WO2023213188A1 - 一种电化学装置 - Google Patents

一种电化学装置 Download PDF

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Publication number
WO2023213188A1
WO2023213188A1 PCT/CN2023/088991 CN2023088991W WO2023213188A1 WO 2023213188 A1 WO2023213188 A1 WO 2023213188A1 CN 2023088991 W CN2023088991 W CN 2023088991W WO 2023213188 A1 WO2023213188 A1 WO 2023213188A1
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lithium
negative electrode
positive electrode
electrolyte
solid electrolyte
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English (en)
French (fr)
Inventor
赵伟
李素丽
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Publication of WO2023213188A1 publication Critical patent/WO2023213188A1/zh
Priority to US18/817,638 priority Critical patent/US20240421428A1/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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 disclosure belongs to the technical field of electrochemical energy storage, and specifically relates to an electrochemical device.
  • Lithium-ion batteries one of the electrochemical devices, are secondary batteries that are widely used.
  • the electrolyte of lithium-ion batteries has an important impact on the performance of the battery, but the composition of the electrolyte is relatively complex. Some components are incompatible with the negative electrode of lithium-ion batteries, and some components are incompatible with the positive electrode of lithium-ion batteries. This greatly shortens the Battery cycle life.
  • the present disclosure provides an electrochemical device.
  • the positive electrolyte and the negative electrolyte are separated by a solid electrolyte membrane, which can realize the connection with the positive electrode.
  • the electrolyte in contact with the electrode sheet is different from the electrolyte in contact with the negative electrode sheet, which solves the problem that some components in the electrolyte are incompatible with the positive electrode sheet or the negative electrode sheet.
  • the electrochemical device designed in this way has a significantly improved cycle life.
  • An electrochemical device which includes a positive electrode sheet, a negative electrode sheet, a solid electrolyte membrane, a positive electrode electrolyte, a negative electrode electrolyte and a packaging shell;
  • the positive electrode sheet and the negative electrode sheet are located on both sides of the solid electrolyte membrane, the positive electrolyte is located on one side of the positive electrode sheet, the negative electrolyte is located on one side of the negative electrode sheet, the positive electrolyte and The negative electrolyte is separated by the solid electrolyte membrane.
  • the solid electrolyte membrane has a dense structure. Specifically, it has a dense non-porous structure or a dense non-penetrating pore structure.
  • the positive electrolyte includes nitrile compounds, and the mass fraction of the nitrile compounds is not less than 5%; the negative electrolyte includes ether compounds, and the mass fraction of the ether compounds is not less than 5%. 4%.
  • the positive electrolyte further includes lithium salt A, solvent A and additive A; the negative electrolyte further includes lithium salt B, solvent B and additive B.
  • the ratio of the remaining amount of the positive electrolyte m1 (unit g) to the design capacity Q (unit Ah) of the electrochemical device satisfies 0.5g/Ah ⁇ m1/Q ⁇ 2.0g/Ah.
  • the ratio of the storage capacity m2 (unit g) of the negative electrolyte to the design capacity Q (unit Ah) of the electrochemical device satisfies 0.5g/Ah ⁇ m2/Q ⁇ 2.0g/Ah.
  • the storage amount m1 of the positive electrolyte ⁇ the storage amount m2 of the negative electrolyte.
  • the lithium salt A contains at least 60 wt% lithium hexafluorophosphate.
  • the lithium salt B contains at least 50 wt% lithium difluoroxalate borate.
  • the lithium salt B contains at least 1 wt% lithium nitrate.
  • the solid electrolyte membrane is an inorganic solid electrolyte membrane with a dense non-porous structure, or the solid electrolyte membrane is an inorganic solid electrolyte membrane with a dense non-penetrating pore structure.
  • the solid electrolyte membrane has an ionic conductivity ⁇ 0.1 ms/cm.
  • the material forming the solid electrolyte membrane is at least one of a Garnet type oxide electrolyte, a NASICON type oxide electrolyte, a perovskite type oxide electrolyte and a sulfide electrolyte.
  • a positive electrode sealing ring is provided between the positive electrode sheet and the solid electrolyte membrane to prevent the positive electrode electrolyte from leaking from the edge of the positive electrode sheet.
  • a negative electrode sealing ring is provided between the negative electrode sheet and the solid electrolyte membrane to prevent the negative electrode electrolyte from leaking from the edge of the negative electrode sheet.
  • the arrangement of the positive electrode sealing ring and the negative electrode sealing ring must ensure that the electrolyte cannot penetrate, and the material forming the positive electrode sealing ring (or defined as sealant) and the material forming the negative electrode sealing ring (or defined as sealants) are the same or different, and are independently selected from at least one of maleic anhydride grafted polypropylene, polyurethane, nitrile rubber, butyl rubber, chloroprene rubber, epoxy resin and silicone rubber.
  • the positive electrode sheet includes a positive electrode current collector, a positive electrode coating area provided on at least one side surface of the positive electrode current collector, and a positive electrode connected to the positive electrode coating area and located on the periphery of the positive electrode coating area. Sealing area; the positive electrode coating area is provided with positive electrode paste, and the positive electrode sealing area is provided with the positive electrode sealing ring.
  • the negative electrode sheet includes a negative electrode current collector, a negative electrode coating area provided on at least one side surface of the negative electrode current collector, and a negative electrode connected to the negative electrode coating area and located on the periphery of the negative electrode coating area.
  • Sealing area the negative electrode coating area is provided with negative electrode paste, and the negative electrode sealing area is provided with the negative electrode sealing ring.
  • the electrochemical device may be a battery or a supercapacitor.
  • the present disclosure separates the positive electrolyte and the negative electrolyte through a solid electrolyte membrane, adds a high content of nitrile compounds to the positive electrolyte, and adds a high content of ether compounds to the negative electrolyte.
  • the nitrile compounds can effectively enhance
  • ether compounds can effectively improve the stability of the negative electrode interface. Nitrile compounds will not penetrate into the negative electrode and cause adverse side reactions, and ether compounds will not penetrate into the positive electrode and cause adverse oxidation reactions.
  • the electrochemical device based on such design has a significantly improved cycle life, especially the cycle life of the electrochemical device containing metallic lithium in the negative electrode.
  • FIG. 1 is a structural cross-sectional view of the lithium-ion battery of the present disclosure (cross-sectional view perpendicular to the stacking direction).
  • FIG. 2 is an expanded view (top view along the stacking direction) of a stacked unit of the lithium-ion battery of the present disclosure.
  • the components of the electrolyte in electrochemical devices are relatively complex. Some components are incompatible with the negative electrode of the electrochemical device, and some components are incompatible with the positive electrode of the electrochemical device, which limits the application of the electrochemical device.
  • Nitrile compounds can effectively stabilize transition metal elements, thereby improving the stability of the cathode interface, but they will cause adverse side reactions on the negative electrode. Therefore, in order to improve cycle life, the amount of nitrile compounds added in electrochemical devices is strictly controlled. Within 5%. Ether compounds can effectively improve the stability of the negative electrode interface, but they will cause adverse side reactions on the high-voltage cathode. Therefore, in order to improve the cycle life, the amount of ether compounds added in the electrochemical device is strictly controlled within 4%. Even in practical applications, no ether compounds are added.
  • the inventor of the present disclosure unexpectedly discovered that if the positive electrolyte and the negative electrolyte are separated by a solid electrolyte membrane, and a high content of nitrile compounds is added to the positive electrolyte, and a high content of ether is added to the negative electrolyte, compounds, thus effectively improving the cycle life of electrochemical devices.
  • the present disclosure provides an electrochemical device, which includes a positive electrode sheet, a negative electrode sheet, a solid electrolyte membrane, a positive electrode electrolyte, a negative electrode electrolyte and a packaging shell;
  • the positive electrode sheet and the negative electrode sheet are located on both sides of the solid electrolyte membrane, the positive electrolyte is located on one side of the positive electrode sheet, the negative electrolyte is located on one side of the negative electrode sheet, the positive electrolyte and The negative electrolyte is separated by the solid electrolyte membrane.
  • the solid electrolyte membrane has a dense structure. Specifically, it has a dense non-porous structure or a dense non-penetrating pore structure.
  • the positive electrode electrolyte and the negative electrode electrolyte have different compositions.
  • the positive electrolyte and the negative electrolyte are separated by the solid electrolyte membrane means that the positive electrolyte and the negative electrolyte are separated by the solid electrolyte membrane and do not contact each other, but Ions can move through the solid electrolyte membrane.
  • the positive electrolyte solution includes nitrile compounds, and the mass fraction of the nitrile compounds is not less than 5%.
  • the mass fraction of the nitrile compound is not less than 5% means that the mass percentage of the nitrile compound in the total mass of the positive electrolyte is not less than 5%, that is, greater than or equal to 5%.
  • the nitrile compound may be It often fully forms a protective layer on the surface of the cathode active material, effectively stabilizing the transition metal elements in the cathode active material and preventing the transition metal elements from being destroyed under high voltage, thereby improving the stability of the cathode interface and improving cycle performance. If it is less than 5%, although the nitrile compound can form a protective layer on the surface of the cathode active material and improve the stability of the cathode interface, the improvement effect is not significant.
  • the mass fraction of the nitrile compound is 5% to 80%, exemplarily 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40% %, 50%, 60%, 70% or 80%.
  • the nitrile compound is selected from the group consisting of acetonitrile, propionitrile, butyronitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, 1,3,6-hexanetrinitrile, 1, 3,5-pentanetricarbonitrile, ethylene glycol dipropionitrile ether, hexafluorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene, pentafluorophenoxycyclotriphosphazene, 1,4-dicyanide -2-Butene, p-fluorobenzonitrile, p-methylbenzonitrile, 2-fluoroadiponitrile, 2,2-difluorosuccinonitrile, tricyanobenzene, acrylonitrile, crotononitrile, trans At least one of butenedonitrile and trans-hexenedonitrile. Further preferred is at least one of acetonitrile, pro
  • the negative electrolyte solution includes ether compounds, and the mass fraction of the ether compounds is not less than 4%.
  • the mass fraction of the ether compound is not less than 4% means that the mass percentage of the ether compound in the total mass of the negative electrolyte is not less than 4%, that is, greater than or equal to 4%.
