WO2024255699A1 - 二次电池和装置 - Google Patents

二次电池和装置 Download PDF

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WO2024255699A1
WO2024255699A1 PCT/CN2024/098028 CN2024098028W WO2024255699A1 WO 2024255699 A1 WO2024255699 A1 WO 2024255699A1 CN 2024098028 W CN2024098028 W CN 2024098028W WO 2024255699 A1 WO2024255699 A1 WO 2024255699A1
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negative electrode
secondary battery
lithium
formula
active material
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French (fr)
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钱伟瑞
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NIO Technology Anhui Co Ltd
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NIO Technology Anhui Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of energy storage, and in particular to a secondary battery and a device.
  • Lithium-ion batteries have been widely used in our daily life and high-tech fields. In order to meet people's needs, lithium-ion batteries need to be developed in the direction of higher energy density, greater safety, and longer life. However, during the battery cycle, the positive and negative electrodes of the battery are prone to side reactions with the electrolyte, which will lead to the attenuation of battery capacity and a significant reduction in cycle life on the one hand, and the generation of gas and expansion of the battery volume on the other hand, thereby reducing the safety of the battery.
  • the present application provides a secondary battery and related devices.
  • the secondary battery of the present application improves its cycle performance, storage performance and safety performance at high temperature while taking into account the low impedance of the secondary battery by controlling the content of phosphorus atoms and sulfur atoms in the solid electrolyte interface film (SEI film) formed on the surface of the negative electrode active material layer.
  • SEI film solid electrolyte interface film
  • a first aspect of the present application provides a secondary battery, which includes a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte includes a sulfur-containing additive and a phosphorus-containing additive; the negative electrode includes a negative electrode active material layer and a solid electrolyte interface film located on the surface of the negative electrode active material layer, and tested by an X-ray photoelectron spectrometer, the atomic percentage of sulfur in the solid electrolyte interface film is S%, and the atomic percentage of phosphorus is P%, wherein 2.5 ⁇ 2S+P/5 ⁇ 10.
  • a second aspect of the present application provides a device, which includes the secondary battery described in the first aspect.
  • the secondary battery of the present application controls the content of sulfur atoms and phosphorus atoms in the solid electrolyte interface film SEI formed on the surface of the negative electrode active material layer, making the SEI film more compact and stable, which can effectively slow down the erosion of the electrolyte on the electrode material, improve the interface lithium ion transmission capacity, reduce the interface impedance, and thus reduce the impedance of the secondary battery.
  • the specific sulfur atoms The SEI film with a coordinated phosphorus atom content can improve the cycle performance and safety performance of lithium-ion secondary batteries, especially the cycle performance and storage performance at high temperatures.
  • any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, and any upper limit can be combined with any other upper limit to form an undefined range.
  • each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an undefined range.
  • a list of items connected by the term "at least one of” or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single component or multiple components.
  • Item B may contain a single component or multiple components.
  • Item C may contain a single component or multiple components.
  • the secondary battery provided by the present application includes a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte includes a sulfur-containing additive and a phosphorus-containing additive; the negative electrode includes a negative electrode active material layer and a solid electrolyte interface film located on the surface of the negative electrode active material layer.
  • the atomic percentage of sulfur in the solid electrolyte interface film is S%, and the atomic percentage of phosphorus is P%, measured by an X-ray photoelectron spectrometer, wherein 2.5 ⁇ 2S+P/5 ⁇ 10.
  • the sulfur atoms from the sulfur-containing additives in the negative electrode solid electrolyte interface film SEI can improve the high temperature stability of the SEI film, thereby improving the high temperature storage performance and high temperature cycle performance of the negative electrode.
  • sulfur is a poor conductor of lithium ions and electrons, when its content is high, it will affect the increase of battery impedance, increase battery polarization, and accelerate the capacity decay of the battery during the cycle.
  • the phosphorus atoms from the phosphorus -containing additives in the SEI can improve the conductivity of lithium ions and electrons, reduce interfacial impedance, and thus reduce the impedance of secondary batteries, but the high-temperature performance of phosphorus-containing additives is poor.
  • the atomic percentage of sulfur refers to the molar percentage of sulfur atoms in the solid electrolyte membrane to all atoms excluding hydrogen atoms.
