WO2025256205A1 - 二次电池和电子装置 - Google Patents

二次电池和电子装置

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Publication number
WO2025256205A1
WO2025256205A1 PCT/CN2025/081930 CN2025081930W WO2025256205A1 WO 2025256205 A1 WO2025256205 A1 WO 2025256205A1 CN 2025081930 W CN2025081930 W CN 2025081930W WO 2025256205 A1 WO2025256205 A1 WO 2025256205A1
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Prior art keywords
mass
electrolyte
lithium
secondary battery
content
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PCT/CN2025/081930
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English (en)
French (fr)
Inventor
庄锐锐
王可飞
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Publication of WO2025256205A1 publication Critical patent/WO2025256205A1/zh
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This application relates to the field of energy storage, specifically to a secondary battery and electronic device.
  • Rechargeable batteries have advantages such as high energy density, high open-circuit voltage, low self-discharge rate, long cycle life, and good safety, and are widely used in portable energy storage, electronic devices, electric vehicles, and other fields.
  • issues such as lifespan and safety have been exposed. Therefore, consumers are placing higher demands on the overall performance of rechargeable batteries, such as simultaneously possessing high energy density, good high-temperature storage performance, cycle performance, and safety performance.
  • a secondary battery including an electrolyte and a separator; the separator includes a polyolefin substrate and a coating disposed on at least one surface of the polyolefin substrate, the coating including inorganic particles.
  • the electrolyte Based on the total mass of the electrolyte, the electrolyte contains: (I) ether nitrile in a content of 0.01% by mass or more and 2% by mass or less, (II) succinate in a content of 0.01% by mass or more and 2% by mass or less, (III) propionate in a content of 25% by mass or more and 65% by mass or less, and (IV) boron-containing lithium salt in a content of 0.01% by mass or more and 3% by mass or less; the total content of the above ether nitrile, succinate and propionate is 25.02% by mass or more and 67.9% by mass or less, and the total content of the above succinate and boron-containing lithium salt is 0.02% by mass or more and 4.6% by mass or less.
  • the inventors discovered that coating inorganic particles onto the separator substrate can improve battery safety.
  • the electrolyte contains specific amounts of ether nitrile, succinic acid nitrile, propionate ester, and boron-containing lithium salt, a stable coating can be formed on the positive electrode surface, which not only improves the heat resistance of the separator but also significantly enhances the safety performance and vibration resistance of the secondary battery.
  • the inorganic particles include at least one selected from aluminum, magnesium, titanium, zirconium, niobium, indium, tungsten, tin, zinc, or antimony. Further, the inorganic particles are selected from at least one selected from alumina, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, titanium dioxide, zirconium dioxide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, indium trioxide, tungsten trioxide, tin dioxide, zinc oxide, or antimony trioxide.
  • the safety of the battery can be significantly improved.
  • the ether nitrile includes at least one selected from ethylene glycol di(propionitrile) ether, 1,2,3-tris(2-cyanoethoxy)propane, 1,2,4-tris(2-cyanoethoxy)butane, 1,1,1-tris(cyanoethoxymethylene)ethane, 1,1,1-tris(cyanoethoxymethylene)propane, 3-methyl-1,3,5-tris(cyanoethoxy)pentane, 1,2,7-tris(cyanoethoxy)heptane, 1,2,6-tris(cyanoethoxy)hexane, or 1,2,5-tris(cyanoethoxy)pentane.
  • the propionate ester includes at least one selected from methyl propionate, ethyl propionate, propyl propionate, or butyl propionate.
  • the boron-containing lithium salts include lithium tetrafluoroborate [CAS:14283-07-9], lithium difluorooxalate borate [CAS:409071-16-5], lithium bis(oxalate borate [CAS:244761-29-3], lithium tetracyanoborate [CAS:294867-26-8], lithium tetra(trifluoromethyl)borate, lithium (trifluoromethyl)trifluoroborate, lithium bis(trifluoromethyl)difluoroborate [CAS:390750-38-6], and lithium pentafluoroethyltrifluoroborate [CAS: [390750-43-3], Lithium dicyanooxalate borate [CAS:1390624-95-9], Lithium dimalonate borate [CAS:291298-96-9], Lithium (2-fluoromalonate) difluoroborate [CAS:1604746-55-5], Lithium malonate oxalate borate [CAS:14283-0
  • the electrolyte includes ether nitrile in a content of 0.01% by mass and less than 1% by mass, based on the total mass of the electrolyte.
  • the electrolyte includes ether nitrile at a content of 0.4% by mass or more and 0.8% by mass or less, based on the total mass of the electrolyte.
  • the electrolyte includes succinic anionylene at a content of 1.2% to 1.8% by mass, based on the total mass of the electrolyte.
  • the electrolyte includes propyl propionate in a concentration of 25% to 65% by mass, based on the total mass of the electrolyte. Adding propyl propionate to the electrolyte in a concentration within this range results in a coating with excellent stability and further improves battery performance.
  • the electrolyte includes ethyl propionate in a concentration of 25% to 65% by mass, based on the total mass of the electrolyte. Adding ethyl propionate to the electrolyte in a concentration within this range results in a coating with excellent stability and further improves battery performance.
  • the electrolyte comprises propyl propionate and ethyl propionate. Adding a mixture of propyl propionate and ethyl propionate to the electrolyte results in a more stable coating and further enhances battery performance.
  • the electrolyte further comprises other nitrile compounds, including at least one selected from adiponitrile, cis-butenedionitrile, trans-butenedionitrile, 1,3,5-pentanetricarbonyl nitrile, 1,2,3-propanetricarbonyl nitrile, 1,3,6-hexanetricarbonyl nitrile, or 1,2,6-hexanetricarbonyl nitrile; the content of the other nitrile compounds is 0.1% by mass and 8% by mass or less based on the total mass of the electrolyte.
  • These other nitrile compounds can improve the stability of the aforementioned coating, enhance lithium-ion charge transport, and improve vibration resistance.
  • the adiponitrile content is 0.1% by mass or more and 1% by mass or less, based on the total mass of the electrolyte.
  • the adiponitrile content is 2.1% by mass or more and 4% by mass or less, based on the total mass of the electrolyte.
  • the content of 1,3,6-hexanetrionitrile is 0.3% by mass or more and 0.9% by mass or less, based on the total mass of the electrolyte.
  • the content of the aforementioned 1,3,6-hexanetricarbonyl nitrile is 1.7% by mass or more and 3.1% by mass or less, based on the total mass of the electrolyte.
  • the electrolyte further includes other additives, including at least one of fluoroethylene carbonate, vinylene carbonate, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propanesulfonate lactone, 1,3-propenesulfonate lactone, vinyl sulfate, 1,3-propanediol cyclosulfonate, fluorobenzene, cyclohexylbenzene, biphenyl, tris(trimethylsilane)phosphate, or tris(trimethylsilane)borate; the content of the other additives is 0.01% by mass or more and 10% by mass or less based on the total mass of the electrolyte.
  • other additives including at least one of fluoroethylene carbonate, vinylene carbonate, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propanesulfonate lactone, 1,3-propenesulfonate lactone, vinyl sulfate
  • the content of the aforementioned fluoroethylene carbonate is 0.01% by mass and 3% by mass or less, based on the total mass of the electrolyte.
  • the content of the aforementioned fluoroethylene carbonate is 4.1% by mass and 6.9% by mass, based on the total mass of the electrolyte.
  • the content of lithium difluorophosphate is 0.01% by mass and 0.3% by mass or less, based on the total mass of the electrolyte.
  • the content of vinyl sulfate is 0.01% by mass and 0.4% by mass, based on the total mass of the electrolyte.
  • Another aspect of this application provides an electronic device that includes the secondary battery described above.
  • the embodiments of this application add a specific amount of succinic anion and boron-containing lithium salt to the electrolyte so that it can just inhibit the decomposition of ether nitrile and propionate, forming a stable coating on the positive electrode surface, thereby not only improving the heat resistance of the separator, but also significantly improving the safety performance and vibration resistance of the secondary battery.
  • this application not only improves the heat resistance of the separator, but also significantly enhances the safety performance and vibration resistance of the secondary battery.
  • the first aspect of this application provides a secondary battery, which includes an electrolyte, a separator, a positive electrode, and a negative electrode as described below.
  • the electrolyte used in the secondary battery embodiments of this application includes an electrolyte and a solvent for dissolving the electrolyte.
  • the electrolyte includes ether nitrile, succinic acid nitrile, propionate ester, and boron-containing lithium salt.
  • the separator used in secondary batteries comprises a polyolefin substrate and a coating on the substrate.
  • the addition of inorganic particles to the coating significantly improves the separator's heat resistance, thereby enhancing battery safety.
  • the inventors unexpectedly discovered that ether nitrile and propionate in the electrolyte can inhibit the swelling of the polyolefin substrate in the electrolyte.
  • the presence of inorganic particles catalyzes the decomposition of ether nitrile and propionate on the positive electrode surface.
  • a specific amount of succinic anionylene and boron-containing lithium salt can precisely inhibit the decomposition of ether nitrile and propionate, forming a stable coating on the positive electrode surface. Using this design not only improves the separator's heat resistance but also significantly enhances the safety performance and vibration resistance of the secondary battery.
  • the ether nitrile includes at least one selected from ethylene glycol di(propionitrile) ether, 1,2,3-tris(2-cyanoethoxy)propane, 1,2,4-tris(2-cyanoethoxy)butane, 1,1,1-tris(cyanoethoxymethylene)ethane, 1,1,1-tris(cyanoethoxymethylene)propane, 3-methyl-1,3,5-tris(cyanoethoxy)pentane, 1,2,7-tris(cyanoethoxy)heptane, 1,2,6-tris(cyanoethoxy)hexane, or 1,2,5-tris(cyanoethoxy)pentane.
  • ether nitrile Only one ether nitrile may be used, or two or more may be used. Ethylene glycol di(propionitrile) ether, 1,2,3-tris(2-cyanoethoxy)propane, or 3-methyl-1,3,5-tris(cyanoethoxy)pentane are preferred.
  • the content of ether nitrile is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.4% by mass or more.
  • the mass content of ether nitrile is 2% by mass or less, preferably 1.9% by mass or less, more preferably 1.6% by mass or less, even more preferably 1.2% by mass or less, and particularly preferably 1% by mass or less. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the content of ether nitrile is set as a1% by mass, where a1 is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, or within a range consisting of any two of the above values. For example, 0.01 to 0.09, 0.05 to 0.1, 0.1 to 0.8, 0.5 to 1.2, 0.7 to 1.9. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the mass content of succinic acid (SNA) based on the total mass of the electrolyte is 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.08% by mass or more.