  • the ether compound has excellent anti-reduction stability, especially the ether compound has high stability with metallic lithium, it can effectively suppress the interface side reaction between the negative electrolyte and the negative electrode material. This significantly improves the stability of the negative electrode interface and improves cycle performance. If it is less than 4%, although the ether compound can also improve the stability of the negative electrode interface, the improvement effect is not significant.
  • the mass fraction of the ether compound is 4% to 80%, exemplarily 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30 %, 40%, 50%, 60%, 70% or 80%.
  • the ether compound is selected from the group consisting of ethylene glycol dimethyl ether, diglyme glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether.
  • ethylene glycol dimethyl ether diglyme glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, dioxane and tetrahydrofuran. .
  • the positive electrolyte further includes lithium salt A, solvent A and additive A.
  • the negative electrolyte further includes lithium salt B, solvent B and additive B.
  • the ratio of the retention amount m1 (unit g) of the positive electrolyte to the design capacity Q (unit Ah) of the electrochemical device satisfies 0.5g/Ah ⁇ m1/Q ⁇ 2.0g/Ah.
  • the ratio of the storage capacity m2 (unit g) of the negative electrolyte to the design capacity Q (unit Ah) of the electrochemical device satisfies 0.5g/Ah ⁇ m2/Q ⁇ 2.0g/Ah.
  • the "retention amount of positive electrolyte” and the “retention amount of negative electrolyte” can be determined by conventional methods. Confirm by weighing.
  • the retention amount m1 of the positive electrode electrolyte ⁇ the retention amount m2 of the negative electrode electrolyte. Since the growth rate of the negative electrode SEI film in the electrochemical device is relatively fast, the consumption rate of the negative electrode electrolyte in the electrochemical device is usually faster than the consumption rate of the positive electrode electrolyte. Such an arrangement can further facilitate The entire electrochemical device obtains better cycle performance.
  • the lithium salt A and the lithium salt B are the same or different, and are independently selected from lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), Lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF 6 ), lithium difluorophosphate (LiPF 2 O 2 ), lithium 4,5-dicyano-2-trifluoromethylimidazole (LiDTI) , lithium dioxalate borate (LiBOB), lithium bis(malonate)borate (LiBMB), lithium difluoroxalate borate (LiDFOB), lithium bis(difluoromalonate)borate (LiBDFMB), (malonic acid Lithium oxalate)borate (LiMOB), lithium (difluoromalonate)bor
  • the solvent A and the solvent B are the same or different, and are independently selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, and fluoroethylene carbonate (FEC). ), difluoroethylene carbonate (DFEC), fluorinated dimethyl carbonate, fluorinated methyl ethyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate Ester (EMC), methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate (EA), propyl acetate, butyl acetate, methyl propionate, ethyl propionate, Propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl difluorate (F
  • the additive A and the additive B are the same or different, and are independently selected from vinylene carbonate (VC), vinylethylene carbonate (VEC), 1,3-propane sulfonic acid.
  • Ester (PS) trifluoromethylethylene carbonate, dimethyl sulfate, vinyl sulfate (DTD), vinyl methyl sulfate, propylene sulfate, vinyl sulfite, succinic anhydride, biphenyl, diphenyl ether , toluene, xylene, cyclohexylbenzene, fluorobenzene, p-fluorotoluene, p-fluoroanisole, tert-butylbenzene, tert-amylbenzene, propylene sultone, butane sultone, methane disulfonate Methylene acid ester, ethylene glycol bis(propionitrile) ether, hexamethyldisilazan
  • the lithium salt A contains at least 60 wt% lithium hexafluorophosphate.
  • Add more than 60wt% hexafluoride Lithium phosphate can significantly reduce the preparation cost of electrochemical devices while ensuring their performance.
  • the lithium salt B contains at least 50 wt% lithium difluoroxalate borate. Adding more than 50wt% lithium difluoroxalate borate can improve the stability of the SEI film of the negative electrode and further increase the cycle life, especially when using lithium metal as the negative electrode, the cycle life of the electrochemical device.
  • the lithium salt B contains at least 1 wt% lithium nitrate. Adding more than 1wt% lithium nitrate can increase the proportion of inorganic components in the negative SEI film, improve the stability of the negative SEI film, and further improve the cycle life, especially when using metallic lithium as the negative electrode. The cycle life of electrochemical devices.
  • the solid electrolyte membrane has a dense structure. Specifically, it has a dense non-porous structure or a dense non-penetrating pore structure.
  • the solid electrolyte membrane is an inorganic solid electrolyte membrane with a dense structure without through-holes.
  • the solid electrolyte membrane is an inorganic solid electrolyte membrane with a dense non-porous structure.
  • the density of the solid electrolyte membrane is greater than or equal to 99%, such as 99% to 100%.
  • the solid electrolyte membrane is different from a conventional separator.
  • the solid electrolyte membrane of the present disclosure has a dense structure, specifically a dense non-porous structure or a dense non-penetrating pore structure.
  • the solid electrolyte with such a structure The arrangement of the membrane makes it impossible for the electrolyte to pass through, but the lithium ions in the electrolyte can migrate and pass through the solid electrolyte membrane. Therefore, the arrangement of the solid electrolyte membrane can ensure that the positive electrode electrolyte on both sides of the solid electrolyte membrane and the negative electrolyte are separated by the solid electrolyte membrane and do not contact each other.
  • the thickness of the solid electrolyte membrane is preferably 5 ⁇ m to 100 ⁇ m.
  • the solid electrolyte membrane with a thickness less than 5 ⁇ m is difficult to realize with existing preparation technology. At the same time, when the thickness is less than 5 ⁇ m, the strength of the solid electrolyte membrane is too low and is easily broken, making it difficult to assemble into the electrochemical device.
  • the solid electrolyte membrane with a thickness greater than 100 ⁇ m has high mechanical strength and is easy to assemble the electrochemical device, a solid electrolyte membrane with a thickness that is too thick will reduce the energy density of the electrochemical device.
  • the solid electrolyte membrane has an ionic conductivity ⁇ 0.1 ms/cm.
  • the ionic conductivity of the solid electrolyte membrane is ⁇ 1 ms/cm.
  • the material forming the solid electrolyte membrane is at least one of a Garnet type oxide electrolyte, a NASICON type oxide electrolyte, a perovskite type oxide electrolyte and a sulfide electrolyte.
  • the Garnet-type oxide electrolyte is preferably lithium lanthanum zirconium oxide (LLZO), tantalum-doped lithium lanthanum zirconium oxide At least one of oxygen (LLZTO) and niobium-doped lithium lanthanum zirconium oxygen (LLZNO).
  • LLZO lithium lanthanum zirconium oxide
  • LLZTO tantalum-doped lithium lanthanum zirconium oxide
  • LLZNO niobium-doped lithium lanthanum zirconium oxygen
  • Preferred is at least one of lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium aluminum titanium germanium phosphate, and lithium silicon germanium phosphate (Li 3 Zr 2 Si 2 PO 12 ).
  • the perovskite oxide electrolyte is preferably lithium lanthanum titanium oxide (LLTO).
  • the solid electrolyte membrane has a thickness of 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, or 100 ⁇ m. More preferably, in some embodiments, the thickness of the solid electrolyte membrane is 15 ⁇ m, 20 ⁇ m, 25 ⁇ m or 30 ⁇ m.
  • the preparation method of the solid electrolyte membrane is as follows:
  • the material forming the solid electrolyte membrane into solid electrolyte powder with a particle size less than 2 ⁇ m by ball milling; then mix and disperse the solid electrolyte powder, the first binder and the first solvent evenly to obtain a solid electrolyte slurry material; apply the solid electrolyte slurry on the polymer base film, dry the first solvent to obtain a composite film; remove the composite film from the polymer base film and cut it into required specifications , and then in an inert gas atmosphere, under pressure conditions, and at high temperature, the solid electrolyte membrane is obtained by debinding and sintering.
  • the solid electrolyte membrane prepared by this method is a fully inorganic solid electrolyte membrane, and due to high-temperature sintering, the solid electrolyte membrane is an inorganic membrane with a dense non-porous structure or a dense non-penetrating pore structure, so liquid cannot directly pass through.
  • the temperature of the debinding ranges from 200°C to 1400°C, and is specifically set according to the type of the first adhesive.
  • the sintering temperature is 200°C to 1400°C, and is specifically set according to the type of material forming the solid electrolyte membrane.
  • the pressure range is 10MPa ⁇ 300MPa.
  • the first binder and the first solvent are not particularly limited, and may be preferred depending on the type of material forming the solid electrolyte membrane.
  • the first binder is preferably polyvinylidene fluoride (PVDF), polyethylene oxide, polyvinyl alcohol, polyvinyl butyral (PVB), ethyl cellulose (EC) and acrylic resin.
  • PVDF polyvinylidene fluoride
  • PVB polyvinyl butyral
  • EC ethyl cellulose
  • acrylic resin acrylic resin
  • the first solvent is preferably one or more of NMP, water, acetonitrile and toluene.
  • a positive electrode sealing ring is provided between the positive electrode sheet and the solid electrolyte membrane to prevent the positive electrode electrolyte from leaking from the edge of the positive electrode sheet.
  • a negative electrode sealing ring is provided between the negative electrode sheet and the solid electrolyte membrane to prevent the negative electrode electrolyte from leaking from the edge of the negative electrode sheet.
  • the positive electrode sealing ring and the negative electrode sealing ring are arranged to ensure that the electrolyte cannot penetrate, and the material forming the positive electrode sealing ring (or defined as sealant) and the material forming the negative electrode sealing ring are
  • the materials (or defined as sealants) are the same or different, preferably at least one of maleic anhydride grafted polypropylene, polyurethane, nitrile rubber, butyl rubber, chloroprene rubber, epoxy resin and silicone rubber.
  • the positive electrode sealing ring may be formed by melt bonding or solidification bonding of the materials forming the positive electrode sealing ring.
  • the negative electrode sealing ring may be formed by melt bonding or solidification bonding of the materials forming the negative electrode sealing ring.
  • the positive electrode sheet includes a positive electrode current collector, a positive electrode coating area provided on at least one side surface of the positive electrode current collector, and a positive electrode coating area connected to the positive electrode coating area and located on the periphery of the positive electrode coating area.