  • the atomic percentage of phosphorus refers to the molar percentage of phosphorus atoms in the solid electrolyte membrane to all atoms excluding hydrogen atoms.
  • 2S+P/5 is 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.2, 7.5, 7.8, 8, 8.2, 8.5, 8.8, 9, 9.2, 9.5, 9.8, 10 or a range consisting of any two of these values.
  • 2S+P/5 is too high, the content of sulfur and phosphorus in the SEI film is large, which increases the active sites on the negative electrode surface, consumes more lithium, and cannot inhibit the continuous decomposition of the electrolyte, thereby affecting the cycle performance of the battery.
  • 2S+P/5 is too low, there are too few active sites on the negative electrode surface, resulting in poor electrode interface kinetics and increased polarization, which in turn affects the cycle performance of the battery.
  • 0.1 ⁇ S ⁇ 8 In some embodiments, 0.1 ⁇ S ⁇ 8. In some embodiments, S is 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.2, 7.5, 7.8, 8 or a range consisting of any two of these values. In some embodiments, 0.5 ⁇ S ⁇ 5. In other embodiments, 1 ⁇ S ⁇ 4.
  • 0.1 ⁇ P ⁇ 15 In some embodiments, P is 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8, 6, 6.2, 6.5, 6.8, 7, 7.2, 7.5, 7.8, 8, 8.2, 8.5, 8.8, 9, 9.2, 9.5, 9.8, 10, 10.2, 10.5, 10.8, 11, 11.2, 11.5, 11.8, 12, 12.2, 12.5, 12.8, 13, 13.2, 13.5, 13.8, 14, 14.2, 14.5, 14.8, 15, or a range consisting of any two of these values. In some embodiments, 0.5 ⁇ P ⁇ 10. In other embodiments, 2 ⁇ P ⁇ 10.
  • the phosphorus-containing additive includes at least one selected from lithium phosphate salts.
  • the phosphorus-containing additive can improve the composition and structure of the interface film, reduce the interface impedance, and make it more effectively exert the above effects, thereby further improving the cycle performance and storage performance of the secondary battery.
  • the phosphorus-containing additive includes at least one selected from lithium difluorobisoxalate phosphate (LiDFOP), lithium tetrafluorooxalate phosphate (LiTFOP), lithium trioxalate phosphate (LiTOP), lithium difluorophosphate (LiDFP).
  • the phosphorus-containing additive includes lithium difluorobisoxalate phosphate and/or lithium difluorophosphate.
  • the sulfur-containing additive includes at least one selected from sulfonates, sulfates and sulfites.
  • the sulfur-containing additive can improve the composition and structure of the interface film, making it more effective in exerting the above effects, thereby further improving the cycle performance and storage performance of the secondary battery.
  • the sulfonate comprises at least one of the compounds shown in Formula I-1,
  • Q1 and Q2 are independently selected from C1-C6 alkylene groups.
  • Q 1 and Q 2 are independently selected from C1-C4 alkylene, such as methylene, ethylene or propylene.
  • the sulfonate comprises at least one of methylene methyl disulfonate (MMDS), ethylene ethyl disulfonate and propylene methyl disulfonate.
  • the sulfonate comprises at least one of the compounds shown in Formula I-2,
  • R 1 and R 2 are independently selected from a hydrogen atom or a C1-C6 alkyl group
  • Q 3 is selected from a C1-C6 alkylene group and a C2-C6 alkenylene group.
  • R 1 and R 2 are independently selected from hydrogen atom or C1-C4 alkyl group, and Q 3 is selected from C1-C4 alkylene group and C2-C4 alkenylene group.
  • the sulfonate ester includes at least one of 1,3-propane sultone (PS), 1-propylene-1,3-sultone (PST), and 1,4-butane sultone (BS).
  • PS 1,3-propane sultone
  • PST 1-propylene-1,3-sultone
  • BS 1,4-butane sultone
  • the sulfate ester includes at least one of the compounds shown in Formula I-3,
  • R 3 , R 4 , R 5 and R 6 are independently selected from a hydrogen atom or a C1-C6 alkyl group, and Q 4 is absent or is selected from a C1-C6 alkylene group.
  • R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen atom or C1-C4 alkyl, and Q 4 is absent or is selected from C1-C4 alkylene.
  • R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, methyl, ethyl, n-propyl, or isopropyl, and Q 4 is absent.