  • the SNA mass content is 2% by mass or less, preferably 1.8% by mass or less, more preferably 1.6% by mass or less, even more preferably 1.4% by mass or less, and particularly preferably 1.2% by mass or less. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the succinic acid content is set as a2% by mass, where a2 is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, or within a range consisting of any two of the above values. For example, 0.01 to 0.09, 0.05 to 0.1, 0.1 to 0.8, 0.6 to 1.2, 0.8 to 1.8. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the propionate ester includes at least one selected from methyl propionate, ethyl propionate, propyl propionate, or butyl propionate. Only one type of propionate may be used, or two or more types may be used. Due to the excellent stability of the formed coating, battery performance is further improved; ethyl propionate and propyl propionate are preferred.
  • the propionate content based on the total mass of the electrolyte, is 25% by mass or more, preferably 28% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.
  • the propionate content is 65% by mass or less, preferably 60% by mass or less, more preferably 56% by mass or less, even more preferably 53% by mass or less, and particularly preferably 48% by mass or less. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the propionate content is set to a3% by mass, where a3 is 25, 28, 29, 30, 32, 33, 35, 39, 40, 42, 45, 48, 50, 53, 56, 60, 63, 65, or within a range consisting of any two of the above values.
  • a3 is 25, 28, 29, 30, 32, 33, 35, 39, 40, 42, 45, 48, 50, 53, 56, 60, 63, 65, or within a range consisting of any two of the above values.
  • 25 to 28, 28 to 36, 33 to 45, 40 to 53, 50 to 65 when within the above ranges, helps to further suppress heat generation during internal short circuits.
  • boron-containing lithium salts include lithium tetrafluoroborate, lithium difluorooxalate borate, lithium bis(oxalate borate), lithium tetracyanoborate, (3-methyl-2,4-pentanedione)oxalate borate (MOAB), lithium tetra(trifluoromethyl)borate, lithium (trifluoromethyl)trifluoroborate, lithium bis(trifluoromethyl)difluoroborate, lithium pentafluoroethyltrifluoroborate, lithium dicyanooxalate borate, lithium bis(malonate)borate, lithium (2-fluoromalonate)difluoroborate, lithium malonate oxalate borate, lithium bis(catechol)borate, and lithium bis(catechol)borate.
  • MOAB 3-methyl-2,4-pentanedione)oxalate borate
  • MOAB 3-methyl-2,4-pentanedione)oxalate bo
  • At least one of lithium boron salts including lithium methoxytricyanoborate, lithium ethoxytricyanoborate, lithium tetramethoxyborate, lithium tetraethoxyborate, lithium tetra(trifluoromethoxy)borate, lithium tetra(2,2,2-trifluoroethoxy)borate, lithium polytetrafluoro(hydroquinoneoxy)borate, lithium di(trifluoroborate)sulfate, lithium difluoroborate, lithium methane disulfonate difluoroborate, lithium difluorophosphoryloxytrifluoroborate, lithium di(difluorophosphoryloxy)difluoroborate, or lithium tetra(difluorophosphoryloxy)borate, is used.
  • the formed coating exhibits excellent stability, and the battery performance is further improved.
  • the boron-containing lithium salt can be only one type, or it can be two or more types, or three or more types.
  • the boron-containing lithium salt preferably includes at least one of lithium tetrafluoroborate, lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), or (3-methyl-2,4-pentanedione) oxalatoborate ester (MOAB).
  • LiBOB lithium bis(oxalato)borate
  • LiDFOB lithium difluorooxalatoborate
  • MOAB 3-methyl-2,4-pentanedione
  • the mass content of boron-containing lithium salt is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.06% by mass or more, and even more preferably 0.1% by mass or more.
  • the mass content of boron-containing lithium salt is 3% by mass or less, preferably 2.3% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.1% by mass or less, and particularly preferably 0.7% by mass or less. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the content of the boron-containing lithium salt is set to a4% by mass, where a4 is 0.01, 0.02, 0.06, 0.1, 0.4, 0.7, 1.1, 1.5, 2.3, 2.8, 3, or within a range consisting of any two of the above values, for example, 0.01 to 0.1, 0.1 to 0.7, 0.4 to 1.1, 0.7 to 2.3, 1.5 to 3. When within the above range, it helps to further suppress heat generation during internal short circuits.
  • the total mass content of (I) ether nitrile, (II) succinate, and (III) propionate is 25.02% by mass or more, preferably 30.3% by mass or more.
  • the upper limit for the total content of (I) ether nitrile, (II) succinate, and (III) propionate is 67.9% by mass or less, preferably 58.3% by mass or less.
  • the total mass content of (I) ether nitrile, (II) succinate, and (III) propionate is a1+a2+a3 mass%, where a1+a2+a3 is 25.02, 28.18, 30.3, 35.6, 39.9, 43.2, 49.7, 55, 58.3, 62.6, 67.9, or within any two of the above values.
  • a1+a2+a3 is 25.02, 28.18, 30.3, 35.6, 39.9, 43.2, 49.7, 55, 58.3, 62.6, 67.9, or within any two of the above values.
  • 25.02 to 39.9, 28.18 to 49.7, 30.3 to 55, 35.6 to 58.3, and 39.9 to 67.9 when within the above ranges, helps to further suppress heat generation during internal short circuits.
  • the total mass content of (II) succinic acid and (IV) boron-containing lithium salt is 0.02% by mass or more, preferably 0.12% by mass or more.
  • the upper limit of the total content of (II) succinic acid and (IV) boron-containing lithium salt is 4.6% by mass or less, preferably 3.9% by mass or less.
  • the total mass content of (II) succinic anion and (IV) boron-containing lithium salt is a2+a4 mass%, where a2+a4 is 0.02, 0.12, 0.26, 0.5, 1, 1.5, 2.3, 2.9, 3.9, 4.6, or within a range of any two of the above values. For example, 0.02 to 0.12, 0.12 to 0.5, 0.26 to 1.5, 1 to 2.9, 1.5 to 4.6. When within the above ranges, it helps to further suppress heat generation during internal short circuits.
  • the electrolyte may also include other nitrile compounds.
  • the inventors also unexpectedly discovered that other nitrile compounds can improve the stability of the aforementioned coating, enhance lithium-ion charge transport, and improve vibration resistance.
  • nitrile compounds include at least one of adiponitrile, cis-butenedionitrile, trans-butenedionitrile, 1,3,5-pentanetricarbonyl nitrile, 1,2,3-propanetricarbonyl nitrile, 1,3,6-hexanetricarbonyl nitrile, or 1,2,6-hexanetricarbonyl nitrile. There may be only one or more of the aforementioned other nitrile compounds.
  • the content of other nitrile compounds is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.6% by mass or more, further preferably 0.9% by mass or more, and particularly preferably 1.4% by mass or more.
  • the content of other nitrile compounds is 8% by mass or less, preferably 7.9% by mass or less, more preferably 7.1% by mass or less, further preferably 6.2% by mass or less, and particularly preferably 5.3% by mass or less.
  • the total content of other nitrile compounds is b% by mass, where b is 0.1, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.4, 1.5, 2, 2.5, 3, 3.1, 3.6, 3.9, 4, 4.6, 5.3, 6.2, 7.1, 7.9, 8, or within a range consisting of any two of the above values.
  • it helps to further improve the vibration resistance characteristics of the secondary battery.
  • the electrolyte may also include other additives.
  • other additives can inhibit the decomposition and regeneration of the coating formed by the reaction of the aforementioned substances (I) to (IV) with the active part of the positive electrode surface during the charging and discharging process, thereby further reducing the positive electrode resistance and improving the vibration resistance characteristics.
  • additives include at least one of the following: fluoroethylene carbonate, vinylene carbonate, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propanesulfonate lactone, 1,3-propenesulfonate lactone, vinyl sulfate, 1,3-propanediol cyclosulfonate, fluorobenzene, cyclohexylbenzene, biphenyl, tris(trimethylsilane) phosphate, or tris(trimethylsilane) borate.
  • fluoroethylene carbonate vinylene carbonate, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propanesulfonate lactone, 1,3-propenesulfonate lactone, vinyl sulfate, 1,3-propanediol cyclosulfonate, fluorobenzene, cyclohexylbenzene, biphenyl, tris(trimethyl
  • the content of other additives is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1.6% by mass or more, and more preferably 2.8% by mass or more.
  • the content of other additives is 10% by mass or less, preferably 9.7% by mass or less, more preferably 8.2% by mass or less, even more preferably 7.1% by mass or less, and particularly preferably 6.7% by mass or less.
  • the total content of other additives is c% by mass, where c is 0.01, 0.03, 0.1, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 1.6, 2, 2.5, 2.9, 3, 3.5, 3.9, 4, 4.5, 5, 5.7, 6, 6.5, 7.1, 7.5, 8.2, 8.6, 9, 9.3, 9.7, 10, or within a range consisting of any two of the above values.
  • the lithium salt used in the electrolyte of this application includes lithium hexafluorophosphate. Based on the total mass of the electrolyte, the content of lithium hexafluorophosphate is 9-15% by mass, preferably 9-13% by mass, and more preferably 9-12% by mass. By setting the content within the above range, the effect of improving high-temperature and low-temperature characteristics can be more balanced.
  • the electrolyte of this application may further comprise any non-aqueous solvent known in the art that can be used as an electrolyte solvent.
  • non-aqueous solvent known in the art that can be used as an electrolyte solvent.
  • examples include chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, cyclic ethers, and chain ethers.
  • Chain carboxylic acid esters, such as ethyl acetate and ethyl fluorocarbonate, are preferred.
  • a separator is typically placed between the positive and negative electrodes.
  • the electrolyte of this application is typically used after penetrating into the separator.
  • the diaphragm includes a polyolefin substrate and a coating on the substrate, the coating including inorganic particles.
  • the polyolefin is polyethylene or polypropylene.
  • the separator may also be a material formed by laminating the above materials, examples of which include, but are not limited to, a three-layer separator formed by laminating polypropylene, polyethylene, and polypropylene in that order.
  • the metallic element in the inorganic particles includes at least one of aluminum, magnesium, titanium, zirconium, niobium, indium, tungsten, tin, zinc, or antimony.
  • the inorganic particles may be selected from at least one of alumina, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, titanium dioxide, zirconium dioxide, niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide, indium trioxide, tungsten trioxide, tin dioxide, zinc oxide, or antimony trioxide.
  • the separator can be in the form of a thin film, examples of which include, but are not limited to, nonwoven fabrics, woven fabrics, microporous membranes, etc.
  • the pore size (diameter) of the separator is 0.01 ⁇ m to 1 ⁇ m, and the thickness is 5 ⁇ m to 50 ⁇ m.
  • separators formed by using a resin-based adhesive to form a composite porous layer containing the above-mentioned inorganic particles on the surface of the positive and/or negative electrodes for example, a separator formed by using fluororesin as an adhesive to form a porous layer of alumina particles with a particle size (Dv90) of less than 1 ⁇ m on both sides of the positive electrode.