  • Positive electrode sealing area; the positive electrode coating area is provided with positive electrode paste, and the positive electrode sealing area is provided with the positive electrode sealing ring.
  • the negative electrode sheet includes a negative electrode current collector, a negative electrode coating area disposed on at least one side surface of the negative electrode current collector, and a negative electrode coating area connected to the negative electrode coating area and located on the periphery of the negative electrode coating area.
  • the cathode active material in the cathode sheet can be a cathode active material known in the art, capable of reversible intercalation/deintercalation of ions.
  • a cathode active material known in the art capable of reversible intercalation/deintercalation of ions.
  • it is a lithium transition metal composite oxide, in which the transition metal can be one or more of Mn, Fe, Ni, Co, Cr, Ti, Zn, V, Al, Zr, Ce and Mg.
  • the lithium transition metal composite oxide can also be doped with elements with high electronegativity, such as one or more of S, F, Cl and I, which can make the cathode active material have higher structural stability. and electrochemical performance.
  • the lithium transition metal composite oxide is LiMn 2 O 4 , LiNiO 2 , LiCoO 2 , LiNi 1-y Co y O 2 (0 ⁇ y ⁇ 1), LiN a Co b Al 1-ab O 2 ( 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ a+b ⁇ 1), LiMn 1-mn Ni m Co n O 2 (0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 1, 0 ⁇ m+n ⁇ 1), one or more of LiMPO 4 (M can be one or more of Fe, Mn, and Co) and Li 3 V 2 (PO 4 ) 3 .
  • the positive electrode sheet may further include a conductive agent.
  • the positive electrode sheet may further include a second adhesive.
  • the second binder is polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), nitrile rubber (NBR), water-based acrylic resin, polyvinyl alcohol, poly At least one of vinyl butyral, polyurethane, fluorinated rubber, carboxymethyl cellulose (CMC) and polyacrylic acid (PAA).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • water-based acrylic resin polyvinyl alcohol
  • the positive electrode sheet can be prepared according to conventional methods in the art.
  • the positive electrode active material and optionally the conductive agent and the second binder are dispersed in a second
  • the negative active material in the negative electrode sheet may be a negative active material known in the art.
  • metallic lithium natural graphite, artificial graphite, mesophase microcarbon balls (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO, Li-Sn alloy, Li-Sn-O alloy, One or more of Sn, SnO, SnO 2 , spinel structure lithium titanate and Li-Al alloy.
  • the negative electrode sheet may further include a conductive agent.
  • the negative electrode sheet may further include a third binder.
  • the third binder includes but is not limited to polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), nitrile rubber (NBR), water-based acrylic resin, polyethylene Alcohol, polyvinyl butyral, polyurethane, fluorinated rubber, carboxymethyl cellulose (CMC), polyacrylic acid (PAA), epoxy resin, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, At least one of carboxylated polyvinyl chloride, polyvinylpyrrolidone and nylon.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • water-based acrylic resin polyethylene Alcohol
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • epoxy resin epoxy resin
  • hydroxypropyl cellulose di
  • the negative electrode active material and optionally the conductive agent and the third binder are dispersed in a third solvent (such as water) to form a uniform negative electrode slurry, and the negative electrode slurry is coated on In the negative electrode coating area of the negative electrode current collector, after drying and other processes, the negative electrode paste is formed to obtain the negative electrode sheet.
  • a third solvent such as water
  • the negative electrode sheet is preferably a metallic lithium negative electrode sheet and a negative electrode sheet containing metallic lithium.
  • the preparation method is as follows: in a low humidity environment (usually in a drying room with a dew point temperature lower than -30°C) , using a roller press or other pressing equipment to mechanically press commercialized metal lithium strips (foils) and/or lithium alloy strips (foils) and copper foils (mesh), so that the metal lithium strips (foils) And/or the lithium alloy strip (foil) and the copper foil (mesh) are closely adhered together, leaving a certain blank area on the edge of the copper foil (mesh) for subsequent tab welding.
  • the conductive agent in the positive electrode sheet includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, or mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from at least one of metal powder, metal fiber, copper, nickel, aluminum, and silver.
  • the conductive polymer is a polyphenylene derivative.
  • the conductive agent in the negative electrode sheet includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, or mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from at least one of metal powder, metal fiber, copper, nickel, aluminum, and silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive current collector in the positive electrode sheet includes, but is not limited to: aluminum foil, carbon-coated aluminum foil, perforated aluminum foil, stainless steel foil, polymer substrate coated with conductive metal, and any combination thereof.
  • the negative electrode current collector in the negative electrode sheet includes, but is not limited to: copper foil, carbon-coated copper foil, perforated copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, Polymer substrates coated with conductive metals and their arbitrary combination.
  • the electrochemical device may be a battery (eg, a lithium-ion battery) or a supercapacitor.
  • the battery assembly method is as follows: in a low-humidity environment (usually in a drying room with a dew point temperature below -30°C), the positive electrolyte is evenly dropped into the positive electrode sheet Apply the paste on the positive electrode, and then apply sealant (that is, the material that forms the positive electrode sealing ring) on the positive electrode sealing area located on the periphery of the positive electrode coating area, and then stack the solid electrolyte membrane on the positive electrode The positive electrode sheet and the solid electrolyte membrane are bonded together through the sealant; the negative electrode electrolyte is evenly dropped on the negative electrode paste in the negative electrode sheet, and then placed on the The negative electrode sealing area outside the negative electrode coating area is coated with sealant (that is, the material forming the negative electrode sealing ring), and then the negative electrode sheet is stacked on the solid electrolyte membrane and the The negative electrode sheet and the solid electrolyte membrane are bonded together, wherein the solid electrolyte membrane serves as an isolation between the positive electrode sheet and the negative electrode
  • Figure 1 is a cross-sectional view of the lithium-ion battery structure (cross-sectional view in the vertical stacking direction), including the positive electrode current collector, positive electrode paste (fully soaked in the positive electrode electrolyte), solid electrolyte membrane, and negative electrode paste (fully soaked in the negative electrode electrolyte) , negative electrode current collector, negative electrode paste (fully soaked with negative electrode electrolyte), solid electrolyte membrane, positive electrode paste (fully soaked with positive electrode electrolyte), positive electrode current collector, positive electrode paste (fully soaked with positive electrode electrolyte), solid The electrolyte membrane, negative electrode paste (fully soaked in the negative electrode electrolyte), negative electrode current collector, negative electrode paste (fully soaked in the negative electrode electrolyte)... are stacked in sequence, and the sealing areas at the edges of the positive electrode paste and negative electrode paste are covered with seals Glue, and bond the positive and negative electrode sheets and the solid electrolyte membrane together to form the battery.
  • the number of layers of the negative electrode sheet is n
  • the number of layers of the positive electrode sheet is n+1, that is, both ends of the stacked structure are the positive electrode sheets.
  • the stacking method can also be changed so that the number of layers of the positive electrode sheet is n and the number of layers of the negative electrode sheet is n+1, that is, both ends of the stacked structure are the negative electrode sheets.
  • the stacking method can also be changed so that the number of layers of the positive electrode sheet is n and the number of layers of the negative electrode sheet is n, that is, one end of the two ends of the stacked structure is the negative electrode sheet and the other end is the positive electrode sheet.
  • n is an integer greater than or equal to 1.
  • the paste on only one side of the pole pieces at both ends of the laminated structure can be utilized and participate in the battery charge and discharge reaction.
  • the pole pieces at both ends are also made of the same double-sided paste-coated pole pieces as the inside.
  • the pole pieces at both ends will be chosen to be single-sided pasted pole pieces (paste facing inward).
  • Figure 2 is an expanded view of a stacked unit of a lithium-ion battery (top view along the stacking direction).
  • a in Figure 2 is a schematic diagram of the positive electrode sheet.
  • the positive electrode paste is located in the central area of the electrode sheet, and the positive electrode current collector is blank around the edges of the positive electrode paste. It is the sealing area, and its surface is coated with sealant;
  • b in Figure 2 is a schematic diagram of the solid electrolyte;
  • c in Figure 2 is a schematic diagram of the negative electrode piece, and the negative electrode paste is located on the electrode piece In the central area, the negative electrode current collector with blank edges around the negative electrode paste is the sealing area, and its surface is coated with sealant.
  • Positive electrode paste area ⁇ negative electrode paste area ( ⁇ here means that the positive electrode paste area can be completely covered by the negative electrode paste area after stacking), negative electrode sheet ⁇ solid electrolyte membrane ( ⁇ here means that after stacking, the negative electrode sheet can Completely covered by solid electrolyte membrane).
  • the present disclosure also provides uses of the electrochemical device.
  • the use of the electrochemical device described in the present disclosure is not particularly limited and can be used for various known uses.
  • any lower limit can be combined with any upper limit to form an unexpressed range; and any lower limit can be combined with other lower limits to form an unexpressed range, and likewise any upper limit can be combined with any other upper limit to form an unexpressed range.
  • every point or individual value between the endpoints of a range is included in the range.
  • each point or single value may serve as a lower or upper limit on its own in combination with any other point or single value or with other lower or upper limits to form a range not expressly recited.
  • Conventional negative electrode sheet preparation Weigh the negative active material (graphite and/or silicon oxide and/or silicon carbon composite), carbon black conductive agent, binder styrene-butadiene rubber (SBR), and thickener carboxymethyl fiber respectively. Disperse 970 grams, 10 grams, 10 grams (based on solid weight), 10 grams of plain sodium (CMC) in 1100 grams of deionized water, stir thoroughly to form a uniform negative electrode slurry, and coat the negative electrode slurry on the negative electrode On the current collector copper foil, it is then dried, rolled and cut to obtain the negative electrode sheet.
  • the negative active material graphite and/or silicon oxide and/or silicon carbon composite
  • carbon black conductive agent carbon black conductive agent
  • SBR binder styrene-butadiene rubber
  • CMC plain sodium
  • step 2 The obtained electrolyte slurry is coated on the PET base film, and the solvent is dried to obtain a composite film; the composite film is removed from the PET base film and cut into the required specifications.