  • the sulfate ester includes at least one of diethylene sulfate (DTD), 4-methylethylene sulfate (PCS), 4-ethylethylene sulfate (PES), 4-propylethylene sulfate (PEGLST), and propylene sulfate (TS).
  • DTD diethylene sulfate
  • PCS 4-methylethylene sulfate
  • PES 4-ethylethylene sulfate
  • PEGLST 4-propylethylene sulfate
  • TS propylene sulfate
  • the sulfite comprises at least one of the compounds shown in Formula I-4,
  • R 7 , R 8 , R 9 and R 10 are independently selected from a hydrogen atom or a C1-C6 alkyl group, and Q 5 is absent or is selected from a C1-C6 alkylene group.
  • R 7 , R 8 , R 9 , and R 10 are independently selected from a hydrogen atom or a C1-C4 alkyl group, and Q 5 is absent or is selected from a C1-C4 alkylene group.
  • the sulfite comprises ethylene sulfite (DTO).
  • the sulfite comprises at least one of the compounds shown in Formula I-5,
  • R 11 and R 12 are independently selected from C1-C6 alkyl groups.
  • R 11 and R 12 are independently selected from C1-C4 alkyl.
  • the sulfite comprises at least one of dimethyl sulfite (DMS) and diethyl sulfite (DES).
  • the content of the phosphorus-containing additive is 0.01-4.5g for every 100g of negative electrode active material. In some embodiments, the content of the phosphorus-containing additive is 0.1g, 0.3g, 0.5g, 0.7g, 0.9g, 1g, 1.2g, 1.4g, 1.6g, 1.8g, 2g, 2.2g, 2.4g, 2.6g, 2.8g, 3.2g, 3.5g, 3.8g, 4g, 4.2g, 4.5g or a range consisting of any two of these values for every 100g of negative electrode active material. In some embodiments, the content of the phosphorus-containing additive is 0.05-4g for every 100g of negative electrode active material. In some embodiments, the content of the phosphorus-containing additive is 0.1-3g for every 100g of negative electrode active material.
  • the content of the sulfur-containing additive is 0.1-6g for every 100g of negative electrode active material. In some embodiments, the content of the sulfur-containing additive is 0.2g, 0.4g, 0.6g, 0.8g, 1g, 1.2g, 1.4g, 1.6g, 1.8g, 2g, 2.2g, 2.4g, 2.6g, 2.8g, 3.2g, 3.5g, 3.8g, 4g, 4.2g, 4.5g, 4.8g, 5g, 5.2g, 5.5g, 5.8g, 6g or a range consisting of any two of these values for every 100g of negative electrode active material. In some embodiments, the content of the sulfur-containing additive is 0.1-5g for every 100g of negative electrode active material. In some embodiments, the content of the sulfur-containing additive is 0.2-4g for every 100g of negative electrode active material.
  • the electrolyte further includes other additives, and the other additives include at least one of vinylene carbonate, vinyl ethylene carbonate, tris(trimethylsilyl)phosphate, tris(trimethylsilyl)borate, fluoroethylene carbonate, difluoroethylene carbonate, trifluoropropylene carbonate, 2,2,2-trifluoromethyl ethyl carbonate, 2,2,2-trifluorodiethyl carbonate, tris(trifluoroethyl)phosphate and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.
  • the other additives include at least one of vinylene carbonate, vinyl ethylene carbonate, tris(trimethylsilyl)phosphate, tris(trimethylsilyl)borate, fluoroethylene carbonate, difluoroethylene carbonate, trifluoropropylene carbonate, 2,2,2-trifluoromethyl ethyl carbonate, 2,2,2-trifluoro
  • the electrolyte further includes an electrolyte lithium salt
  • the lithium salt is selected from at least one of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), trifluoromethylsulfonyl lithium (LiOTf), lithium bis(fluorosulfonyl)imide (LiFSI), lithium (trifluoromethylsulfonyl)(perfluorobutylsulfonyl)imide (LiFNFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium bis(pentafluoroethylsulfonic acid)imide (LiBETI), lithium bis(oxalatoborate) (LiBOB), lithium bis(fluoromalonate)borate (LiBFMB), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium (LiTDI), and
  • the lithium salt includes lithium hexafluorophosphate.