  • the thickness of the separator is arbitrary. In some embodiments, the thickness of the separator is greater than 1 ⁇ m, greater than 5 ⁇ m, or greater than 8 ⁇ m. In some embodiments, the thickness of the separator is less than 50 ⁇ m, less than 40 ⁇ m, or less than 30 ⁇ m. When the thickness of the separator is within the above ranges, insulation and mechanical strength can be ensured, and the rate characteristics and energy density of the secondary battery can be ensured.
  • the positive electrode includes a positive electrode current collector and a positive electrode additive layer disposed on the surface of the positive electrode current collector.
  • the positive electrode flux layer contains the positive electrode active material, and the positive electrode flux layer can be one or more layers.
  • the positive electrode active material is any substance capable of reversibly inserting and deintercalating lithium ions.
  • lithium-containing composite metal oxides containing one or more of the group consisting of cobalt, manganese, and nickel, or lithium-containing olivine-type phosphates containing one or more of the group consisting of iron, cobalt, nickel, and manganese are used.
  • These positive electrode active materials can be used alone or in combination of two or more.
  • lithium-containing complex metal oxides or lithium-containing olivine phosphates may be replaced by other elements, or a portion of cobalt, nickel, manganese, and iron may be replaced by one or more elements selected from Co, Mn, Ni, Mg, Al, B, Ti, V, Nb, Cu, Zn, Mo, Ca, Sr, W, and Zr, or coated with compounds containing these other elements or carbon materials.
  • the positive electrode potential is preferably 4.4V (vs. Li/Li + ) or higher, more preferably 4.5V (vs. Li/Li + ) or higher, and particularly preferably 4.6V (vs. Li/Li + ) or higher.
  • the conductive agent used in the positive electrode there are no particular restrictions on the conductive agent used in the positive electrode, as long as it is an electron-conducting material that does not cause chemical changes. Examples include natural graphite (flake graphite, etc.), artificial graphite, acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal cracking black, etc. Furthermore, graphite and carbon black can be appropriately mixed.
  • the mass content of the conductive agent in the positive electrode mixture is preferably 1 to 10% by mass, and particularly preferably 1.5 to 5% by mass.
  • the positive electrode can be manufactured as follows: The above-mentioned positive electrode active material is mixed with conductive agents such as acetylene black and carbon black, and binders such as polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, copolymer of styrene and butadiene, and carboxymethyl cellulose. A high-boiling-point solvent such as 1-methyl-2-pyrrolidone is added and the mixture is kneaded to form a positive electrode slurry. This slurry is then coated onto aluminum foil or other materials used as a positive electrode current collector, dried, and pressurized to form a positive electrode slurry layer.
  • conductive agents such as acetylene black and carbon black
  • binders such as polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, copolymer of styrene and butadiene, and carboxymethyl cellulose.
  • the density of the portion of the positive electrode excluding the positive current collector is typically 3.5 g/ cm3 or higher. To further improve the battery capacity, it is preferably 3.8 g/ cm3 or higher, more preferably 4 g/ cm3 or higher, and even more preferably 4.1 g/ cm3 or higher. Furthermore, as an upper limit, it is preferably 4.6 g/ cm3 or lower.
  • positive electrode current collector there are no particular limitations on the type of positive electrode current collector; it can be any material known to be suitable for use as a positive electrode current collector.
  • positive electrode current collectors may include, but are not limited to, metallic materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper.
  • the positive electrode current collector is a metallic material.
  • the positive electrode current collector is aluminum.
  • the surface of the positive current collector may include a conductive additive or a conductive coating.
  • conductive additives include, but are not limited to, carbon and precious metals such as gold, platinum, and silver.
  • conductive coatings may include a mixture layer containing inorganic oxides, conductive agents, and binders.
  • the positive electrode can be manufactured by forming a positive electrode mixture layer containing positive electrode active material and binder on the positive electrode current collector.
  • the manufacture of a positive electrode using positive electrode active material can be carried out by conventional methods, namely, dry mixing the positive electrode active material, binder, and conductive material and thickener as needed, forming a sheet, and pressing the resulting sheet onto the positive electrode current collector; or dissolving or dispersing these materials in a liquid medium to form a slurry, coating the slurry onto the positive electrode current collector and drying it, thereby forming a positive electrode mixture layer on the positive electrode current collector, thus obtaining the positive electrode.
  • the negative electrode includes a negative electrode current collector and a negative electrode additive layer disposed on the surface of the negative electrode current collector, the negative electrode additive layer containing a negative electrode active material.
  • the rechargeable capacity of the negative electrode active material is greater than the discharge capacity of the positive electrode active material to prevent unintentional deposition of lithium metal on the negative electrode during charging.
  • negative electrode active material examples include carbon-based negative electrode active materials, metal-based negative electrode active materials, and negative electrode active materials that combine these elements.
  • Carbon-based anode active materials refer to active materials with a carbon-based backbone that can insert lithium.
  • Examples of carbon-based anode active materials include carbonaceous materials and graphitic materials.
  • Examples of carbonaceous materials include easily graphitized carbon and non-graphitized carbon with a similar amorphous structure, such as glassy carbon.
  • easily graphitized carbons examples include carbon materials derived from petroleum or coal using tar pitch as a raw material. Specific examples include coke, mesophase carbon microspheres (MCMB), mesophase pitch-based carbon fibers, and pyrolysis-grown carbon fibers.
  • examples of non-graphitized carbons include phenolic resin sintered bodies, polyacrylonitrile-based carbon fibers, quasi-isotropic carbon, furfuryl alcohol resin sintered bodies (PFA), and hard carbon.
  • examples of graphitic materials include natural graphite and artificial graphite.
  • examples of artificial graphite include: artificial graphite formed by heat-treating carbon containing easily graphitizable carbon primarily at temperatures above 2800°C; graphitic MCMB formed by heat-treating MCMB at temperatures above 2000°C; and graphitic mesophase pitch-based carbon fiber formed by heat-treating mesophase pitch-based carbon fiber at temperatures above 2000°C.
  • natural graphite amorphously coated natural graphite
  • metal-based anode active materials are active materials containing metals, generally referring to active materials whose structure contains elements capable of intercalating into or alloying with lithium, and whose theoretical current capacity per unit mass is 500 mAh/g or more when intercalated into or alloyed with lithium.
  • metal-based anode active materials include: lithium metal, elemental metals capable of forming lithium alloys (e.g., Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, Ti, etc.) and their alloys, as well as their oxides, sulfides, nitrides, silicides, carbides, phosphides, etc.
  • active materials containing silicon are preferred as metal-based anode active materials. This is because using silicon-based anode active materials enables high-capacity lithium-ion secondary batteries.
  • silicon-based anode active materials include: silicon (Si), silicon-containing alloys, silicon oxides, and silicon-containing materials coated or composited with conductive carbon.
  • silicon-carbon materials are preferred, such as porous carbon-supported silicon composites.
  • the negative electrode active material can be used alone or in combination of two or more in any ratio.
  • the negative electrode mixture layer may also include a negative electrode binder.
  • the negative electrode binder improves the bonding between the negative electrode active material particles and the bonding between the negative electrode active material and the current collector.
  • the type of negative electrode binder there are no particular limitations on the type of negative electrode binder, as long as it is a material stable to the electrolyte or the solvent used in electrode manufacturing.
  • the negative electrode binder includes a resin binder.
  • resin binders include, but are not limited to, fluoropolymers, polyacrylonitrile (PAN), polyimide resins, acrylic resins, polyolefin resins, etc.
  • the negative electrode binder When preparing the negative electrode mixture slurry using an aqueous solvent, the negative electrode binder includes, but is not limited to, carboxymethyl cellulose (CMC) or its salts, styrene-butadiene rubber (SBR), polyacrylic acid (PAA) or its salts, polyvinyl alcohol, etc.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • PAA polyacrylic acid
  • polyvinyl alcohol etc.
  • any known current collector can be used.
  • examples of negative electrode current collectors include, but are not limited to, metallic materials such as copper, nickel, stainless steel, and nickel-plated steel. In some embodiments, the negative electrode current collector is copper.
  • the negative electrode can be prepared by coating a negative electrode slurry containing negative electrode active material, resin binder, etc. onto the negative electrode current collector, drying it, and then calendering it to form a negative electrode slurry layer on both sides of the negative electrode current collector, thereby obtaining the negative electrode.
  • a second aspect of this application provides an electronic device that includes a secondary battery as described in this application.
  • the secondary battery in this application is not particularly limited, and it can be used in any electronic device known in the prior art.
  • the secondary battery of this application can be used in, but is not limited to, laptops, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headphones, video recorders, LCD TVs, portable cleaners, portable CD players, mini CDs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, electric bicycles, bicycles, lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, household large-capacity batteries, and lithium-ion capacitors, etc.
  • Lithium cobalt oxide (97% by mass) and acetylene black (1.5% by mass) were mixed and added to a solution obtained by dissolving polyacrylonitrile (1.5% by mass) in 1-methyl-2-pyrrolidone, and then mixed to prepare a positive electrode paste.
  • This positive electrode paste was then coated onto one side of an aluminum foil (current collector), dried, pressurized, and cut to the specified size to fabricate the positive electrode.
  • a 5 ⁇ m porous polyethylene membrane was used as the diaphragm substrate.
  • Deionized water and the inorganic particles listed in Table 1-1 were added to a dual planetary mixer and dispersed at high speed at 40°C for 1 hour. Then, sodium carboxymethyl cellulose binder was added, and the mixture was stirred at low speed at room temperature for 1 hour to obtain an inorganic particle slurry with a solid content of 3%, wherein the inorganic particles accounted for 2% of the total weight of the slurry, and sodium carboxymethyl cellulose accounted for 1% of the total weight of the slurry.
  • the inorganic particle slurry was then coated onto one side of the 5 ⁇ m porous polyethylene membrane using a printing coating method and dried to obtain the diaphragm with an inorganic particle layer thickness of 1.5 ⁇ m.
  • LiPF6 used as the supporting electrolyte, was dissolved in a solution containing (I) ether nitrile, (II) succinate, (III) propionate, (IV) boron-containing lithium salt, other nitrile compounds, and other additives. Based on 100 parts by mass of the total electrolyte, the contents and composition of (I) to (IV), other nitrile compounds, and other additives are shown in Tables 1-2 and 1-3. The content of LiPF6 was 14%, with the remainder being ethylene carbonate and propylene carbonate (mass ratio 1.2:1).
  • the positive and negative electrodes, as prepared above, are each connected to a wire.
  • the electrodes are then layered and wound using the aforementioned separator.
  • the wound assembly, along with 3.2g of electrolyte, is then housed within an aluminum laminated casing.
  • the opening of the casing is heat-sealed, and a secondary battery is manufactured through formation and capacity testing.
  • This secondary battery is a pouch-shaped secondary battery with a width of 35mm, a height of 48mm, and a thickness of 5mm.