  • the composite film is first heated at 300°C and 20MPa pressure. Debind (to fully decompose the binder) for 6 hours, and then sinter at 1200°C and 300MPa to obtain a solid electrolyte film with a thickness of 30 ⁇ m and an ionic conductivity of 1.3 ms/cm at room temperature.
  • Li 6 PS 5 Cl solid electrolyte Take 200 grams of Li 6 PS 5 Cl solid electrolyte, place it in an argon-filled ball milling tank, put it into the ball milling equipment, set the rotation speed to 800 rpm, and obtain Li 6 PS with an average particle size of 800nm after full ball milling for 24 hours.
  • EIS AC impedance
  • ⁇ is the conductivity of the solid electrolyte membrane
  • Rb is the bulk resistance obtained by fitting the impedance spectrum data
  • d is the thickness of the solid electrolyte membrane
  • S is the electrode area
  • S ⁇ r 2 .
  • Z1 to Z14 are positive electrode electrolytes
  • F1 to F14 are negative electrode electrolytes.
  • Weigh 50% Z1 and 50% F1 and mix uniformly to obtain the electrolyte solution H1 weigh 50% Z2 and 50% F2 and mix uniformly to obtain the electrolyte solution H2, and so on to obtain the electrolyte solutions H3 to H14.
  • the area is coated with sealant (that is, the material that forms the positive electrode sealing ring), and then the solid electrolyte membrane is stacked on the positive electrode sheet and the positive electrode sheet and the solid electrolyte membrane are bonded together through the sealant; the negative electrode electrolyte is evenly dropped on the negative electrode Apply paste to the negative electrode in the film, and then apply sealant (that is, the material that forms the negative electrode sealing ring) on the negative electrode sealing area located on the periphery of the negative electrode coating area. Then stack the negative electrode sheet on the solid electrolyte membrane and seal the negative electrode through the sealant. The sheet is bonded to the solid electrolyte membrane, and the solid electrolyte membrane is located between the positive electrode sheet and the negative electrode sheet to act as an isolation.
  • sealant that is, the material that forms the positive electrode sealing ring
  • the laminated battery core can be obtained.
  • the positive and negative electrode tabs of the battery core are welded, placed in the packaging shell, and sealed. After aging, chemical formation, and separation Select to get the battery.
  • the positive electrode sheet, negative electrode sheet and PP separator are stacked through a lamination machine to prepare a conventional lithium battery.
  • the positive and negative electrode tabs of the battery core are welded, placed in the packaging shell and sealed, and then the electrolyte is injected, aged, After forming and sorting, conventional lithium-ion batteries can be obtained.
  • Normal temperature cycle life Place the lithium-ion battery at 25°C, discharge it to the lower limit voltage (3.0V) at a constant current of 0.5C, and let it stand for 5 minutes; then charge it to the upper limit voltage (4.5V) at a constant current of 0.5C, and then Charge at a constant voltage of 4.5V until the current is 0.05C and leave it for 5 minutes; then discharge it at a constant current of 0.5C until the voltage is 3.0V and leave it for 5 minutes.

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Abstract

本公开属于电化学储能技术领域，具体涉及一种电化学装置。本公开通过固态电解质膜将正极电解液与负极电解液分隔开，在正极电解液中添加高含量的腈类化合物，在负极电解液中添加高含量的醚类化合物，腈类化合物可有效提升正极界面的稳定性，醚类化合物可有效提升负极界面的稳定性，腈类化合物不会穿透至负极与负极发生不良副反应，醚类化合物不会穿透至正极与正极发生不良的氧化反应，从而提高电化学装置的循环寿命，尤其是提升负极中含有金属锂的电化学装置的循环寿命。

Description

一种电化学装置 技术领域
本公开属于电化学储能技术领域，具体涉及一种电化学装置。
背景技术
作为电化学装置之一的锂离子电池是应用非常广泛的二次电池。锂离子电池的电解液对电池的性能具有重要影响，但是电解液的成分比较复杂，有一些成分与锂离子电池的负极不兼容，有一些成分与锂离子电池的正极不兼容，这大大缩短了电池的循环寿命。
发明内容
为了解决电解液与电化学装置电极不兼容的问题，本公开提供一种电化学装置，所述电化学装置中，通过固态电解质膜将正极电解液与负极电解液分隔开，可以实现与正极片接触的电解液和与负极片接触的电解液不同，解决了电解液中部分成分与正极片或负极片不兼容的问题，通过这样设计的电化学装置具备显著提高的循环寿命。
本公开目的是通过如下技术方案实现的：
一种电化学装置，其包括正极片、负极片、固态电解质膜、正极电解液、负极电解液和包装壳；
所述正极片和所述负极片位于所述固态电解质膜两侧，所述正极电解液位于所述正极片一侧，所述负极电解液位于所述负极片一侧，所述正极电解液和所述负极电解液通过所述固态电解质膜隔开。
在一实例中，所述固态电解质膜具有致密结构。具体的，具有致密无孔结构或具有致密无贯穿孔结构。
在一实例中，所述正极电解液包括腈类化合物，所述腈类化合物的质量分数不低于5％；所述负极电解液包括醚类化合物，所述醚类化合物的质量分数不低于4％。
在一实例中，所述正极电解液中还包括锂盐A、溶剂A和添加剂A；所述负极电解液中还包括锂盐B、溶剂B和添加剂B。
在一实例中，所述正极电解液的保有量m1(单位g)与所述电化学装置的设计容量Q(单位Ah)的比值满足0.5g/Ah≤m1/Q≤2.0g/Ah。
在一实例中，所述负极电解液的保有量m2(单位g)与所述电化学装置的设计容量Q(单位Ah)的比值满足0.5g/Ah≤m2/Q≤2.0g/Ah。
在一实例中，所述正极电解液的保有量m1≤所述负极电解液的保有量m2。
在一实例中，所述锂盐A中至少含有60wt％的六氟磷酸锂。
在一实例中，所述锂盐B中至少含有50wt％的二氟草酸硼酸锂。
在一实例中，所述锂盐B中至少含有1wt％的硝酸锂。