  • the concentration of the lithium hexafluorophosphate is 0.3-1.2 mol/L. Wherein, the concentration represents the number of moles of lithium hexafluorophosphate contained in a unit volume of electrolyte.
  • the electrolyte further comprises a solvent.
  • the solvent comprises at least one of a linear carbonate, a cyclic carbonate, and a carboxylic acid ester.
  • the linear carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate and fluorinated linear carbonate.
  • the cyclic carbonate includes at least one of ethylene carbonate, propylene carbonate and butylene carbonate.
  • the carboxylate is selected from at least one of methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone and fluorinated carboxylate.
  • the solvent includes linear carbonate and/or cyclic carbonate, and based on the mass of the solvent, the mass content of the linear carbonate and/or cyclic carbonate is more than 90%, such as more than 95%, more than 98%.
  • the solvent does not include carboxylate. In some embodiments, the solvent does not include ether.
  • the negative electrode includes a negative electrode active material layer, and the negative electrode active material includes a silicon-based material.
  • the silicon-based material includes at least one of silicon, a silicon alloy, a silicon oxide compound, and a silicon carbon compound.
  • the silicon-based material is a silicon-oxygen compound and/or a silicon-carbon compound.
  • the negative electrode active material further comprises a mixture of at least one of a carbon-based material, a tin-based material, a phosphorus-based material, and metallic lithium.
  • the carbon-based material comprises at least one of graphite, soft carbon, hard carbon, carbon nanotubes, and graphene.
  • the tin-based material comprises at least one of tin, tin oxide, and a tin alloy.
  • the phosphorus-based material comprises phosphorus and/or a phosphorus complex.
  • the mass content g% of the silicon-based material satisfies: 10 ⁇ g ⁇ 100.
  • g is 11, 13, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or a range consisting of any two of these values.
  • 12 ⁇ g ⁇ 35 is a range consisting of any two of these values.
  • the negative electrode active material layer further comprises a binder and a conductive agent.
  • the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic (ester) styrene-butadiene rubber, epoxy resin or nylon, etc.
  • the conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and 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 metal powder, metal fiber, copper, nickel, aluminum, or silver.
  • the conductive polymer is a polyphenylene derivative.
  • the negative electrode further includes a negative electrode current collector
  • the negative electrode current collector includes: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or any combination thereof.
  • the negative electrode has a compacted density of 1.5-1.8 g/cm 3 . In some embodiments, the negative electrode has a compacted density of 1.5 g/cm 3 , 1.55 g/cm 3 , 1.6 g/cm 3 , 1.65 g/cm 3 , 1.7 g/cm 3 , 1.75 g/cm 3 , 1.8 g/cm 3 or a range consisting of any two of these values.
  • the compacted density of the electrode can be adjusted according to the characteristics of the selected active material by conventional technical means in the art, such as controlling the electrode rolling pressure, rolling temperature, rolling speed and rolling times.
  • the surface density of the negative electrode is 6-10 mg/cm 2 . In some embodiments, the surface density of the negative electrode is 6 mg/cm 2 , 6.5 mg/cm 2 , 7 mg/cm 2 , 7.5 mg/cm 2 , 8 mg/cm 2 , 8.5 mg/cm 2 , 9 mg/cm 2 , 9.5 mg/cm 2 , 10 mg/cm 2 or a range consisting of any two of these values. In the embodiment, the surface density of the negative electrode is 7-10 mg/cm 2 . In the present application, the surface density of the negative electrode can be adjusted according to the characteristics of the selected active material by conventional techniques in the art, such as coating knife thickness, coating temperature, and coating speed.
  • the positive electrode includes a positive electrode active material layer, and the positive electrode active material includes at least one selected from lithium nickel transition metal oxides.
  • the chemical formula of the lithium nickel transition metal oxide is shown in the formula LiNi m Co n A (1-mn) O 2 , wherein A is selected from at least one of manganese, aluminum, magnesium, chromium, calcium, zirconium, molybdenum, silver or niobium, 0.5 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 0.5, and m+n ⁇ 1.
  • m is 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or a range consisting of any two of these values.
  • n is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or a range consisting of any two of these values.
  • the lithium nickel transition metal oxide includes at least one of NCA, NCM111, NCM523, NCM622, NCM811, Ni90, Ni92, or Ni95.