  • the electrolytes prepared using electrolytes numbered 1 to 35 in the above steps were matched with the membranes prepared using membranes numbered 1 to 12 to prepare secondary batteries, resulting in Examples 1 to 35; the electrolytes prepared using electrolytes numbered 36 to 43 in the above steps were matched with the membrane prepared using membrane 1 to prepare secondary batteries, resulting in Comparative Examples 1 to 8; the electrolyte prepared using electrolyte 43 in the above steps was matched with the membrane prepared using membrane 13 to prepare secondary batteries, resulting in Comparative Example 9; and the electrolyte prepared using electrolyte 1 in the above steps was matched with the membrane prepared using membrane 13 to prepare secondary batteries, resulting in Comparative Example 10.
  • the secondary batteries prepared in Examples 1 to 35 and Comparative Examples 1 to 9 were tested for their heat resistance, safety, and vibration resistance using the following methods. The test results are shown in Table 2.
  • the negative electrode and separator obtained in the examples and comparative examples were cut into slices 50 mm wide and 50 mm long.
  • the negative electrode slices and separator slices were overlapped and pressed using a roller press under conditions of 10 kN/m load and 80°C to obtain a test piece integrating the negative electrode slices and separator slices.
  • the test piece and the electrolyte specified above were sealed in a laminated packaging material to obtain the sample.
  • the amount of electrolyte was set to be 4 g/Ah relative to the negative electrode capacity.
  • the laminated packaging material was opened and the test piece was removed.
  • the dimensions of the diaphragm on the test piece were measured. Based on the area A0 of the diaphragm before heating and the area A1 of the diaphragm after heating, the shrinkage rate of the diaphragm ((A0-A1)/A0) ⁇ 100 (%) was calculated.
  • A Shrinkage rate less than 0.5%.
  • B Shrinkage rate greater than 0.5% and less than 1.0%.
  • C Shrinkage rate greater than 1.0% and less than 5.0%.
  • D Shrinkage rate greater than 5.0% and less than 10.0%.
  • E Shrinkage rate greater than 10.0%.
  • A The number of test subjects that did not rupture or catch fire was 4 or 5.
  • a charge-discharge test was performed five times, consisting of charging to 4.6V at 60°C using a constant current method with a charging rate of 0.1C, followed by discharging to 3.0V at a discharging rate of 0.1C.
  • the discharge capacity of the fifth cycle was taken as the initial capacity.
  • the secondary battery was fixed on a sieve with an inner diameter of 200mm and vibrated for 1 hour using a Ro-tap type sieve vibrator.
  • the same charge-discharge test as described above was then performed, and the discharge capacity after the vibration test was measured.
  • the ratio of the discharge capacity after the vibration test to the initial discharge capacity was calculated as the capacity retention rate. The larger this value, the less capacity loss caused by the vibration test.
  • Capacity retention rate is over 95%.
  • Capacity retention rate is above 90% and below 95%.
  • Capacity retention rate is above 85% and less than 90%.
  • Capacity retention rate is less than 85%.
  • the electrolyte contains specific amounts of ether nitrile, succinic acid ester, propionate, and boron-containing lithium salt provided in this application.
  • the total content of ether nitrile, succinic acid ester, and propionate in the electrolyte is set to a specific range, and the total content of succinic acid ester and boron-containing lithium salt is set to a specific range.
  • the resulting secondary battery separator exhibits good heat resistance and significantly improves the safety performance and vibration resistance of the secondary battery.
  • the impedance of the coating can be reduced, further improving the safety performance and vibration resistance of the secondary battery. Furthermore, when the mass content of other nitrile compounds in the electrolyte meets the above-mentioned range, the impedance of the coating can be further reduced, improving vibration resistance.
  • the inventors unexpectedly discovered that these additives can inhibit the decomposition and regeneration of the coating during charge and discharge, thereby further improving the safety performance and vibration resistance of the secondary battery.
  • the mass content of other additives in the electrolyte meets the aforementioned range, it can further inhibit the decomposition and regeneration of the coating during charge and discharge, thereby significantly improving the safety performance and vibration resistance of the secondary battery.