在一实例中，所述固态电解质膜为具有致密无孔结构的无机固态电解质膜，或者，所述固态电解质膜为具有致密无贯穿孔结构的无机固态电解质膜。
在一实例中，所述固态电解质膜的离子电导率≥0.1ms/cm。
在一实例中，形成所述固态电解质膜的材料为Garnet型氧化物电解质、NASICON型氧化物电解质、钙钛矿型氧化物电解质和硫化物电解质中的至少一种。
在一实例中，所述正极片与所述固态电解质膜之间设置有正极密封圈，用于防止所述正极电解液从所述正极片边缘泄露。
在一实例中，所述负极片与所述固态电解质膜之间设置有负极密封圈，用于防止所述负极电解液从所述负极片边缘泄露。
在一实例中，所述正极密封圈和所述负极密封圈的设置须保证电解液无法穿透，形成所述正极密封圈的材料(或定义为密封胶)和形成所述负极密封圈的材料(或定义为密封胶)相同或不同，彼此独立地选自马来酸酐接枝聚丙烯、聚氨酯、丁腈橡胶、丁基橡胶、氯丁橡胶、环氧树脂和硅橡胶中的至少一种。
在一实例中，所述正极片包括正极集流体、设置在所述正极集流体至少一侧表面的正极涂覆区域和与所述正极涂覆区域相连的位于所述正极涂覆区域外围的正极密封区域；所述正极涂覆区域内设置正极涂膏，所述正极密封区域内设置所述正极密封圈。
在一实例中，所述负极片包括负极集流体、设置在所述负极集流体至少一侧表面的负极涂覆区域和与所述负极涂覆区域相连的位于所述负极涂覆区域外围的负极密封区域；所述负极涂覆区域内设置负极涂膏，所述负极密封区域内设置所述负极密封圈。
在一实例中，所述电化学装置可以为电池或超级电容器。
本公开的有益效果：
本公开通过固态电解质膜将正极电解液与负极电解液分隔开，在正极电解液中添加高含量的腈类化合物，在负极电解液中添加高含量的醚类化合物，腈类化合物可有效提升正极界面的稳定性，醚类化合物可有效提升负极界面的稳定性，腈类化合物不会穿透至负极与负极发生不良副反应，醚类化合物不会穿透至正极与正极发生不良的氧化反应，基于这样设计的电化学装置具有显著提高的循环寿命，尤其是提升负极中含有金属锂的电化学装置的循环寿命。
附图说明
图1为本公开的锂离子电池的结构截面图(垂直层叠方向的剖面图)。
图2为本公开的锂离子电池的一个层叠单元的展开图(沿层叠方向的俯视图)。
具体实施方式
通常，电化学装置中电解液的成分比较复杂，有一些成分与电化学装置的负极不兼容，有一些成分与电化学装置的正极不兼容，限制了电化学装置的应用。腈类化合物可有效稳定过渡金属元素，从而提升正极界面的稳定性，但其会在负极上发生不良副反应，因此为了提升循环寿命，在电化学装置中腈类化合物的添加量被严格控制在5％以内。醚类化合物可有效提升负极界面的稳定性，但其在高电压正极上会发生不良副反应，因此为了提升循环寿命，在电化学装置中醚类化合物的添加量被严格控制在4％以内，甚至在实际应用中不添加任何醚类化合物。
本公开的发明人出人意料地发现，若通过固态电解质膜将正极电解液与负极电解液分隔开，同时在正极电解液中添加高含量的腈类化合物，在负极电解液中添加高含量的醚类化合物，从而有效提升了电化学装置的循环寿命。
<电化学装置>
本公开提供一种电化学装置，其包括正极片、负极片、固态电解质膜、正极电解液、负极电解液和包装壳；
所述正极片和所述负极片位于所述固态电解质膜两侧，所述正极电解液位于所述正极片一侧，所述负极电解液位于所述负极片一侧，所述正极电解液和所述负极电解液通过所述固态电解质膜隔开。
在一实例中，所述固态电解质膜具有致密结构。具体的，具有致密无孔结构或具有致密无贯穿孔结构。
本公开中，所述正极电解液和所述负极电解液的组成不同。
本公开中，所述正极电解液和所述负极电解液通过所述固态电解质膜隔开是指所述正极电解液和所述负极电解液被所述固态电解质膜阻隔开且互相不接触，但离子可以通过所述固态电解质膜进行移动。
<正极电解液和负极电解液>
在一些实施例中，所述正极电解液包括腈类化合物，所述腈类化合物的质量分数不低于5％。
在一些实施例中，所述腈类化合物的质量分数不低于5％是指所述腈类化合物的质量占所述正极电解液总质量的质量百分含量不低于5％，即大于等于5％。此时，所述腈类化合物可以非 常充分地在正极活性材料表面形成保护层，有效稳定正极活性材料中的过渡金属元素，防止过渡金属元素在高电压下被破坏，从而提升正极界面的稳定性，提升循环性能。若小于5％时，所述腈类化合物虽然也可以在正极活性材料表面形成保护层，提升正极界面的稳定性，但是改善效果不显著。
在一些实施例中，所述腈类化合物的质量分数为5％～80％，示例性地为5％、6％、7％、8％、9％、10％、20％、30％、40％、50％、60％、70％或80％。
在一些实施例中，所述腈类化合物选自乙腈、丙腈、丁腈、丙二腈、丁二腈、戊二腈、己二腈、1,3,6-己烷三腈、1,3,5-戊烷三甲腈、乙二醇双丙腈醚、六氟环三磷腈、五氟乙氧基环三磷腈、五氟苯氧基环三磷腈、1,4-二氰基-2-丁烯、对氟苯甲腈、对甲基苯甲腈、2-氟己二腈、2,2-二氟丁二腈、三氰基苯、丙烯腈、巴豆腈、反式丁烯二腈和反式己烯二腈中的至少一种。进一步优选为乙腈和丁二腈中的至少一种。
在一些实施例中，所述负极电解液包括醚类化合物，所述醚类化合物的质量分数不低于4％。
在一些实施例中，所述醚类化合物的质量分数不低于4％是指所述醚类化合物的质量占所述负极电解液总质量的质量百分含量不低于4％，即大于等于4％。此时，所述醚类化合物因为其具有优异的抗还原稳定性，尤其所述醚类化合物与金属锂具有较高的稳定性，可有效抑制所述负极电解液与负极材料的界面副反应，从而显著提升负极界面稳定性，提升循环性能。若小于4％时，所述醚类化合物虽然也能改善负极界面稳定性，但是改善效果不显著。
在一些实施例中，所述醚类化合物的质量分数为4％～80％，示例性地为4％、5％、6％、7％、8％、9％、10％、20％、30％、40％、50％、60％、70％或80％。
在一些实施例中，所述醚类化合物选自乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、三丙二醇二甲醚、1,3-二氧环戊烷、二氧六环、四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃、2-乙基四氢呋喃、3-乙基四氢呋喃和二甲基四氢呋喃中的至少一种。进一步优选为乙二醇二甲醚、二乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、1,3-二氧环戊烷、二氧六环和四氢呋喃中的至少一种。
在一些实施例中，所述正极电解液中还包括锂盐A、溶剂A和添加剂A。
在一些实施例中，所述负极电解液中还包括锂盐B、溶剂B和添加剂B。
在一些实施例中，所述正极电解液的保有量m1(单位g)与所述电化学装置的设计容量Q(单位Ah)的比值满足0.5g/Ah≤m1/Q≤2.0g/Ah。
在一些实施例中，所述负极电解液的保有量m2(单位g)与所述电化学装置的设计容量Q(单位Ah)的比值满足0.5g/Ah≤m2/Q≤2.0g/Ah。
在本公开中，所述“正极电解液的保有量”和所述“负极电解液的保有量”可以通过常规 称重的方法来确认。
在一些实施例中，所述正极电解液的保有量m1≤所述负极电解液的保有量m2。由于所述电化学装置中负极SEI膜的生长速度较快，通常在所述电化学装置中所述负极电解液的消耗速度通常会比所述正极电解液的消耗速度快，这样设置可以进一步使整个电化学装置获得更加优异的循环性能。
在一些实施例中，所述锂盐A和所述锂盐B相同或不同，彼此独立地选自六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、高氯酸锂(LiClO4)、六氟砷酸锂(LiAsF6)、六氟锑酸锂(LiSbF6)、二氟磷酸锂(LiPF2O2)、4,5-二氰基-2-三氟甲基咪唑锂(LiDTI)、双乙二酸硼酸锂(LiBOB)、双(丙二酸)硼酸锂(LiBMB)、二氟草酸硼酸锂(LiDFOB)、双(二氟丙二酸)硼酸锂(LiBDFMB)、(丙二酸草酸)硼酸锂(LiMOB)、(二氟丙二酸草酸)硼酸锂(LiDFMOB)、三(草酸)磷酸锂(LiTOP)、三(二氟丙二酸)磷酸锂(LiTDFMP)、四氟草酸磷酸锂(LiTFOP)、二氟二草酸磷酸锂(LiDFOP)、双氟磺酰亚胺锂(LiFSI)、双三氟甲烷磺酰亚氨锂(LiTFSI)、(氟磺酰)(三氟甲磺酰)亚氨锂(LiN(SO2F)(SO2CF3))、硝酸锂(LiNO3)、氟化锂(LiF)、LiN(SO2CnF2n+1)2和LiN(SO2F)(SO2CnF2n+1)中的一种或多种(n为2～10的整数)。
在一些实施例中，所述溶剂A和所述溶剂B相同或不同，彼此独立地选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸丁烯酯、氟代碳酸乙烯酯(FEC)、二氟代碳酸乙烯酯(DFEC)、氟代碳酸二甲酯、氟代碳酸甲乙酯、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯(EA)、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、二氟乙酸甲酯、二氟乙酸乙酯、γ-丁内酯(GBL)、γ-戊内酯、δ-戊内酯、氟代醚F-EPE、氟代醚D2、氟代醚HFPM、氟代醚MFE、氟代醚EME、环丁砜、二甲亚砜(DMSO)、二氯甲烷和二氯乙烷中的一种或多种。
在一些实施例中，所述添加剂A和所述添加剂B相同或不同，彼此独立地选自碳酸亚乙烯酯(VC)、碳酸乙烯基亚乙酯(VEC)、1,3-丙烷磺酸内酯(PS)、三氟甲基碳酸乙烯酯、硫酸二甲酯、硫酸乙烯酯(DTD)、甲基硫酸乙烯酯、硫酸丙烯酯、亚硫酸乙烯酯、丁二酸酐、联苯、联苯醚、甲苯、二甲苯、环已基苯、氟苯、对氟甲苯、对氟苯甲醚、叔丁基苯、叔戊基苯、丙烯磺酸内酯、丁烷磺酸内酯、甲烷二磺酸亚甲酯、乙二醇双(丙腈)醚、六甲基二硅氮烷、七甲基二硅氮烷、甲基膦酸二甲酯、乙基膦酸二乙酯、磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、亚磷酸三苯酯、三(三甲基硅基)硼酸酯、三(三甲基硅基)磷酸酯、1,2-二(氰乙氧基)乙烷、1,2,3-三(氰乙氧基)丙烷、双(氰乙基)砜和3-(三甲基硅氧基)丙腈中的一种或多种。
在一些实施例中，所述锂盐A中至少含有60wt％的六氟磷酸锂。添加60wt％以上含量的六氟 磷酸锂可以在保证电化学装置性能的基础上大幅降低其制备成本。
在一些实施例中，所述锂盐B中至少含有50wt％的二氟草酸硼酸锂。添加50wt％以上含量的二氟草酸硼酸锂可以改善负极SEI膜稳定性，进一步提升循环寿命，尤其是提升采用金属锂作负极时电化学装置的循环寿命。
