-13
除了按照表2调整相关制备参数以外，其余与实施例2-1相同。
实施例2-14
<电解液的制备>与实施例1-3相同。
其余除了在<负极极片的制备>中，将Li7La3Zr2O12替换为Li6.5La3Zr1.5Ta0.5O12以外，与实施例2-1相同。
实施例2-15
除了在<电解液的制备>中，按照表2调整聚合单体的质量百分含量n％，有机溶剂的质量含量随之发生变化以外，其余与实施例2-14相同。
实施例3-1
除了在<电解液的制备>中还加入表3含量的引发剂偶氮二异丁腈，有机溶剂的质量百分含量随之减少，式(I)化合物、锂盐、聚合单体的质量百分含量不变以外，其余与实施例2-1相同。
实施例3-2至实施例3-6
除了按照表3调整引发剂的质量百分含量y％，有机溶剂的质量百分含量随之减少，式(I)化合物、锂盐、聚合单体的质量百分含量不变以外，其余与实施例3-1相同。
实施例3-7
除了按照表3调整相关制备参数以外，其余与实施例3-5相同。
实施例3-8
除了在<电解液的制备>中还加入表3含量的含不饱和键的添加剂，有机溶剂的质量百分含量随之减少，式(I)化合物、锂盐、聚合单体的质量百分含量不变以外，其余与实施例2-1相同。
实施例3-9至实施例3-13
除了按照表3调整含不饱和键的添加剂的种类和质量百分含量h％，有机溶剂的质量百分含量随之减少，式(I)化合物、锂盐、聚合单体的质量百分含量不变以外，其余与实施例3-8相同。
实施例3-14
除了在<电解液的制备>中还加入表3含量和种类的含不饱和键的添加剂，有机溶剂的质量百分含量随之减少，式(I)化合物、锂盐、聚合单体、引发剂的质量百分含量不变以外，其余与实施例3-4相同。
实施例3-15
除了按照表3调整相关制备参数以外，其余与实施例3-14相同。
对比例1至对比例9
除了按照表1调整相关制备参数以外，其余与实施例1-1相同。
对比例1至对比例9中，式(I)化合物的质量百分含量和/或聚合单体的质量百分含量发生变化时，有机溶剂的质量含量随之发生变化，其余组分的质量百分含量不变，有机溶剂、锂盐、式(I)化合物和聚合单体的质量百分含量之和为100％。
各实施例和对比例的制备参数和性能参数如表1至表3所示。
表1


注：表1中的“\”表示无相应参数。
从实施例1-1至实施例1-20和对比例1至对比例9可以看出，选用电解液中同时加入本申请的式(I)化合物和聚合单体，且式(I)化合物和聚合单体的质量百分含量在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有更高的循环圈数，表明实施例的锂离子电池具有更高的循环性能和更宽的充电倍率窗口，其循环性能和充电倍率窗口得到提高。而对比例1的电解液中未加入本申请的式(I)化合物和聚合单体；对比例2和对比例3的电解液中，加入了本申请的聚合单体，但未加入本申请的式(I)化合物；对比例4至对比例6的电解液中，加入了本申请的式(I)化合物，未加入本申请的聚合单体；对比例7和对比例8的电解液中同时加入了本申请的式(I)化合物和聚合单体，但聚合单体的质量百分含量不在本申请范围内；对比例9的电解液中同时加入了本申请的式(I)化合物和聚合单体，但式(I)化合物的质量百分含量不在本申请范围内，对比例1至对比例9的锂离子电池，在0.2C、0.5C和1C的充电倍率下均具有更低的循环圈数，或者在0.5C、1C的充电倍率下均具有更低的循环圈数，或者在1C的高充电倍率下具有更低的循环圈数，表明锂离子电池的循环性能或者说在高倍率下的循环性能较差，锂离子电池的充电倍率窗口较小，锂离子电池的循环性能和充电倍率窗口未能得到提高。
式(I)化合物的质量百分含量m％通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-1至实施例1-7和对比例9可以看出，选用式(I)化合物的质量百分含量m％ 在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
式(I)化合物的种类通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-4、实施例1-8至实施例1-13可以看出，选用式(I)化合物的种类在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
聚合单体的质量百分含量n％通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-14至实施例1-18、对比例7和对比例8可以看出，选用聚合单体的质量百分含量n％在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
聚合单体的种类通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-8、实施例1-16、实施例1-19和实施例1-20可以看出，选用聚合单体的的种类在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
(n/M单)/(m/M(I))的值通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-1至实施例1-25可以看出，选用(n/M单)/(m/M(I))的值在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
表2

注：表2中的“\”表示无相应参数。