  • references to “embodiment,” “partial embodiment,” “one embodiment,” “another example,” “example,” “specific example,” or “partial example” mean that at least one embodiment or example in this application includes a specific feature, structure, material, or characteristic described in that embodiment or example. Therefore, descriptions appearing throughout this specification, such as “in some embodiments,” “in an embodiment,” “in one embodiment,” “in another example,” “in one example,” “in a specific example,” or “example,” do not necessarily refer to the same embodiments or examples in this application. Furthermore, specific features, structures, materials, or characteristics in this application can be combined in any suitable manner in one or more embodiments or examples.

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Abstract

本申请公开了一种二次电池和电子装置，二次电池包括电解液和隔膜，隔膜包括聚烯烃基材以及设置在聚烯烃基材至少一个表面上的涂层，涂层包括无机颗粒，电解液含有特定量的醚腈、丁二腈、丙酸酯、以及含硼锂盐。本申请通过将电解液中的醚腈、丁二腈与丙酸酯的合计含量设定为特定的范围，将丁二腈与含硼锂盐的合计含量设定为特定的范围，抑制醚腈与丙酸酯的分解，帮助其在正极表面形成稳定的覆膜，从而不仅能够改善隔膜的耐热性，还能显著提高二次电池的安全性能和耐振动特性。

Description

二次电池和电子装置
本申请要求2024年6月14日提交至中国专利局、申请号为2024107693283、申请名称为“二次电池和电子装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及储能领域，具体涉及一种二次电池和电子装置。
背景技术
二次电池具有储能密度大、开路电压高、自放电率低、循环寿命长、安全性好等优点，广泛应用于便携式电能储存、电子设备、电动汽车等各个领域。但随着二次电池的应用，其暴露出寿命、安全等问题，因此消费者对二次电池的综合性能提出更高的要求，例如同时具有高的能量密度、良好的高温存储性能、循环性能及安全性能等。
然而，目前传统的提升二次电池能量密度方法有提升涂布重量、提升极片压实密度、提升电压等，但上述方法在提升二次电池能量密度的同时降低了二次电池的安全性能，因此针对高能量密度的二次电池，如何保障其安全性能是电池行业亟需解决的问题。
发明内容
本申请实施例通过调整在二次电池中应用的隔膜组成和电解液中的成分以在某种程度上解决存在于现有技术的问题。
本申请实施例一方面提出一种二次电池，包括电解液和隔膜；隔膜包括聚烯烃基材以及设置在聚烯烃基材至少一个表面上的涂层，涂层包括无机颗粒。基于电解液总质量，电解液中含有：(I)含量为0.01质量％以上且2质量％以下的醚腈、(II)含量为0.01质量％以上且2质量％以下的丁二腈、(III)含量为25质量％以上且65质量％以下的丙酸酯、(IV)含量为0.01质量％以上且3质量％以下的含硼锂盐；上述醚腈、丁二腈与上述丙酸酯的合计含量为25.02质量％以上且67.9质量％以下，上述丁二腈与上述含硼锂盐的合计含量为0.02质量％以上且4.6质量％以下。发明人发现，隔膜基材上涂布无机颗粒可以提高电池的安全性，当电解液含有特定量的醚腈、丁二腈、丙酸酯以及含硼锂盐，能够在正极表面形成稳定的覆膜，从而不仅能够改善隔膜的耐热性，还显著提高二次电池的安全性能和耐振动特性。
在其中一些实施例中，无机颗粒包括铝元素、镁元素、钛元素、锆元素、铌元素、铟元素、钨元素、锡元素、锌元素或锑元素中的至少一种。进一步地，无机颗粒选自氧化铝、氢氧化铝、勃姆石、氧化镁、氢氧化镁、二氧化钛、二氧化锆、一氧化铌、二氧化铌、三氧化二铌、五氧化二铌、三氧化二铟、三氧化钨、二氧化锡、氧化锌或三氧化二锑中的至少一种。通过在隔膜的基材上涂布上述无机颗粒，可以明显提高电池的安全性。
在其中一些实施例中，醚腈包括乙二醇二(丙腈)醚、1,2,3-三(2-氰基乙氧基)丙烷、1,2,4-三(2-氰基乙氧基)丁烷、1,1,1-三(氰基乙氧基亚甲基)乙烷、1,1,1-三(氰基乙氧基亚甲基)丙烷、3-甲基-1,3,5-三(氰基乙氧基)戊烷、1,2,7-三(氰基乙氧基)庚烷、1,2,6-三(氰基乙氧基)己烷或1,2,5-三(氰基乙氧基)戊烷中的至少一种。通过在电解液中添加上述醚腈，可以抑制隔膜的聚烯烃基材在电解液中的溶胀。
在其中一些实施例中，丙酸酯包括丙酸甲酯、丙酸乙酯、丙酸丙酯或丙酸丁酯中的至少一种。通过在电解液中添加上述丙酸酯，可以抑制隔膜的聚烯烃基材在电解液中的溶胀。
在其中一些实施例中，含硼锂盐包括四氟硼酸锂[CAS:14283-07-9]、二氟草酸硼酸锂[CAS:409071-16-5]、双草酸硼酸锂[CAS:244761-29-3]、四氰基硼酸锂[CAS:294867-26-8]、四(三氟甲基)硼酸锂、(三氟甲基)三氟硼酸锂、双(三氟甲基)二氟硼酸锂[CAS:390750-38-6]、五氟乙基三氟硼酸锂[CAS:390750-43-3]、二氰基草酸硼酸锂[CAS:1390624-95-9]、双丙二酸根合硼酸锂[CAS:291298-96-9]、(2-氟代丙二酸根)合二氟硼酸锂[CAS:1604746-55-5]、丙二酸根草酸根合硼酸锂[CAS:383187-24-4]、二(水杨酸根合)硼酸锂[CAS:161589-07-7]、二(邻苯二酚根)合硼酸锂[CAS:156762-86-6]、甲氧基三氰基硼酸锂、乙氧基三氰基硼酸锂[CAS:1390624-92-6]、四甲氧基硼酸锂[CAS:6867-35-2]、四乙氧基硼酸锂[CAS:66350-36-5]、四(三氟甲氧基)硼酸锂[CAS:291541-83-8]、四(2,2,2-三氟乙氧基)硼酸锂[CAS:291541-84-9]、聚四(对苯二酚氧)硼酸锂、硫酸二(三氟硼酸)二锂[CAS:2295884-18-1]、二氟硼酸锂[CAS:288611-80-3]、甲烷二磺酸根合二氟硼酸锂[CAS:1630816-00-0]、二氟磷酰氧基三氟硼酸锂[CAS:1253288-53-7]、二(二氟磷酰氧基)二氟硼酸锂[CAS:1253288-56-0]或四(二氟磷酰氧基)硼酸锂[CAS:1253288-57-1]中的至少一种。在电解液中添加上述含硼锂盐，此时所形成覆膜的稳定性优异，电池性能得到进一步提升。作为含硼锂盐可以仅为1种，也可以为2种以上或3种以上。
在其中一些实施例中，基于电解液总质量，上述电解液包括含量为0.01质量％以上且1质量％以下的醚腈。通过调整电解液中醚腈的含量在上述范围内，可以进一步抑制隔膜的聚烯烃基材在电解液中的溶胀。
在其中一些实施例中，基于电解液总质量，上述电解液包括含量为0.4质量％以上且0.8质量％以下的醚腈。通过调整电解液中醚腈的含量在上述范围内，可以进一步抑制隔膜的聚烯烃基材在电解液中的溶胀。
在其中一些实施例中，基于电解液总质量，上述电解液包括含量为1.2质量％以上且1.8质量％以下的丁二腈。通过调整电解液中丁二腈的含量在上述范围内，可以改善隔膜的耐热性和抑制内部短路时发热。
在其中一些实施例中，基于电解液总质量，上述电解液包括含量为25质量％以上且65质量％以下的丙酸丙酯。向电解液中加入含量在上述范围内的丙酸丙酯，所形成覆膜的稳定性优异，电池性能得到进一步提升。
在其中一些实施例中，基于电解液总质量，上述电解液包括含量为25质量％以上且65质量％以下的丙酸乙酯。向电解液中加入含量在上述范围内的丙酸乙酯，所形成覆膜的稳定性优异，电池性能得到进一步提升。
在其中一些实施例中，上述电解液包括丙酸丙酯和丙酸乙酯。向电解液中加入丙酸丙酯和丙酸乙酯的混合物，所形成覆膜的稳定性更为优异，电池性能得到更进一步的提升。
在其中一些实施例中，上述电解液进一步包含其他腈基化合物，上述其他腈基化合物包括己二腈、顺式丁烯二腈、反式丁烯二腈、1,3,5-戊三甲腈、1,2,3-丙三甲腈、1,3,6-己三甲腈或1,2,6-己三甲腈中的至少一种；基于电解液总质量，上述其他腈基化合物的含量为0.1质量％以上且8质量％以下。其他腈基化合物可以提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述己二腈的含量为0.1质量％以上且1质量％以下。通过调整电解液中己二腈的含量在上述范围内，可以进一步提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述己二腈的含量为2.1质量％以上且4质量％以下。通过调整电解液中己二腈的含量在上述范围内，可以进一步提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述1,3,6-己三甲腈的含量为0.3质量％以上且0.9质量％以下。通过调整电解液中1,3,6-己三甲腈的含量在上述范围内，可以进一步提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述1,3,6-己三甲腈的含量为1.7质量％以上且3.1质量％以下。通过调整电解液中1,3,6-己三甲腈的含量在上述范围内，可以进一步提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
在其中一些实施例中，上述电解液进一步包括其他添加剂，上述其他添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、二氟磷酸锂、氟磺酸锂、1,3-丙烷磺酸内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、1,3-丙二醇环硫酸酯、氟苯、环己基苯、联苯、三(三甲基硅烷)磷酸酯或三(三甲基硅烷)硼酸酯中的至少一种；基于电解液总质量，上述其他添加剂的含量为0.01质量％以上且10质量％以下。其他添加剂可以抑制前述(I)～(IV)物质与正极表面的活性部分反应形成覆膜的在充放电过程种的分解再生，从而进一步降低正极电阻并改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述氟代碳酸乙烯酯的含量为0.01质量％以上且3质量％以下。通过调整电解液中氟代碳酸乙烯酯含量在上述范围内，可以改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述氟代碳酸乙烯酯的含量为4.1质量％以上且6.9质量％以下。通过调整电解液中氟代碳酸乙烯酯含量在上述范围内，可以改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述二氟磷酸锂的含量为0.01质量％以上且0.3质量％以下。通过调整电解液中二氟磷酸锂的含量在上述范围内，可以改善耐振动特性。
在其中一些实施例中，基于电解液总质量，上述硫酸乙烯酯的含量为0.01质量％以上且0.4质量％以下。通过调整电解液中硫酸乙烯酯的含量在上述范围内，可以改善耐振动特性。
本申请实施例另一方面提供一种电子装置，其包括本申请上述的二次电池。
基于本申请实施例的二次电池及电子装置，由于电解液中的醚腈与丙酸酯能够抑制聚烯烃基材在电解液中的溶胀，但是无机颗粒的存在会催化醚腈与丙酸酯在正极表面的分解，本申请实施例通过向电解液中添加特定量的丁二腈与含硼锂盐，使其恰好能够抑制醚腈与丙酸酯的分解，在正极表面形成稳定的覆膜，从而不仅能够改善隔膜的耐热性，还显著提高二次电池的安全性能和耐振动特性。
本申请实施例的额外层面及优点将部分地在后续说明中描述、显示、或是经由本申请实施例的实施而阐释。