在一些实施例中，所述锂盐B中至少含有1wt％的硝酸锂。添加1wt％以上含量的硝酸锂可以提升负极SEI膜中的无机成分占比，改善负极SEI膜的稳定性，可进一步提升循环寿命，尤其是提升采用金属锂作负极时电化学装置的循环寿命。
<固态电解质膜>
如上所述，所述固态电解质膜具有致密结构。具体的，具有致密无孔结构或具有致密无贯穿孔结构。
在一些实施例中，所述固态电解质膜为具有致密无贯穿孔结构的无机固态电解质膜。
在一些实施例中，所述固态电解质膜为具有致密无孔结构的无机固态电解质膜。
在一些实施例中，所述固态电解质膜的致密度大于等于99％，例如为99％～100％。
在本公开中，所述固态电解质膜的致密度可以通过以下方法测试得到，具体的：致密度的计算公式为：致密度＝D表/D×100％，其中D表为固态电解质的表观密度，D为固态电解质的理论密度；固态电解质的表观密度D表可以采用阿基米德排水法测量并计算。
在一些实施例中，所述固态电解质膜不同于常规的隔膜，本公开的所述固态电解质膜具有致密结构，具体为具有致密无孔结构或致密无贯穿孔结构，这样结构的所述固态电解质膜的设置使得电解液无法穿过，但是电解液中的锂离子可以迁移并穿过所述固态电解质膜，因此该固态电解质膜的设置可以保证所述固态电解质膜两侧的所述正极电解液和所述负极电解液被所述固态电解质膜阻隔开且互相不接触。
在一些实施例中，所述固态电解质膜的厚度优选为5μm～100μm。厚度低于5μm的所述固态电解质膜以现有的制备技术难以实现，同时厚度低于5μm时，所述固态电解质膜的强度太低，容易破裂，难以组装成所述电化学装置。厚度高于100μm的所述固态电解质膜虽然机械强度高，容易组装所述电化学装置，但厚度太大的所述固态电解质膜会降低所述电化学装置的能量密度。
在一些实施例中，所述固态电解质膜的离子电导率≥0.1ms/cm。优选地，所述固态电解质膜的离子电导率≥1ms/cm。
在一些实施例中，形成所述固态电解质膜的材料为Garnet型氧化物电解质、NASICON型氧化物电解质、钙钛矿型氧化物电解质和硫化物电解质中的至少一种。
在一些实施例中，所述Garnet型氧化物电解质优选为锂镧锆氧(LLZO)、钽掺杂的锂镧锆 氧(LLZTO)和铌掺杂的锂镧锆氧(LLZNO)中的至少一种。
在一些实施例中，所述NASICON型氧化物电解质选自Li1+2x’Zr2-x’Cax’(PO4)3，其中0.1≤x’≤0.4；Li1+x+yAlx(TimZrnGer)2-xSiyP3-yO12，其中0≤x≤2，0≤y≤3，0≤m≤1，0≤n≤1，0≤r≤1，m+n+r＝1。优选为磷酸钛铝锂(LATP)、磷酸锗铝锂(LAGP)、磷酸钛锗铝锂和磷酸硅锗锂(Li3Zr2Si2PO12)中的至少一种。
在一些实施例中，所述钙钛矿型氧化物电解质优选为锂镧钛氧(LLTO)。
在一些实施例中，所述硫化物电解质优选为Li3PS4、Li7P3S11、Li4-x”Ge1-x”Px”S4(X”＝0.4或X”＝0.6)和Li6PS5X(X选自F、Cl、Br或I中的至少一种)中的至少一种。
在一些实施例中，所述固态电解质膜的厚度为5μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm或100μm。作为更优，在一些实施例中，所述固态电解质膜的厚度为15μm、20μm、25μm或30μm。
在一些实施例中，所述固态电解质膜的制备方法如下：
将形成所述固态电解质膜的材料通过球磨研磨成粒径低于2μm的固态电解质粉体；再将所述固态电解质粉体、第一粘结剂与第一溶剂混合分散均匀，得到固态电解质浆料；将所述固态电解质浆料涂布在聚合物基膜上，烘干所述第一溶剂得到复合薄膜；将所述复合薄膜从所述聚合物基膜上取下并裁剪成所需规格，再在惰性气体氛围下，在加压力条件下，同时在高温条件下，排胶并烧结得到所述固态电解质膜。采用这种方法制备的固态电解质膜为全无机固态电解质膜，且由于高温烧结，所述固态电解质膜为具有致密无孔结构或致密无贯穿孔结构的无机膜，因此液体无法直接穿过。
其中，所述排胶的温度为200℃～1400℃，具体根据所述第一粘结剂种类进行设定。
其中，所述烧结的温度为200℃～1400℃，具体根据形成所述固态电解质膜的材料的种类进行设定。
其中，所述压力的范围为10MPa～300MPa。
其中，对所述第一粘结剂与所述第一溶剂无特别限定，可根据形成所述固态电解质膜的材料的种类进行优选。
其中，所述第一粘结剂优选为聚偏氟乙烯(PVDF)、聚氧化乙烯、聚乙烯醇、聚乙烯醇缩丁醛(PVB)、乙基纤维素(EC)和丙烯酸类树脂中的一种或几种。
其中，所述第一溶剂优选为NMP、水、乙腈和甲苯中的一种或几种。
<正极密封圈和负极密封圈>
在一些实施例中，所述正极片与所述固态电解质膜之间设置有正极密封圈，用于防止所述正极电解液从所述正极片边缘泄露。
在一些实施例中，所述负极片与所述固态电解质膜之间设置有负极密封圈，用于防止所述负极电解液从所述负极片边缘泄露。
在一些实施例中，所述正极密封圈和所述负极密封圈的设置须保证电解液无法穿透，形成所述正极密封圈的材料(或定义为密封胶)和形成所述负极密封圈的材料(或定义为密封胶)相同或不同，优选为马来酸酐接枝聚丙烯、聚氨酯、丁腈橡胶、丁基橡胶、氯丁橡胶、环氧树脂和硅橡胶中的至少一种。
在一些实施例中，所述正极密封圈可以为形成所述正极密封圈的材料经过熔融粘结或固化粘结而成。
在一些实施例中，所述负极密封圈可以为形成所述负极密封圈的材料经过熔融粘结或固化粘结而成。
<正极片和负极片>
在一些实施例中，所述正极片包括正极集流体、设置在所述正极集流体至少一侧表面的正极涂覆区域和与所述正极涂覆区域相连的位于所述正极涂覆区域外围的正极密封区域；所述正极涂覆区域内设置正极涂膏，所述正极密封区域内设置所述正极密封圈。
在一些实施例中，所述负极片包括负极集流体、设置在所述负极集流体至少一侧表面的负极涂覆区域和与所述负极涂覆区域相连的位于所述负极涂覆区域外围的负极密封区域；所述负极涂覆区域内设置负极涂膏，所述负极密封区域内设置所述负极密封圈。
在一些实施例中，所述正极片中的正极活性材料可以采用本领域已知的正极活性材料，能够进行离子的可逆嵌入/脱嵌。例如为锂过渡金属复合氧化物，其中过渡金属可以是Mn、Fe、Ni、Co、Cr、Ti、Zn、V、Al、Zr、Ce及Mg中的一种或多种。所述锂过渡金属复合氧化物中还可以掺杂电负性大的元素，如S、F、Cl及I中的一种或多种，能够使所述正极活性材料具有较高的结构稳定性和电化学性能。作为示例，所述锂过渡金属复合氧化物为LiMn2O4、LiNiO2、LiCoO2、LiNi1-yCoyO2(0<y<1)、LiNiaCobAl1-a-bO2(0<a<1，0<b<1，0<a+b<1)、LiMn1-m-nNimConO2(0<m<1，0<n<1，0<m+n<1)、LiMPO4(M可以为Fe、Mn、Co中的一种或多种)及Li3V2(PO4)3中的一种或多种。可选地，所述正极片还可以包括导电剂。可选地，所述正极片还可以包括第二粘结剂。作为示例，所述第二粘结剂为聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、丁苯橡胶(SBR)、丁腈橡胶(NBR)、水系丙烯酸树脂、聚乙烯醇、聚乙烯醇缩丁醛、聚氨酯、氟化橡胶、羧甲基纤维素(CMC)和聚丙烯酸(PAA)中的至少一种。所述正极片可以按照本领域常规方法制备。通常将所述正极活性材料及可选的所述导电剂、所述第二粘结剂分散于第二溶剂(例如N-甲基吡咯烷酮，简称为NMP)中，形成均匀的正极浆料，将所述正极浆料涂覆在所述正极集流体的所述正极涂覆区域中，经烘干等工序后，形成所述正极涂膏，得到所述正 极片。
在一些实施例中，所述负极片中的负极活性材料可以采用本领域已知的负极活性材料。例如为金属锂、天然石墨、人造石墨、中间相微碳球(简写为MCMB)、硬碳、软碳、硅、硅-碳复合物、SiO、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的钛酸锂及Li-Al合金中的一种或多种。可选地，所述负极片还可以包括导电剂。可选地，所述负极片还可以包括第三粘结剂。作为示例，所述第三粘结剂包括但不限于聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、丁苯橡胶(SBR)、丁腈橡胶(NBR)、水系丙烯酸树脂、聚乙烯醇、聚乙烯醇缩丁醛、聚氨酯、氟化橡胶、羧甲基纤维素(CMC)、聚丙烯酸(PAA)、环氧树脂、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚乙烯吡咯烷酮和尼龙中的至少一种。所述负极片可以按照本领域常规方法制备。通常将所述负极活性材料及可选的所述导电剂、所述第三粘结剂分散于第三溶剂(例如水)中，形成均匀的负极浆料，将所述负极浆料涂覆在所述负极集流体的所述负极涂覆区域中，经烘干等工序后，形成所述负极涂膏，得到所述负极片。
为了获得更高的能量密度，所述负极片优选金属锂负极片和含有金属锂的负极片，其制备方法如下：在低湿度环境下(通常在露点温度低于-30℃的干燥室内进行)，采用辊压机或其他压合设备，将商业化的金属锂带(箔)和/或锂合金带(箔)与铜箔(网)进行机械压合，使得所述金属锂带(箔)和/或所述锂合金带(箔)与所述铜箔(网)紧密附着在一起，所述铜箔(网)边缘留出一定的空白区域用于后续极耳焊接。
在一些实施例中，所述正极片中的导电剂包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物或它们的混合物。在一些实施例中，所述基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，所述基于金属的材料选自金属粉、金属纤维、铜、镍、铝和银中的至少一种。在一些实施例中，所述导电聚合物为聚亚苯基衍生物。
在一些实施例中，所述负极片中的导电剂包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物或它们的混合物。在一些实施例中，所述基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，所述基于金属的材料选自金属粉、金属纤维、铜、镍、铝和银中的至少一种。在一些实施例中，所述导电聚合物为聚亚苯基衍生物。
在一些实施例中，所述正极片中的所述正极集流体包括，但不限于：铝箔，涂炭铝箔、打孔铝箔、不锈钢箔、覆有导电金属的聚合物基底和它们的任意组合。