从实施例1-19、实施例2-1至实施例2-13可以看出，在负极材料层中进一步添加无机物固态电解质，无机固态电解质与包含有式(I)化合物和聚合单体的电解液协同作用，能够进一步提高锂离子电池的循环性能和充电倍率窗口。
无机固态电解质的质量百分含量θ％通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-19、实施例2-1至实施例2-7可以看出，选用无机固态电解质的质量百分含量θ％在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
n/θ的值通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-19、实施例2-1至实施例2-7可以看出，选用n/θ的值在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
无机固态电解质的种类通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例1-3和实施例2-14，实施例1-19、实施例2-1、实施例2-8至实施例2-13，实施例1-20和实施例2-15可以看出，选用无机固态电解质的种类在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
表3
注：表3中的“\”表示无相应参数；表3中的“y(％)”表示：基于电解液的质量，引发剂的质量百分含量；表3中的“h(％)”表示：基于电解液的质量，含不饱和键的添加剂的质量百分含量。
从实施例2-1、实施例3-1至实施例3-7可以看出，在电解液中进一步添加引发剂，使电解液中的聚合单体采用引发剂进行引发聚合时，锂离子电池的循环性能和充电倍率窗口得到进一步提高。
引发剂的质量百分含量y％通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例2-1、实施例3-1至实施例3-6可以看出，选用引发剂的质量百分含量y％在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明 锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
引发剂的种类通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例3-5和实施例3-7可以看出，选用引发剂的种类在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
从实施例2-1、实施例3-8至实施例3-11可以看出，在电解液中进一步加入含不饱和键的添加剂，锂离子电池的循环性能和充电倍率窗口能够进一步提高。
含不饱和键的添加剂的质量百分含量h％通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例2-1、实施例3-8至实施例3-12可以看出，选用含不饱和键的添加剂的质量百分含量h％在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
含不饱和键的添加剂的种类通常也会影响锂离子电池的循环性能和充电倍率窗口。从实施例3-8和实施例3-13可以看出，选用含不饱和键的添加剂的种类在本申请范围内的锂离子电池，其在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
从实施例3-4、实施例3-13至实施例3-15可以看出，在电解液中同时加入引发剂和含不饱和键的添加剂时，锂离子电池在0.2C、0.5C和1C的充电倍率下均具有较高的循环圈数，表明锂离子电池具有良好的循环性能和较宽的充电倍率窗口。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (15)

  1. 一种电化学装置，包括电解液、负极极片、隔膜和正极极片；
    所述电解液包括式(I)化合物和聚合单体：
    其中，X1、X2、X3、X4、Y1、Y2、Y3和Y4各自独立地选自O、C1至C3碳链或单键，X1和Y1不同时为O或单键，X2和Y2不同时为O或单键，X3和Y3不同时为O或单键，X4和Y4不同时为O或单键，X1、X2、Y1和Y2中的至少一个为O，X3、X4、Y3和Y4中的至少一个为O；
    Z1和Z2各自独立地选自卤素或末端具有聚合功能基团的C1至C4碳链，所述聚合功能基团包括羧基、羟基、醛基、酰氧基、氨基、烯基或炔基；
    所述聚合单体包括丙烯酸甲酯、甲基丙烯酸甲酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、乙烯、丙烯、醋酸乙烯酯、二氟乙烯、四氟乙烯、六氟丙烯、丙烯腈、乙二醇、乙二醇双丙烯酸酯、二乙二醇双丙烯酸酯、环氧乙烷、二氧戊烷、2,6-二甲基苯酚、3,4-乙烯二氧噻吩或4,6-二氨基-1,3-间二苯酚中的至少一种；
    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m％，0.01≤m≤6，所述聚合单体的质量百分含量为n％，0.5≤n≤10；
    所述负极极片包括负极集流体以及设置于所述负极集流体至少一个表面上的负极材料层，所述负极材料层包括含硅负极活性材料。
  2. 根据权利要求1所述的电化学装置，其中，所述式(I)化合物包括以下式(I-1)化合物至式(I-8)化合物中的至少一个：