具体实施方式
本申请的实施例将会被详细的描示在下文中。本申请的实施例不应该被解释为对本申请的限制。
二次电池
除非另外明确指明，本申请使用的下述术语具有下文指出的含义。
本申请通过使用特定的隔膜构成和电解液的组合，该设计不仅能够改善隔膜的耐热性，还显著提高二次电池的安全性能和耐振动特性。
在一个实施例中，本申请实施例第一方面提供了一种二次电池，其包括如下所述的电解液、隔膜、正极和负极。
I、电解液
本申请实施例二次电池中使用的电解液包括电解质和溶解该电解质的溶剂。在一些实施例中，电解液包括醚腈、丁二腈、丙酸酯、以及含硼锂盐。
二次电池中使用的隔膜包括聚烯烃基材以及基材上的涂层，涂层添加无机颗粒，能够明显提高隔膜的耐热性，从而提高电池的安全性。发明人意外发现，电解液中的醚腈与丙酸酯能够抑制聚烯烃基材在电解液中的溶胀，但是无机颗粒的存在会催化醚腈与丙酸酯在正极表面的分解，而特定量的丁二腈与含硼锂盐恰好能够抑制醚腈与丙酸酯的分解，在正极表面形成稳定的覆膜。通过使用该设计，不仅能够改善隔膜的耐热性，还显著提高二次电池的安全性能和耐振动特性。
在一些实施例中，醚腈包括乙二醇二(丙腈)醚、1,2,3-三(2-氰基乙氧基)丙烷、1,2,4-三(2-氰基乙氧基)丁烷、1,1,1-三(氰基乙氧基亚甲基)乙烷、1,1,1-三(氰基乙氧基亚甲基)丙烷、3-甲基-1,3,5-三(氰基乙氧基)戊烷、1,2,7-三(氰基乙氧基)庚烷、1,2,6-三(氰基乙氧基)己烷或1,2,5-三(氰基乙氧基)戊烷中的至少一种。由于所形成覆膜的稳定性优异，电池性能得到进一步提升。作为醚腈可以仅为1种，也可以为2种以上。优选乙二醇二(丙腈)醚、1,2,3-三(2-氰基乙氧基)丙烷或3-甲基-1,3,5-三(氰基乙氧基)戊烷。
具体而言，从改善隔膜的耐热性的观点出发，基于电解液的总质量，醚腈的含量为0.01质量％以上，优选为0.1质量％以上，更优选为0.2质量％以上，进一步优选为0.4质量％以上。此外，作为醚腈的质量含量的上限，从抑制内部短路时发热的观点出发，醚腈的质量含量为2质量％以下，优选为1.9质量％以下，更优选为1.6质量％以下，进一步优选为1.2质量％以下，特别优选为1质量％以下。当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，醚腈的含量设为a1质量％，a1为0.01、0.02、0.03、0.04、0.05、0.06、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2或在由上述任意两个数值所组成的范围内。例如0.01至0.09、0.05至0.1、0.1至0.8、0.5至1.2、0.7至1.9，当在上述范围内时，有助于进一步抑制内部短路时发热。
具体而言，从改善隔膜的耐热性的观点出发，基于电解液的总质量，丁二腈的质量含量为0.01质量％以上，优选为0.03质量％以上，更优选为0.05质量％以上，进一步优选为0.08质量％以上。此外，作为丁二腈的质量含量的上限，从抑制内部短路时发热的观点出发，丁二腈的质量含量为2质量％以下，优选为1.8质量％以下，更优选为1.6质量％以下，进一步优选为1.4质量％以下，特别优选为1.2质量％以下。当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，丁二腈的含量设为a2质量％，a2为0.01、0.02、0.03、0.04、0.05、0.06、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2或在由上述任意两个数值所组成的范围内。例如0.01至0.09、0.05至0.1、0.1至0.8、0.6至1.2、0.8至1.8，当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，丙酸酯包括丙酸甲酯、丙酸乙酯、丙酸丙酯或丙酸丁酯中的至少一种。作为丙酸酯可以仅为1种，也可以为2种以上。由于所形成覆膜的稳定性优异，电池性能得到进一步提升，优选丙酸乙酯、丙酸丙酯。
具体而言，从改善二次电池的耐振动特性的观点出发，基于电解液的总质量，丙酸酯的含量为25质量％以上，优选为28质量％以上，更优选为30质量％以上，进一步优选为35质量％以上。此外，作为丙酸酯的质量含量的上限，从抑制内部短路时发热的观点出发，丙酸酯的质量含量为65质量％以下，优选为60质量％以下，更优选为56质量％以下，进一步优选为53质量％以下，特别优选为48质量％以下。当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，丙酸酯的含量设为a3质量％，a3为25、28、29、30、32、33、35、39、40、42、45、48、50、53、56、60、63、65或在由上述任意两个数值所组成的范围内。例如25至28、28至36、33至45、40至53、50至65，当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，含硼锂盐包括四氟硼酸锂、二氟草酸硼酸锂、双草酸硼酸锂、四氰基硼酸锂、(3-甲基-2,4-戊二酮)合草酸硼酸酯(MOAB)、四(三氟甲基)硼酸锂、(三氟甲基)三氟硼酸锂、双(三氟甲基)二氟硼酸锂、五氟乙基三氟硼酸锂、二氰基草酸硼酸锂、双丙二酸根合硼酸锂、(2-氟代丙二酸根)合二氟硼酸锂、丙二酸根草酸根合硼酸锂、二(水杨酸根合)硼酸锂、二(邻苯二酚根)合硼酸锂、甲氧基三氰基硼酸锂、乙氧基三氰基硼酸锂、四甲氧基硼酸锂、四乙氧基硼酸锂、四(三氟甲氧基)硼酸锂、四(2,2,2-三氟乙氧基)硼酸锂、聚四(对苯二酚氧)硼酸锂、硫酸二(三氟硼酸)二锂、二氟硼酸锂、甲烷二磺酸根合二氟硼酸锂、二氟磷酰氧基三氟硼酸锂、二(二氟磷酰氧基)二氟硼酸锂或四(二氟磷酰氧基)硼酸锂中的至少一种，此时，所形成覆膜的稳定性优异，电池性能得到进一步提升。作为含硼锂盐可以仅为1种，也可以为2种以上或3种以上。
在一些实施例中，含硼锂盐优选包括四氟硼酸锂、双草酸硼酸锂(LiBOB)、二氟草酸硼酸锂(LiDFOB)或(3-甲基-2,4-戊二酮)合草酸硼酸酯(MOAB)中的至少一种。
具体而言，从改善二次电池的耐振动特性的观点出发，基于电解液的总质量，含硼锂盐的质量含量为0.01质量％以上，优选为0.02质量％以上，更优选为0.06质量％以上，进一步优选为0.1质量％以上。此外，作为含硼锂盐的质量含量的上限，从抑制内部短路时发热的观点出发，含硼锂盐的质量含量为3质量％以下，优选为2.3质量％以下，更优选为1.5质量％以下，进一步优选为1.1质量％以下，特别优选为0.7质量％以下。当在上述范围内时，有助于进一步抑制内部短路时发热。
在一些实施例中，含硼锂盐的含量设为a4质量％，a4为0.01、0.02、0.06、0.1、0.4、0.7、1.1、1.5、2.3、2.8、3或在由上述任意两个数值所组成的范围内，例如0.01至0.1、0.1至0.7、0.4至1.1、0.7至2.3、1.5至3。当在上述范围内时，有助于进一步抑制内部短路时发热。
进而，从抑制内部短路时发热的观点出发，基于电解液质量，(I)醚腈、(II)丁二腈与(III)丙酸酯的合计质量含量为25.02质量％以上，优选为30.3质量％以上。此外，作为(I)醚腈、(II)丁二腈与(III)丙酸酯的合计含量的上限，为67.9质量％以下，优选为58.3质量％以下。
在一些实施例中，(I)醚腈、(II)丁二腈与(III)丙酸酯的合计质量含量为a1+a2+a3质量％，a1+a2+a3为25.02、28.18、30.3、35.6、39.9、43.2、49.7、55、58.3、62.6、67.9或在由上述任意两个数值所组成的范围内。例如25.02至39.9、28.18至49.7、30.3至55、35.6至58.3、39.9至67.9，当在上述范围内时，有助于进一步抑制内部短路时发热。
进而，从抑制内部短路时发热的观点出发，基于电解液质量，(II)丁二腈与(IV)含硼锂盐的合计质量含量为0.02质量％以上，优选为0.12质量％以上。此外，作为(II)丁二腈与(IV)含硼锂盐的合计含量的上限，为4.6质量％以下，优选为3.9质量％以下。
在一些实施例中，(II)丁二腈与(IV)含硼锂盐的合计质量含量为a2+a4质量％，a2+a4为0.02、0.12、0.26、0.5、1、1.5、2.3、2.9、3.9、4.6或在由上述任意两个数值所组成的范围内。例如0.02至0.12、0.12至0.5、0.26至1.5、1至2.9、1.5至4.6，当在上述范围内时，有助于进一步抑制内部短路时发热。
此外，电解液还可以包括其他腈基化合物，发明人还意外发现，其他腈基化合物可以提高前述覆膜的稳定性，提高锂离子电荷传输，改善耐振动特性。
其他腈基化合物包括己二腈、顺式丁烯二腈、反式丁烯二腈、1,3,5-戊三甲腈、1,2,3-丙三甲腈、1,3,6-己三甲腈或1,2,6-己三甲腈中的至少一种。上述其他腈基化合物可以仅为1种，也可以为2种以上。
具体而言，从改善二次电池的耐振动特性的观点出发，基于电解液总质量，其他腈基化合物的含量为0.1质量％以上，优选为0.3质量％以上，更优选为0.6质量％以上，进一步优选为0.9质量％以上，特别优选为1.4质量％以上。此外，从抑制内短路放热的观点出发，作为其他腈基化合物的含量的上限，其他腈基化合物的含量为8质量％以下，优选为7.9质量％以下，更优选为7.1质量％以下，进一步优选为6.2质量％以下，特别优选为5.3质量％以下。
在一些实施例中，其他腈基化合物的总含量为b质量％，b为0.1、0.3、0.35、0.4、0.45、0.5、0.6、0.7、0.8、0.9、1、1.4、1.5、2、2.5、3、3.1、3.6、3.9、4、4.6、5.3、6.2、7.1、7.9、8或在由上述任意两个数值所组成的范围内。例如0.1至7.1、0.3至5.3、0.6至4.6、0.9至3.1、0.4至2、0.45至3.6、0.8至2.5、1.4至3.9、2.5至8、0.9至6.2、0.45至5.3、0.6至1.4，当在上述范围内时，有助于进一步改善改善二次电池的耐振动特性。
此外，电解液还可以包括其他添加剂，发明人还意外发现，其他添加剂可以抑制前述(I)～(IV)物质与正极表面的活性部分反应形成覆膜的在充放电过程种的分解再生，从而进一步降低正极电阻并改善耐振动特性。
其他添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、二氟磷酸锂、氟磺酸锂、1,3-丙烷磺酸内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、1,3-丙二醇环硫酸酯、氟苯、环己基苯、联苯、三(三甲基硅烷)磷酸酯或三(三甲基硅烷)硼酸酯中的至少一种。上述其他添加剂可以仅为1种，也可以为2种以上。
具体而言，从改善耐振动特性的观点出发，基于电解液总质量，其他添加剂的含量为0.01质量％以上，优选其他添加剂的含量为0.1质量％以上，优选为1.6质量％以上，更优选为2.8质量％以上。
此外，从改善耐振动特性的观点出发，其他添加剂的含量为10质量％以下，优选为9.7质量％以下，更优选为8.2质量％以下，进一步优选为7.1质量％以下，特别优选为6.7质量％以下。
在一些实施例中，其他添加剂总含量为c质量％，c为0.01、0.03、0.1、0.3、0.35、0.4、0.45、0.5、0.6、0.7、0.8、0.9、1、1.5、1.6、2、2.5、2.9、3、3.5、3.9、4、4.5、5、5.7、6、6.5、7.1、7.5、8.2、8.6、9、9.3、9.7、10或在由上述任意两个数值所组成的范围内。例如0.3至18.2、0.45至7.5、0.6至9.7、5.5至9.7、6至8.6、2.8至6.5、1至6.5、0.7至7.1、1.5至9.3、0.45至3.9、0.7至4.5，当在上述范围内时，有助于进一步改善耐振动特性。