在一些实施例中，所述负极片中的所述负极集流体包括，但不限于：铜箔、涂炭铜箔、打孔铜箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜、覆有导电金属的聚合物基底和它们的任意 组合。
<电池或超级电容器>
在一些实施例中，所述电化学装置可以为电池(例如为锂离子电池)或超级电容器。
在一些实施例中，所述电池组装方法如下：在低湿度环境下(通常在露点温度低于-30℃的干燥室内进行)，将所述正极电解液均匀地滴加在所述正极片中的所述正极涂膏上，然后在位于所述正极涂覆区域外围的所述正极密封区域涂上密封胶(即形成正极密封圈的材料)，然后将所述固态电解质膜堆叠在所述正极片上并通过所述密封胶将所述正极片与所述固态电解质膜粘结在一起；将所述负极电解液均匀地滴加在所述负极片中的所述负极涂膏上，然后在位于所述负极涂覆区域外围的所述负极密封区域涂上密封胶(即形成负极密封圈的材料)，然后将所述负极片堆叠在所述固态电解质膜上并通过所述密封胶将所述负极片与所述固态电解质膜粘结在一起，其中所述固态电解质膜处于所述正极片和所述负极片之间起到隔离的作用；经过多层堆叠，即可得到层叠电芯，将电芯焊接正负极耳、置于包装外壳中并封口，经过陈化、化成、分选，即可得到电池。
图1为锂离子电池结构的截面图(垂直层叠方向的剖面图)，正极集流体、正极涂膏(充分浸润了正极电解液)、固态电解质膜、负极涂膏(充分浸润了负极电解液)、负极集流体、负极涂膏(充分浸润了负极电解液)、固态电解质膜、正极涂膏(充分浸润了正极电解液)、正极集流体、正极涂膏(充分浸润了正极电解液)、固态电解质膜、负极涂膏(充分浸润了负极电解液)、负极集流体、负极涂膏(充分浸润了负极电解液)……依次层叠，正极涂膏与负极涂膏边缘的密封区均覆盖有密封胶，并将正负极片与固态电解质膜粘结在一起，即构成了所述电池。
这里的层叠结构中，所述负极片的层数为n，所述正极片的层数为n+1，即层叠结构的两端均为所述正极片。也可以改变层叠方式，使得所述正极片的层数为n，所述负极片的层数为n+1，即层叠结构的两端均为所述负极片。还可以改变层叠方式，使得所述正极片的层数为n，所述负极片的层数为n，即层叠结构的两端中有一端为所述负极片，另一端为所述正极片，n为大于等于1的整数。
由层叠结构可知，层叠结构两端的极片只有一个面的涂膏可以被利用并参与电池充放电反应。通常为了方便制造，会将两端的极片也采用与内部相同的双面涂膏极片。为了进一步节省空间提升能量密度，则会选择将两端的极片采用单面涂膏极片(涂膏朝内)。
图2为锂离子电池的一个层叠单元的展开图(沿层叠方向的俯视图)，图2中的a是正极片示意图，正极涂膏位于极片中央区域，正极涂膏四周边缘空白的正极集流体为密封区，其表面涂覆有密封胶；图2中的b是固态电解质示意图；图2中的c是负极片示意图，负极涂膏位于极片 中央区域，负极涂膏四周边缘空白的负极集流体为密封区，其表面涂覆有密封胶。正极涂膏区≤负极涂膏区(这里的≤指的是层叠后正极涂膏区可以完全被负极涂膏区覆盖)，负极片≤固态电解质膜(这里的≤指的是层叠后负极片可以完全被固态电解质膜覆盖)。
<电化学装置的用途>
本公开还提供所述电化学装置的用途，对本公开所述的电化学装置的用途没有特别限定，可以用于公知的各种用途。例如：移动电脑、笔记本电脑、便携式电话、电子书播放器、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、计算器、存储卡、便携式录音机、收音机、备用电源、汽车、摩托车、电动船舶、自行车、照明器具、玩具、游戏机、钟表、电动工具、照相机、家庭用大型蓄电池、储能电站等。
<实施例和对比例>
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本文的描述中，需要说明的是，除非另有说明，“以上”、“以下”为包含本数，“一种或多种”中“多种”的含义是两个以上。
本公开的发明内容并不意欲描述本公开中的每个公开的实施方式或每种实现方式。如下描述更具体地举例说明示例性实施方式。在整篇申请中的多处，通过一系列实施例提供了指导，这些实施例可以以各种组合形式使用。在各个实例中，列举仅作为代表性组，不应解释为穷举。
通过下述实施例和对比例对本公开公开的内容进一步具体地说明，这些实施例仅仅用于阐述性说明，因为在本公开公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
制备例1
(1)正极片制备
分别称取正极活性材料钴酸锂、炭黑导电剂、粘结剂聚偏氟乙烯(PVDF)972克、14克、14克，分散于400克的N-甲基吡咯烷酮(NMP)中，充分搅拌形成均匀的正极浆料，将正极浆料涂覆在正极集流体铝箔上，然后经烘干，辊压，裁切，得到正极片。
(2)负极片制备
常规负极片制备：分别称取负极活性材料(石墨和/或氧化亚硅和/或硅碳复合材料)、炭黑导电剂、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC)970克、10克、10克(以固形物重量计)、10克，分散于1100克的去离子水中，充分搅拌形成均匀的负极浆料，将负极浆料涂覆在负极集流体铜箔上，然后经烘干，辊压，裁切，得到负极片。
金属锂负极片制备：在低湿度环境下(本次实验在露点温度-40℃的干燥室内进行)，采用辊压机或其他压合设备，将商业化的金属锂带(箔)、锂合金带(箔)与铜箔(网)进行机械压合，使得金属锂带(箔)、锂合金带(箔)与铜箔(网)紧密附着在一起，铜箔(网)边缘留出一定的空白区域用于后续极耳焊接，裁切后得到负极片。
(3)固态电解质膜的制备
a.锂镧锆钽氧(LLZTO)固态电解质膜的制备
①取200克锂镧锆钽氧固态电解质，置于充氮气的球磨罐中，放入球磨设备中，设置转速为800转/min，充分球磨12h后获得平均粒径600nm的的锂镧锆钽氧固态电解质粉；②称取96克步骤①所得的锂镧锆钽氧固态电解质粉、4克分子量500万的聚氧化乙烯、200克乙腈充分混合分散均匀得到固态电解质浆料；③将步骤②所得电解质浆料涂布在PET基膜上，烘干溶剂得到复合薄膜；将复合薄膜从PET基膜上取下并裁剪成所需规格，在氩气氛围下，先300℃、20MPa压力条件下排胶(使粘结剂充分分解)6h，然后1200℃、300MPa烧结得到固态电解质薄膜，厚度30μm，室温离子电导率1.3ms/cm。
b.Li6PS5Cl固态电解质膜的制备
①取200克Li6PS5Cl固态电解质，置于充氩气的球磨罐中，放入球磨设备中，设置转速为800转/min，充分球磨24h后获得平均粒径800nm的的Li6PS5Cl固态电解质粉；②称取97克步骤①所得的Li6PS5Cl固态电解质粉、3克分子量丁腈橡胶、150克甲苯充分混合分散均匀得到固态电解质浆料；③将步骤②所得电解质浆料涂布在PTFE基膜上，烘干溶剂得到复合薄膜；将复合薄膜从PTFE基膜上取下并裁剪成所需规格，在氩气氛围下，先350℃、25MPa压力条件下排胶(使粘结剂充分分解)10h，然后550℃、300MPa烧结得到固态电解质薄膜，厚度30μm，室温离子电导率4.6ms/cm。
c.离子电导率的测试方法
离子电导率的测试方法如下：将固态电解质膜用冲片机冲切成半径为r＝8mm的圆片，然后用离子溅射仪对固态电解质膜圆片两侧进行喷金处理，然后在喷金处理后的固态电解质膜原片两侧分别贴紧放置半径r＝8mm的不锈钢圆片(SS)，将其密封组装成SS/固态电解质膜/SS对称阻塞电池。用电化学工作站对上述的对称阻塞电池进行交流阻抗(EIS)测试，测试条件：振 幅为10mV，频率为10Hz～106Hz，温度25℃，测试前需将电池在测试温度下静置1h使电池稳定，得到阻抗谱并进行数据拟合可得到本体电阻Rb。固态电解质膜的电导率可按照以下方程计算得出：δ＝d/(Rb×S)，
其中，δ为固态电解质膜的电导率，Rb为阻抗谱数据拟合得到的本体电阻，d为固态电解质膜的厚度，S为电极面积，S＝πr2。
(4)电解液的制备
a.正极电解液的制备
在含水量<1ppm的充有氩气的手套箱中，将锂盐A、溶剂A、添加剂A和腈类化合物按照一定质量比混合均匀。
b.负极电解液的制备
在含水量<1ppm的充有氩气的手套箱中，将锂盐B、溶剂B、添加剂B和醚类化合物按照一定质量比混合均匀。
c.对比组电解液的制备
分别取正极电解液与负极电解液按照质量比1:1混合均匀得到对比组电解液。
表1 电解液的配比

表1中Z1～Z14是正极电解液，F1～F14是负极电解液。称取50％Z1与50％F1混合均匀得到电解液即为H1，称取50％Z2与50％F2混合均匀得到电解液即为H2，以此类推，得到电解液H3～H14。称取50％Z1与50％F9混合均匀得到电解液即为H15，称取50％Z2与50％F10混合均匀得到电解液即为H16，称取50％Z3与50％F11混合均匀得到电解液即为H17，称取50％Z4与50％F12混合均匀得到电解液即为H18。
(5)锂离子电池的制备
在低湿度环境下(本次实验在露点温度-40℃的干燥室内进行)，将正极电解液均匀地滴加在正极片中的正极涂膏上，然后在位于正极涂覆区域外围的正极密封区域涂上密封胶(即形成正极密封圈的材料)，然后将固态电解质膜堆叠在正极片上并通过密封胶将正极片与固态电解质膜粘结在一起；将负极电解液均匀地滴加在负极片中的负极涂膏上，然后在位于负极涂覆区域外围的负极密封区域涂上密封胶(即形成负极密封圈的材料)，然后将负极片堆叠在固态电解质膜上并通过密封胶将负极片与固态电解质膜粘结在一起，其中固态电解质膜处于正极片、负极片之间起到隔离的作用。经过11层正极片、20层固态电解质膜、10层负极片交替堆叠，即可得到层叠电芯，将电芯焊接正负极耳、置于包装外壳中并封口，经过陈化、化成、分选，即可得到所述电池。
(6)常规锂离子电池的制备
将正极片、负极片和PP隔膜(厚度20μm)通过叠片机叠片制备得到常规锂电芯，将电芯焊接正负极耳、置于包装外壳中并封口，然后注电解液、陈化、化成、分选，即可得到常规锂离子电池。
2.电池性能测试
常温循环寿命：将锂离子电池置于25℃下，以0.5C恒流放电至下限电压(3.0V)，静置5分钟；再以0.5C恒流充电至上限电压(4.5V)，然后以4.5V恒压充电至电流为0.05C，放置5分钟；接着以0.5C恒流放电至电压为3.0V，静置5分钟，此为一个充放电循环。如此充电/放电，直至某一次循环时放电容量与首次放电容量的比值≤80％时，经历的循环次数即为循环寿命。
表2 电池信息及性能测试

表3 常规电池信息及性能测试

从表2的实施例与对比例电池的循环寿命测试结果可知，采用本公开的电池，在正极与负极采用组分不同的电解液，可显著地提高电池循环寿命。