  3. 根据权利要求1所述的电化学装置，其中，所述电化学装置满足以下条件中的至少一者：
    (1)0.05≤m≤4；
    (2)1≤n≤6。
  4. 根据权利要求1所述的电化学装置，其中，所述式(I)化合物的摩尔质量为M(I)g/mol，所述聚合单体的摩尔质量为M单g/mol，所述m、所述n、所述M(I)和所述M单之间满足：2≤(n/M单)/(m/M(I))≤200。
  5. 根据权利要求1所述的电化学装置，其中，所述式(I)化合物的摩尔质量为M(I)g/mol，所述聚合单体的摩尔质量为M单g/mol，所述m、所述n、所述M(I)和所述M单之间满足：3≤(n/M单)/(m/M(I))≤30。
  6. 根据权利要求1所述的电化学装置，其中，所述负极材料层还包括无机固态电解质，所述无机固态电解质包括无机氧化物材料或无机硫化物材料中的任一种；
    基于所述负极材料层的质量，所述无机固态电解质的质量百分含量为θ％，0.01≤θ≤5。
  7. 根据权利要求6所述的电化学装置，其中，0.5≤n/θ≤100。
  8. 根据权利要求6所述的电化学装置，其中，0.1≤θ≤5，和/或1≤n/θ≤30。
  9. 根据权利要求6所述的电化学装置，其中，所述无机氧化物材料的晶型结构包括NASICON型、LISICON型、钙钛矿型或石榴石型中的至少一种；
    所述NASICON型无机氧化物材料的化学式为Li1+xM1xD12-x(PO4)3，其中，0.01≤x≤0.5，M1包括Al、Y、Ga、Cr、In、Fe、Se或La中的至少一种，D1包括Ti、Ge、Ta、Zr、Sn、Fe、V、Hf中的至少一种；
    所述LISICON型无机氧化物材料的化学式为Li14M2(D2O4)4，其中，M2包括Zr、Cr、Sn或Zn中的至少一种，D2包括Si、Ge、S或P中的至少一种；
    所述钙钛矿型无机氧化物材料的化学式为Li3yM32/3-yD3O3，其中，0.01≤y≤0.5，M3包括La、Al、Mg、Fe或Ta中的至少一种，D3包括Ti、Nb、Sr或Pr中的至少一种；
    所述石榴石型无机氧化物材料的化学式为LiZM43D42O12，其中，6≤z≤7，M4包括La、Ca、Sr、Ba或K中的至少一种，D4包括Zr、Ta、Nb或Hf中的至少一种；
    所述无机硫化物材料包括锂锗磷硫、锂磷硫、锂磷硫氯、锂锡磷硫、锂硅磷硫、锂锗硅磷硫、锂铝磷硫、锂锗硫或锂硅硫中的至少一种。
  10. 根据权利要求1所述的电化学装置，其中，所述电解液还包括引发剂，所述引发剂包括偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯或过氧化甲乙酮中的至少一种；
    基于所述电解液的质量，所述引发剂的质量百分含量为0.001％至2％。
  11. 根据权利要求1所述的电化学装置，其中，所述电解液还包括含不饱和键的添加剂，所述含不饱和键的添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙烯磺酸内酯、1,3-丙烷磺酸内酯、3-己烯二氰、反丁烯二酸酐或三烯丙基甲氧基硅烷中的至少一种；
    基于所述电解液的质量，所述含不饱和键的添加剂的质量百分含量为0.01％至40％。
  12. 根据权利要求1所述的电化学装置，其中，所述含硅负极活性材料包括SiOw、硅碳化合物或硅单质中的至少一种，0.5≤w≤1.5。
  13. 根据权利要求1所述的电化学装置，其中，所述电解液还包括碳酸酯、羧酸酯或醚中的至少一种；
    所述碳酸酯包括碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸丙烯酯、碳酸乙烯酯、碳酸二丙酯、碳酸甲丙酯、氟代碳酸乙烯酯、二氟代碳酸乙烯酯、五氟丙基碳酸乙烯酯、甲基三氟乙基碳酸酯、三氟甲基碳酸乙烯酯或二(2,2,2-三氟乙基)碳酸酯中的至少一种，所述羧酸酯包括丙酸丙酯、丙酸乙酯、乙酸乙酯、甲酸乙酯、乙酸甲酯、丙酸甲酯、乙酸丙酯、丁酸丁酯、二氟乙酸乙酯、乙酸二氟乙酯、三氟乙酸乙酯、乙酸三氟乙酯或三氟丙酸甲酯中的至少一种，所述醚包括1,3-二氧六环、1,4-二氧六环、1,3-二氧戊环、4-甲基-1,3-二氧戊环、二乙醚、乙二醇二乙醚、二乙二醇二甲醚、三甘醇二甲醚、乙二醇甲酸乙醚、二乙氧基甲烷、1,3-二甲氧基丙烷、1,1,3,3-四乙氧基丙烷醚或1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚中的至少一种；
    基于所述电解液的质量，所述碳酸酯的质量百分含量为20％至80％，所述羧酸酯的质量百分含量为0％至40％，所述醚的质量百分含量为0％至60％。
  14. 根据权利要求1所述的电化学装置，其中，所述电解液还包括锂盐，所述锂盐包括六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、高氯酸锂、四苯基硼酸锂、甲基磺酸锂、三氟甲磺酸锂、双三氟甲磺酰亚胺锂、三(三氟甲基磺酰)甲基锂、六氟硅酸锂、二草酸硼酸锂或二氟草酸硼酸锂中的至少一种；
    基于所述电解液的质量，所述锂盐的质量百分含量为6％至20％。
  15. 一种电子装置，其包括权利要求1至14中任一项所述的电化学装置。
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