本申请电解液中使用的锂盐包括六氟磷酸锂，基于电解液总质量，六氟磷酸锂的含量为9～15质量％，优选为9～13质量％，更优选为9～12质量％。通过设为上述含量范围，可以更平衡地发挥改善高温和低温特性的作用。
本申请的电解液还可以进一步包含现有技术中已知的任何可作为电解液的溶剂的非水溶剂。例如链状碳酸酯、环状羧酸酯、链状羧酸酯、环状醚、链状醚。优选链状羧酸酯，如乙酸乙酯、氟代乙酸乙酯。
II、隔膜
为了防止短路，在正极与负极之间通常设置有隔离膜。这种情况下，本申请的电解液通常渗入该隔离膜而使用。
在一些实施例中，从改善隔膜的耐热性的观点出发，隔膜包括聚烯烃基材以及基材上的涂层，涂层包括无机颗粒。
在一些实施例中，聚烯烃为聚乙烯或聚丙烯。隔离膜还可为上述材料层积而成的材料，其实例包括，但不限于，按照聚丙烯、聚乙烯、聚丙烯的顺序层积而成的三层隔离膜等。
具体而言，无机颗粒中的金属元素包括铝元素、镁元素、钛元素、锆元素、铌元素、铟元素、钨元素、锡元素、锌元素或锑中的至少一种。例如，无机颗粒选自氧化铝、氢氧化铝、勃姆石、氧化镁、氢氧化镁、二氧化钛、二氧化锆、一氧化铌、二氧化铌、三氧化二铌、五氧化二铌、三氧化二铟、三氧化钨、二氧化锡、氧化锌或三氧化二锑中的至少一种。
隔离膜的形态可为薄膜形态，其实例包括，但不限于，无纺布、织布、微多孔性膜等。在薄膜形态中，隔离膜的孔径(直径)为0.01μm至1μm，厚度为5μm至50μm。除了上述独立的薄膜状隔离膜以外，还可以使用下述隔离膜：通过使用树脂类的粘合剂在正极和/或负极的表面形成含有上述无机物颗粒的复合多孔层而形成的隔离膜，例如，将氟树脂作为粘合剂使90％粒径(Dv90)小于1μm的氧化铝颗粒在正极的两面形成多孔层而形成的隔离膜。
隔离膜的厚度是任意的。在一些实施例中，隔离膜的厚度为大于1μm、大于5μm或大于8μm。在一些实施例中，隔离膜的厚度为小于50μm、小于40μm或小于30μm。当隔离膜的厚度在上述范围内时，则可以确保绝缘性和机械强度，并可以确保二次电池的倍率特性和能量密度。
III、正极
正极包括正极集流体和设置在正极集流体的表面上的正极合剂层。
正极合剂层包含正极活性物质，正极合剂层可以是一层或多层。正极活性物质为任何能够可逆地嵌入和脱嵌锂离子的物质。
例如，作为二次电池用正极活性物质，使用含有选自由钴、锰、及镍组成的组中的1种或2种以上的与锂的复合金属氧化物、或包含选自铁、钴、镍及锰中的一种或两种以上的含锂的橄榄石型磷酸盐。这些正极活性物质可以单独使用1种或将2种以上组合使用。
作为这样的锂复合金属氧化物，可适宜列举出例如选自LiCoO2、LiMn2O4、LiNiO2、LiCo1-xNixO2(0.01<x<1)、LiNixMnyCozO2(x+y+z＝1)、Li2MnO3与LiMO2(M为Co、Ni、Mn、Fe等过渡金属)的固溶体、LiNi1/2Mn3/2O4、LiFePO4、LiMnPO4、及LiMn1-xFexPO4(0.01<x<1)中的1种以上，更优选为2种以上。这些与锂的复合金属氧化物或含锂的橄榄石型磷酸盐的一部分可以以其他元素取代，也可以将钴、镍、锰、铁的一部分以选自Co、Mn、Ni、Mg、Al、B、Ti、V、Nb、Cu、Zn、Mo、Ca、Sr、W及Zr中的一种或两种以上的元素取代、或者以含有这些其他元素的化合物或碳材料被覆。
作为充电时的电压，从高电压化的观点出发，正极电位优选为4.4V(vs.Li/Li+)以上，更优选为4.5V(vs.Li/Li+)以上，特别优选为4.6V(vs.Li/Li+)以上。
正极的导电剂只要是不引起化学变化的电子传导材料则没有特别限制。可列举出例如天然石墨(鳞片状石墨等)、人造石墨等石墨、乙炔黑、科琴黑、槽法碳黑、炉黑、灯黑、或热裂法碳黑等炭黑等。此外，也可以将石墨与炭黑适当混合使用。导电剂在正极合剂中的质量含量优选为1～10质量％，特别优选为1.5～5质量％。
正极可以按照如下方法制作：将上述的正极活性物质与乙炔黑、炭黑等导电剂、及聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、苯乙烯与丁二烯的共聚物、羧甲基纤维素等粘结剂混合，在其中加入1-甲基-2-吡咯烷酮等高沸点溶剂并进行混炼而制成正极合剂浆料后，将其涂布于正极集流体的铝箔等上，干燥，加压而形成正极合剂层，从而制作。
正极的除正极集流体以外的部分的密度通常为3.5g/cm3以上，为了进一步提高电池的容量，优选为3.8g/cm3以上，更优选为4g/cm3以上，进一步优选为4.1g/cm3以上。另外，作为其上限，优选为4.6g/cm3以下。
正极集流体的种类没有特别限制，其可为任何已知适于用作正极集流体的材质。正极集流体的实例可包括，但不限于，铝、不锈钢、镍镀层、钛、钽等金属材料；碳布、碳纸等碳材料。在一些实施例中，正极集流体为金属材料。在一些实施例中，正极集流体为铝。
为了降低正极集流体和正极合剂层的电子接触电阻，正极集流体的表面可包括导电助剂或导电涂层。导电助剂的实例可包括，但不限于，碳和金、铂、银等贵金属类。导电涂层的实例可包括含有无机氧化物、导电剂、粘结剂的混合物层。
正极可以通过在正极集流体上形成含有正极活性物质和粘结剂的正极合剂层来制作。使用正极活性物质的正极的制造可以通过常规方法来进行，即，将正极活性物质和粘结剂、以及根据需要的导电材料和增稠剂等进行干式混合，制成片状，将所得到的片状物压接至正极集流体上；或者将这些材料溶解或分散于液体介质中而制成浆料，将该浆料涂布到正极集流体上并进行干燥，从而在正极集流体上形成正极合剂层，由此可以得到正极。
IV、负极
负极包括负极集流体和设置在负极集流体表面上的负极合剂层，负极合剂层包含负极活性物质。在一些实施例中，负极活性物质的可充电容量大于正极活性物质的放电容量，以防止在充电期间锂金属无意地析出在负极上。
此外，作为负极活性物质，没有特别限定，可举出碳系负极活性物质、金属系负极活性物质以及将它们组合的负极活性物质等。
碳系负极活性物质在此，碳系负极活性物质是指可以插入锂的以碳为主骨架的活性物质，作为碳系负极活性物质，可举出例如碳质材料和石墨质材料。
作为碳质材料，可举出例如：易石墨化碳、以玻璃状碳为代表的具有类似无定形结构的难石墨化碳等。在此，作为易石墨化碳，可举出例如：从石油或煤中得到的以焦油沥青为原料的碳材料。当举出具体例子时，可举出焦炭、中间相碳微球(MCMB)、中间相沥青系碳纤维和热解气相生长碳纤维等。此外，作为难石墨化碳，可举出例如：酚醛树脂烧结体、聚丙烯腈系碳纤维、准各向同性碳、糠醇树脂烧结体(PFA)、硬碳等。
进而，作为石墨质材料，可举出例如天然石墨、人造石墨等。其中，作为人造石墨，可举出例如：将包含易石墨性碳的碳主要在2800℃以上进行热处理而成的人造石墨、将MCMB在2000℃以上进行热处理而成的石墨性MCMB、将中间相沥青系碳纤维在2000℃以上进行热处理而成的石墨性中间相沥青系碳纤维等。另外，在本申请中，作为碳系负极活性物质，可以使用其表面的至少一部分被无定形碳被覆而成的天然石墨(无定形包覆天然石墨)。
此外，金属系负极活性物质是包含金属的活性物质，通常是指在结构中包含能够插入锂或与锂合金化的元素、插入锂或与锂合金化的情况下的每单位质量的理论电流容量为500mAh/g以上的活性物质。作为金属系负极活性物质，可使用例如：锂金属、可形成锂合金的单质金属(例如Ag、Al、Ba、Bi、Cu、Ga、Ge、In、Ni、P、Pb、Sb、Si、Sn、Sr、Zn、Ti等)及其合金、以及它们的氧化物、硫化物、氮化物、硅化物、碳化物、磷化物等。在它们中，作为金属系负极活性物质，优选包含硅的活性物质(硅系负极活性物质)。这是因为，通过使用硅系负极活性物质能够使锂离子二次电池高容量化。
作为硅系负极活性物质，可举出例如：硅(Si)、包含硅的合金、硅氧化物、含硅材料被导电性碳被覆或复合化而成的含硅材料与导电性碳的复合物。
从电池容量提高的观点出发，优选硅碳材料，例如多孔碳负载硅的复合材料。
另外，负极活性物质可以单独使用一种，也可以以任意的比率组合使用两种以上。
负极合剂层还可包括负极粘合剂。负极粘合剂可提高负极活性物质颗粒彼此间的结合和负极活性物质与集流体的结合。负极粘合剂的种类没有特别限制，只要是对于电解液或电极制造时使用的溶剂稳定的材料即可。在一些实施例中，负极粘合剂包括树脂粘合剂。树脂粘合剂的实例包括，但不限于，氟树脂、聚丙烯腈(PAN)、聚酰亚胺树脂、丙烯酸系树脂、聚烯烃树脂等。当使用水系溶剂制备负极合剂浆料时，负极粘合剂包括，但不限于，羧甲基纤维素(CMC)或其盐、苯乙烯-丁二烯橡胶(SBR)、聚丙烯酸(PAA)或其盐、聚乙烯醇等。
作为保持负极活性物质的负极集流体，可以任意使用公知的集流体。负极集流体的实例包括，但不限于，铜、镍、不锈钢、镀镍钢等金属材料。在一些实施例中，负极集流体为铜。
负极可以通过以下方法制备：在负极集流体上涂布包含负极活性物质、树脂粘合剂等的负极合剂浆料，干燥后，进行压延而在负极集流体的两面形成负极合剂层，由此可以得到负极。
电子装置
本申请实施例第二方面提供了一种电子装置，其包括根据本申请所述的二次电池。
本申请的二次电池的用途没有特别限定，其可用于现有技术中已知的任何电子装置。在一些实施例中，本申请的二次电池可用于，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
下面结合具体的实施例说明二次电池的制备，本领域的技术人员将理解，本申请中描述的制备方法仅是实例，其他任何合适的制备方法均在本申请的范围内。
实施例 二次电池的制备及性能测试
以下，示出本申请的非水电解液的实施例，但本申请并不限定于这些实施例。
1.正极制作
将正极活性材料钴酸锂(97质量％)和乙炔黑(1.5质量％)混合，添加到预先使聚丙烯腈(1.5质量％)溶解于1-甲基-2-吡咯烷酮中而得到的溶液中并进行混合，制备正极合剂膏糊。将该正极合剂膏糊涂布于铝箔(集流体)上的一面上，干燥、加压处理后剪切成规定的大小，制作正极。
2.负极制作
将负极活性材料人造石墨和硅碳(质量比90：10，总共占96质量％)、丁苯橡胶(2质量％)混合，添加到预先使羧甲基纤维素锂(2质量％)溶解于去离子水中而得到的溶液中并进行混合，制备负极合剂膏糊。将该负极合剂膏糊涂布于铜箔(集流体)上的一面上，干燥、加压处理后剪切成规定的大小，制作负极。
3.隔膜制作
将5μm的聚乙烯多孔膜作为隔膜基材；将去离子水和表1-1无机颗粒加入双行星搅拌机中，在40℃下高速分散1小时；之后加入粘结剂羧甲基纤维素钠，在室温下低速搅拌1小时，得到固含量为3％的无机颗粒浆料，其中无机颗粒占浆料总重量的2％，羧甲基纤维素钠占浆料总重量的1％。然后采用印刷涂覆的方式将无机颗粒浆料涂覆在5μm的聚乙烯多孔膜的其中一个面上，干燥，得到隔膜，无机颗粒层厚度1.5μm。
4.电解液制作
将作为支持电解质的LiPF6溶解在包含(I)醚腈、(II)丁二腈、(III)丙酸酯、(IV)含硼锂盐、其他腈基化合物、其他添加剂的溶液中。基于电解液总质量100质量份，(I)～(IV)、其他腈基化合物、其他添加剂的含量和组分如表1-2和表1-3所示，LiPF6的含量为14％，其余为碳酸乙烯酯和碳酸丙烯酯(质量比1.2：1)。
5.电池制作
将如上制作的正极和负极各自与导线连接。经由上述隔膜进行层叠卷绕。然后，将卷绕体与3.2g的电解液一起收纳在铝制层压壳体内。将壳体的开口部进行热封口，并通过化成、容量等步骤，制成二次电池。该二次电池为宽35mm、高48mm、厚5mm的袋形二次电池。
表1-1隔膜种类
表1-2电解液种类


*上表中：a1代表(I)醚腈的含量，a2代表(II)丁二腈的含量，a3代表(III)丙
酸酯的含量，a4代表(IV)含硼锂盐的总含量，b代表其他腈基化合物的总含量，c代表其他添加剂的总含量。
表1-3电解液组分代码
6.测试方法