从表2实施例与表3中常规电池的循环寿命测试结果可知，采用本公开的电池，循环寿命显著地高于常规锂电池。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本公开。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本公开的精神或范围的情况下，在其它实施例中实现。因此，本公开将不会被限制于本文所示的实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽范围。

Claims (15)

  1. 一种电化学装置，其特征在于，所述电化学装置包括正极片、负极片、固态电解质膜、正极电解液、负极电解液和包装壳；
    所述正极片和所述负极片位于所述固态电解质膜两侧，所述正极电解液位于所述正极片一侧，所述负极电解液位于所述负极片一侧，所述正极电解液和所述负极电解液通过所述固态电解质膜隔开。
  2. 根据权利要求1所述的电化学装置，其特征在于，所述正极电解液包括腈类化合物，所述腈类化合物的质量分数不低于5％；
    和/或，所述负极电解液包括醚类化合物，所述醚类化合物的质量分数不低于4％。
  3. 根据权利要求2所述的电化学装置，其特征在于，所述腈类化合物的质量分数为5％～80％；
    和/或，所述醚类化合物的质量分数为4％～80％。
  4. 根据权利要求2或3所述的电化学装置，其特征在于，所述腈类化合物选自乙腈、丙腈、丁腈、丙二腈、丁二腈、戊二腈、己二腈、1,3,6-己烷三腈、1,3,5-戊烷三甲腈、乙二醇双丙腈醚、六氟环三磷腈、五氟乙氧基环三磷腈、五氟苯氧基环三磷腈、1,4-二氰基-2-丁烯、对氟苯甲腈、对甲基苯甲腈、2-氟己二腈、2,2-二氟丁二腈、三氰基苯、丙烯腈、巴豆腈、反式丁烯二腈和反式己烯二腈中的至少一种；
    和/或，所述醚类化合物选自乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、丙二醇二甲醚、二丙二醇二甲醚、三丙二醇二甲醚、1,3-二氧环戊烷、二氧六环、四氢呋喃、2-甲基四氢呋喃、3-甲基四氢呋喃、2-乙基四氢呋喃、3-乙基四氢呋喃和二甲基四氢呋喃中的至少一种。
  5. 根据权利要求1-4中任一项所述的电化学装置，其特征在于，所述正极电解液中还包括锂盐A、溶剂A和添加剂A；所述负极电解液中还包括锂盐B、溶剂B和添加剂B；
    优选地，所述锂盐A和所述锂盐B相同或不同，彼此独立地选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、六氟锑酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪唑锂、双乙二酸硼酸锂、双(丙二酸)硼酸锂、二氟草酸硼酸锂、双(二氟丙二酸)硼酸锂、(丙二酸草酸)硼酸锂、(二氟丙二酸草酸)硼酸锂、三(草酸)磷酸锂、三(二氟丙二酸)磷酸锂、四氟草酸磷酸锂、二氟二草酸磷酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚氨锂、(氟磺酰)(三氟甲磺酰)亚氨锂、硝酸锂、氟化锂、LiN(SO2CnF2n+1)2和LiN(SO2F)(SO2CnF2n+1)中的一种或多种，其中n为2～10的整数；
    优选地，所述溶剂A和所述溶剂B相同或不同，彼此独立地选自碳酸乙烯酯、碳酸丙烯酯、 碳酸丁烯酯、氟代碳酸乙烯酯、二氟代碳酸乙烯酯、氟代碳酸二甲酯、氟代碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、二氟乙酸甲酯、二氟乙酸乙酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、氟代醚F-EPE、氟代醚D2、氟代醚HFPM、氟代醚MFE、氟代醚EME、环丁砜、二甲亚砜、二氯甲烷和二氯乙烷中的一种或多种；
    优选地，所述添加剂A和所述添加剂B相同或不同，彼此独立地选自碳酸亚乙烯酯、碳酸乙烯基亚乙酯、1,3-丙烷磺酸内酯、三氟甲基碳酸乙烯酯、硫酸二甲酯、硫酸乙烯酯、甲基硫酸乙烯酯、硫酸丙烯酯、亚硫酸乙烯酯、丁二酸酐、联苯、联苯醚、甲苯、二甲苯、环已基苯、氟苯、对氟甲苯、对氟苯甲醚、叔丁基苯、叔戊基苯、丙烯磺酸内酯、丁烷磺酸内酯、甲烷二磺酸亚甲酯、乙二醇双(丙腈)醚、六甲基二硅氮烷、七甲基二硅氮烷、甲基膦酸二甲酯、乙基膦酸二乙酯、磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、亚磷酸三苯酯、三(三甲基硅基)硼酸酯、三(三甲基硅基)磷酸酯、1,2-二(氰乙氧基)乙烷、1,2,3-三(氰乙氧基)丙烷、双(氰乙基)砜和3-(三甲基硅氧基)丙腈中的一种或多种。
  6. 根据权利要求5所述的电化学装置，其特征在于，所述锂盐A中至少含有60wt％的六氟磷酸锂；
    和/或，所述锂盐B中至少含有50wt％的二氟草酸硼酸锂；
    和/或，所述锂盐B中至少含有1wt％的硝酸锂。
  7. 根据权利要求1-6中任一项所述的电化学装置，其特征在于，所述正极电解液的保有量m1与所述电化学装置的设计容量Q的比值满足0.5g/Ah≤m1/Q≤2.0g/Ah；
    和/或，所述负极电解液的保有量m2与所述电化学装置的设计容量Q的比值满足0.5g/Ah≤m2/Q≤2.0g/Ah；
    优选地，所述正极电解液的保有量m1≤所述负极电解液的保有量m2。
  8. 根据权利要求1-7中任一项所述的电化学装置，其特征在于，所述固态电解质膜具有致密无孔结构或具有致密无贯穿孔结构；
    优选地，所述固态电解质膜为具有致密无贯穿孔结构的无机固态电解质膜；
    优选地，所述固态电解质膜为具有致密无孔结构的无机固态电解质膜；
    优选地，所述固态电解质膜的致密度大于等于99％。
  9. 根据权利要求1-8中任一项所述的电化学装置，其特征在于，形成所述固态电解质膜的材料为Garnet型氧化物电解质、NASICON型氧化物电解质、钙钛矿型氧化物电解质和硫化物电解质中的至少一种；
    优选地，所述Garnet型氧化物电解质选自锂镧锆氧、钽掺杂的锂镧锆氧和铌掺杂的锂镧 锆氧中的至少一种；
    优选地，所述NASICON型氧化物电解质选自磷酸钛铝锂、磷酸锗铝锂、磷酸钛锗铝锂和磷酸硅锗锂中的至少一种；
    优选地，所述钙钛矿型氧化物电解质为锂镧钛氧；
    优选地，所述硫化物电解质选自Li3PS4、Li7P3S11、Li4-x”Ge1-x”Px”S4和Li6PS5X中的至少一种，其中，X”＝0.4或X”＝0.6；X选自F、Cl、Br或I中的至少一种。
  10. 根据权利要求1-9中任一项所述的电化学装置，其特征在于，所述固态电解质膜的离子电导率≥0.1ms/cm；
    优选地，所述固态电解质膜的离子电导率≥1ms/cm；
    和/或，所述固态电解质膜的厚度为5μm～100μm。
  11. 根据权利要求1-10中任一项所述的电化学装置，其特征在于，所述正极片与所述固态电解质膜之间设置有正极密封圈，用于防止所述正极电解液从所述正极片边缘泄露；
    和/或，所述负极片与所述固态电解质膜之间设置有负极密封圈，用于防止所述负极电解液从所述负极片边缘泄露；
    优选地，形成所述正极密封圈的材料和形成所述负极密封圈的材料相同或不同，彼此独立地选自马来酸酐接枝聚丙烯、聚氨酯、丁腈橡胶、丁基橡胶、氯丁橡胶、环氧树脂和硅橡胶中的至少一种。
  12. 根据权利要求11所述的电化学装置，其特征在于，所述正极片包括正极集流体、设置在所述正极集流体至少一侧表面的正极涂覆区域和与所述正极涂覆区域相连的位于所述正极涂覆区域外围的正极密封区域；所述正极涂覆区域内设置正极涂膏，所述正极密封区域内设置所述正极密封圈；
    和/或，所述负极片包括负极集流体、设置在所述负极集流体至少一侧表面的负极涂覆区域和与所述负极涂覆区域相连的位于所述负极涂覆区域外围的负极密封区域；所述负极涂覆区域内设置负极涂膏，所述负极密封区域内设置所述负极密封圈。
  13. 根据权利要求1-12中任一项所述的电化学装置，其特征在于，所述正极片还包括正极活性材料，所述正极活性材料包括LiMn2O4、LiNiO2、LiCoO2、LiNi1-yCoyO2、LiNiaCobAl1-a-bO2、LiMn1-m-nNimConO2、LiMPO4及Li3V2(PO4)3中的一种或多种，其中，0<y<1；0<a<1，0<b<1，0<a+b<1；0<m<1，0<n<1，0<m+n<1；M为Fe、Mn和Co中的一种或多种；
    和/或，所述负极片还包括负极活性材料，所述负极活性材料包括金属锂、天然石墨、人造石墨、中间相微碳球、硬碳、软碳、硅、硅-碳复合物、SiO、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的钛酸锂及Li-Al合金中的一种或多种；
    优选地，所述正极片还包括第二粘结剂，所述第二粘结剂为聚偏氟乙烯、聚四氟乙烯、丁 苯橡胶、丁腈橡胶、水系丙烯酸树脂、聚乙烯醇、聚乙烯醇缩丁醛、聚氨酯、氟化橡胶、羧甲基纤维素和聚丙烯酸中的至少一种；
    优选地，所述负极片还包括第三粘结剂，所述第三粘结剂包括聚偏氟乙烯、聚四氟乙烯、丁苯橡胶、丁腈橡胶、水系丙烯酸树脂、聚乙烯醇、聚乙烯醇缩丁醛、聚氨酯、氟化橡胶、羧甲基纤维素、聚丙烯酸、环氧树脂、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚乙烯吡咯烷酮和尼龙中的至少一种。
  14. 根据权利要求1-13中任一项所述的电化学装置，其特征在于，所述正极片还包括导电剂；
    和/或，所述负极片还包括导电剂；
    优选地，所述正极片的导电剂和所述负极片的导电剂彼此独立地包括基于碳的材料、基于金属的材料、导电聚合物或它们的混合物；
    优选地，所述基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合；
    优选地，所述基于金属的材料选自金属粉、金属纤维、铜、镍、铝和银中的至少一种；
    优选地，所述导电聚合物为聚亚苯基衍生物。
  15. 根据权利要求1-14中任一项所述的电化学装置，其特征在于，所述电化学装置为电池或超级电容器。
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