按照表2将上述步骤中采用编号为电解液1至35制备的电解液与编号为隔膜1至12制备的隔膜相匹配，分别制作二次电池，得到实施例1至35；将上述步骤中采用编号为电解液36至43制备的电解液与编号为隔膜1制备的隔膜相匹配，分别制作二次电池，得到对比例1至8；将上述步骤中采用编号为电解液43制备的电解液与编号为隔膜13制备的隔膜相匹配，制作二次电池得到对比例9，将上述步骤中采用编号为电解液1制备的电解液与编号为隔膜13制备的隔膜相匹配，制作二次电池得到对比例10。
将上述实施例1至35、对比例1至9制得的二次电池采用如下方法分别测试其耐热、安全、耐振动性能，测试结果见表2。
6.1电解液中的耐热收缩性测试
将实施例和对比例中得到的负极和隔膜切成宽50mm×长50mm的切片。将负极的切片和隔膜的切片重叠，使用辊式压制机，以负载10kN/m、温度80℃的条件进行压制，从而得到负极的切片和隔膜的切片一体化的试验片。
将试验片及上述规定的电解液密封在层压包材中，得到样品。电解液的量设为相对于负极容量为4g/Ah的量。将得到的样品在140℃加热1小时后，将层压包材开封，取出试验片。测定试验片上的隔膜的尺寸。根据加热前的隔膜的面积A0和加热后的隔膜的面积A1，求出隔膜的收缩率((A0-A1)/A0)×100(％)。
A：收缩率小于0.5％。B：收缩率为0.5％以上且小于1.0％。C：收缩率为1.0％以上且小于5.0％。D：收缩率为5.0％以上且小于10.0％。E：收缩率为10.0％以上。
6.2内部短路时的放热抑制(强制内部短路试验)安全测试
将实施例、比较例中制作的二次电池以0.2C的恒流法进行CC-CV充电(上限电池单元电压为4.6V)，以0.2C的恒流法进行CC放电至3.0V。该0.2C的充放电重复实施3次。然后，在25℃的气氛下，以0.2C的充电倍率通过恒压恒流(CC-CV)的方式充电至4.6V(终止条件：0.02C)。然后，在二次电池的中央附近，通过将直径3mm、长度10cm的铁制的钉子以5m/分钟的速度贯穿，强制地使其短路。对以同样的操作分别制作的5个二次电池进行该强制的短路，根据没有产生破裂也没有着火的试验体的数量，按照下述的基准进行评价。没有产生破裂也没有着火的试验体的数量越多，表示二次电池在内部短路时的放热抑制性能越优异。
A：没有产生破裂也没有着火的试验体的数量为4个或5个。
B：没有产生破裂也没有着火的试验体的数量为3个。
C：没有产生破裂也没有着火的试验体的数量为2个。
D：没有产生破裂也没有着火的试验体的数量为1个或0个。
6.3振动试验后的容量保持率测试
对于实施例和比较例中得到的二次电池，进行重复5次下述循环的充放电试验，上述循环为在60℃通过充电倍率0.1C的恒电流法，进行充电至4.6V后，以放电倍率0.1C放电至3.0V。将第5次的放电容量作为初始容量。接着，将该二次电池固定在内径200mm的筛上，用罗太普(Ro-tap)型筛振荡机振动1小时后，进行与上述相同的充放电试验，测定振动试验后的放电容量。求出振动试验后的放电容量相对于初始放电容量的比例作为容量保持率。该值越大，则表示由振动试验引起的容量减少越少。
A：容量保持率为95％以上。
B：容量保持率为90％以上且小于95％。
C：容量保持率为85％以上且小于90％。
D：容量保持率小于85％。
表2

7.测试结果
由上表2可知，实施例1至35中：当隔膜包括聚烯烃基材以及隔膜基材上的涂层包括无机颗粒时，电解液含有本申请提供的特定量的醚腈、丁二腈、丙酸酯、以及含硼锂盐，将上述电解液中的醚腈、丁二腈与丙酸酯的合计含量设定为特定的范围，将丁二腈与含硼锂盐的合计含量设定为特定的范围。通过使用该设计，不仅能够改善隔膜的耐热性，还显著提高二次电池的安全性能和耐振动特性。
特别地，电解液中采用丙酸丙酯和丙酸乙酯混合使用的方式时可以显著提高耐热性。进一步地，当电解液中醚腈、丁二腈、丙酸酯以及含硼锂盐含量在本申请提供的上述范围内，所制得的二次电池的隔膜具有良好的耐热性，还显著提高了二次电池的安全性能和耐振动特性。
特别地，当电解液还包含其他腈基化合物，可以降低覆膜的阻抗，进一步提高二次电池的安全性能和耐振动特性。进一步地，电解液中其他腈基化合物的质量含量满足上述范围时，可以进一步降低覆膜的阻抗，改善耐振动性能。
特别地，当电解液还包含其他添加剂，发明人还意外发现，其他添加剂可以抑制覆膜的在充放电过程中的分解再生，从而进一步提高二次电池的安全性能和耐振动特性。尤其是，电解液中其他添加剂的质量含量满足上述范围，可以进一步抑制覆膜的在充放电过程中的分解再生，从而显著提高二次电池的安全性能和耐振动特性。
整个说明书中对“实施例”、“部分实施例”、“一个实施例”、“另一举例”、“举例”、“具体举例”或“部分举例”的引用，其所代表的意思是在本申请中的至少一个实施例或举例包含了该实施例或举例中所描述的特定特征、结构、材料或特性。因此，在整个说明书中的各处所出现的描述，例如：“在一些实施例中”、“在实施例中”、“在一个实施例中”、“在另一个举例中”，“在一个举例中”、“在特定举例中”或“举例”，其不必然是引用本申请中的相同的实施例或示例。此外，本申请中的特定特征、结构、材料或特性可以以任何合适的方式在一个或多个实施例或举例中结合。
尽管已经演示和描述了说明性实施例，本领域技术人员应该理解上述实施例不能被解释为对本申请的限制，并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变，替代和修改。

Claims (23)

  1. 一种二次电池，其特征在于，包括正极、负极、电解液和隔膜；
    所述隔膜包括聚烯烃基材以及设置在所述聚烯烃基材至少一个表面上的涂层，所述涂层包括无机颗粒；
    基于电解液总质量，所述电解液中含有：
    (I)含量为0.01质量％以上且2质量％以下的醚腈、
    (II)含量为0.01质量％以上且2质量％以下的丁二腈、
    (III)含量为25质量％以上且65质量％以下的丙酸酯、
    (IV)含量为0.01质量％以上且3质量％以下的含硼锂盐；
    所述醚腈、所述丁二腈与所述丙酸酯的合计含量为25.02质量％以上且67.9质量％以下，所述丁二腈与所述含硼锂盐的合计含量为0.02质量％以上且4.6质量％以下。
  2. 根据权利要求1所述的二次电池，其特征在于，所述无机颗粒包括铝元素、镁元素、钛元素、锆元素、铌元素、铟元素、钨元素、锡元素、锌元素或锑元素中的至少一种。
  3. 根据权利要求1所述的二次电池，其特征在于，所述无机颗粒选自氧化铝、氢氧化铝、勃姆石、氧化镁、氢氧化镁、二氧化钛、二氧化锆、一氧化铌、二氧化铌、三氧化二铌、五氧化二铌、三氧化二铟、三氧化钨、二氧化锡、氧化锌或三氧化二锑中的至少一种。
  4. 根据权利要求1所述的二次电池，其特征在于，所述醚腈包括乙二醇二(丙腈)醚、1,2,3-三(2-氰基乙氧基)丙烷、1,2,4-三(2-氰基乙氧基)丁烷、1,1,1-三(氰基乙氧基亚甲基)乙烷、1,1,1-三(氰基乙氧基亚甲基)丙烷、3-甲基-1,3,5-三(氰基乙氧基)戊烷、1,2,7-三(氰基乙氧基)庚烷、1,2,6-三(氰基乙氧基)己烷或1,2,5-三(氰基乙氧基)戊烷中的至少一种。
  5. 根据权利要求1所述的二次电池，其特征在于，所述丙酸酯包括丙酸甲酯、丙酸乙酯、丙酸丙酯或丙酸丁酯中的至少一种。
  6. 根据权利要求1所述的二次电池，其特征在于，所述含硼锂盐包括四氟硼酸锂、二氟草酸硼酸锂、双草酸硼酸锂、四氰基硼酸锂、四(三氟甲基)硼酸锂、(三氟甲基)三氟硼酸锂、双(三氟甲基)二氟硼酸锂、五氟乙基三氟硼酸锂、二氰基草酸硼酸锂、双丙二酸根合硼酸锂、(2-氟代丙二酸根)合二氟硼酸锂、丙二酸根草酸根合硼酸锂、二(水杨酸根合)硼酸锂、二(邻苯二酚根)合硼酸锂、甲氧基三氰基硼酸锂、乙氧基三氰基硼酸锂、四甲氧基硼酸锂、四乙氧基硼酸锂、四(三氟甲氧基)硼酸锂、四(2,2,2-三氟乙氧基)硼酸锂、聚四(对苯二酚氧)硼酸锂、硫酸二(三氟硼酸)二锂、二氟硼酸锂、甲烷二磺酸根合二氟硼酸锂、二氟磷酰氧基三氟硼酸锂、二(二氟磷酰氧基)二氟硼酸锂或四(二氟磷酰氧基)硼酸锂中的至少一种。
  7. 根据权利要求1或2所述的二次电池，其特征在于，基于电解液总质量，所述电解液包括含量为0.01质量％以上且1质量％以下的醚腈。
  8. 根据权利要求1或2所述的二次电池，其特征在于，基于电解液总质量，所述电解液包括含量为0.4质量％以上且0.8质量％以下的醚腈。
  9. 根据权利要求1或2所述的二次电池，其特征在于，基于电解液总质量，所述电解液包括含量为1.2质量％以上且1.8质量％以下的丁二腈。
  10. 根据权利要求1或2所述的二次电池，其特征在于，基于电解液总质量，所述电解液包括含量为25质量％以上且65质量％以下的丙酸丙酯。
  11. 根据权利要求1或2所述的二次电池，其特征在于，基于电解液总质量，所述电解液包括含量为25质量％以上且65质量％以下的丙酸乙酯。
  12. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液包括丙酸丙酯和丙酸乙酯。
  13. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液进一步包含其他腈基化合物，所述其他腈基化合物包括己二腈、顺式丁烯二腈、反式丁烯二腈、1,3,5-戊三甲腈、1,2,3-丙三甲腈、1,3,6-己三甲腈或1,2,6-己三甲腈中的至少一种；
    基于电解液总质量，所述其他腈基化合物的含量为0.1质量％以上且8质量％以下。
  14. 根据权利要求13所述的二次电池，其特征在于，所述电解液包括己二腈，基于电解液总质量，所述己二腈的含量为0.1质量％以上且1质量％以下。
  15. 根据权利要求13所述的二次电池，其特征在于，所述电解液包括己二腈，基于电解液总质量，所述己二腈的含量为2.1质量％以上且4质量％以下。
  16. 根据权利要求13所述的二次电池，其特征在于，所述电解液包括1,3,6-己三甲腈，基于电解液总质量，所述1,3,6-己三甲腈的含量为0.3质量％以上且0.9质量％以下。
  17. 根据权利要求13所述的二次电池，其特征在于，所述电解液包括1,3,6-己三甲腈，基于电解液总质量，所述1,3,6-己三甲腈的含量为1.7质量％以上且3.1质量％以下。
  18. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液进一步包括其他添加剂，所述其他添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、二氟磷酸锂、氟磺酸锂、1,3-丙烷磺酸内酯、1,3-丙烯磺酸内酯、硫酸乙烯酯、1,3-丙二醇环硫酸酯、氟苯、环己基苯、联苯、三(三甲基硅烷)磷酸酯或三(三甲基硅烷)硼酸酯中的至少一种；
    基于电解液总质量，所述其他添加剂的含量为0.01质量％以上且10质量％以下。
  19. 根据权利要求18所述的二次电池，其特征在于，所述电解液包括氟代碳酸乙烯酯，基于电解液总质量，所述氟代碳酸乙烯酯的含量为0.01质量％以上且3质量％以下。
  20. 根据权利要求18所述的二次电池，其特征在于，所述电解液包括氟代碳酸乙烯酯，基于电解液总质量，所述氟代碳酸乙烯酯的含量为4.1质量％以上且6.9质量％以下。
  21. 根据权利要求18所述的二次电池，其特征在于，所述电解液包括二氟磷酸锂，基于电解液总质量，所述二氟磷酸锂的含量为0.01质量％以上且0.3质量％以下。
  22. 根据权利要求18所述的二次电池，其特征在于，所述电解液包括硫酸乙烯酯，基于电解液总质量，所述硫酸乙烯酯的含量为0.01质量％以上且0.4质量％以下。
  23. 一种电子装置，其特征在于，包括根据权利要求1至22中任一项所述的二次电池。
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