  • the positive electrode active material may also include at least one of the phosphate compounds, the chemical formula of the phosphate compound is shown in the formula LiMn k B (1-k) PO 4 , wherein 0 ⁇ k ⁇ 1, and the B element is selected from at least one of iron, cobalt, magnesium, calcium, zinc, chromium or lead.
  • k is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or a range consisting of any two of these values.
  • the phosphate compound includes at least one of lithium iron phosphate, LiMn 0.6 Fe 0.4 PO 4 or LiMn 0.8 Fe 0.2 PO 4 .
  • the positive electrode active material layer further includes a binder, and optionally a conductive agent.
  • the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
  • the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin or nylon, etc.
  • the conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and 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 metal powder, metal fiber, copper, nickel, aluminum, or silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive electrode further includes a positive electrode current collector, which may be a metal foil or a composite current collector.
  • a positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used.
  • the composite current collector may be prepared by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a polymer substrate.
  • a separator is provided between the positive electrode and the negative electrode to prevent short circuit.
  • the material and shape of the separator that can be used in the embodiments of the present application are not particularly limited, and it can be any technology disclosed in the prior art.
  • the separator includes a polymer or an inorganic substance formed of a material that is stable to the electrolyte of the present application.
  • the isolation film may include a substrate layer and a surface treatment layer.
  • the substrate layer is a non-woven fabric, a film or a composite film having a porous structure
  • the material of the substrate layer includes at least one of polyethylene, polypropylene, polyethylene terephthalate or polyimide.
  • a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric or a polypropylene-polyethylene-polypropylene porous composite film can be selected.
  • a surface treatment layer is disposed on at least one surface of the substrate layer.
  • the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic layer.
  • the inorganic layer includes inorganic particles and a binder, wherein the inorganic particles include at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium sulfate.
  • the binder includes at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the polymer layer contains polymers, and the polymer material includes at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly(vinylidene fluoride-hexafluoropropylene).
  • the preparation method of the secondary battery includes providing an electrode assembly, injecting, packaging and forming.
  • the temperature of the formation is 40°C to 50°C, such as 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C or 49°C.
  • the pressure of the formation is 150kgf to 250kgf, such as 160kgf, 170kgf, 180kgf, 190kgf, 200kgf, 210kgf, 220kgf, 230kgf or 240kgf.
  • the charging current of the formation is 0.05C-0.1C
  • the discharge current of the formation is 0.1C-0.3C.
  • the formation includes: charging to 4.2V with a current of 0.05C and standing for 60 minutes at a temperature of 40°C-50°C, such as 45°C, and a pressure of 150kgf-250kgf, such as 200kgf, followed by charging to 4.2V with a current of 0.1C, and then discharging to 3.0V with a current of 0.2C.
  • the secondary battery is a lithium secondary battery or a sodium secondary battery.
  • the lithium secondary battery includes, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • the secondary battery may include an outer package, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer package of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
  • the shape of the secondary battery is not particularly limited, and it can be cylindrical, square, or any other shape.
  • the present application further provides a battery module.
  • the battery module includes the above-mentioned secondary battery.
  • the battery module of the present application uses the above-mentioned secondary battery, and therefore has at least the same advantages as the secondary battery.
  • the number of secondary batteries contained in the battery module of the present application can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • the present application further provides a battery pack, which includes the above-mentioned battery module.
  • the number of battery modules included in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • the present application also provides a device, which includes at least one of the above-mentioned secondary battery, battery module or battery pack.
  • the device includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, etc.
  • a battery pack or battery module may be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device is usually required to be light and thin, and a secondary battery may be used as a power source.
  • the lithium-ion battery was charged to 4.25V at 0.5C constant current, then charged to 0.05C at 4.25V, and then discharged to 2.5V at 1C constant current.
  • the capacity retention rate after the 400th cycle at 45°C was calculated according to the following formula: discharge capacity after the 400th cycle/discharge capacity in the first cycle ⁇ 100%.
  • the lithium-ion battery was discharged at 1C constant current to 2.5V at 25°C, then charged at 0.5C constant current to 4.25V, and then charged at 4.25V to 0.05C constant voltage.
  • the thickness of the battery at this time was measured using a PPG soft pack battery thickness gauge and recorded as a.
  • the battery was placed in an oven and stored at 60°C at a constant voltage of 4.25V for 30 days. The thickness after 30 days of testing was recorded as b.
  • the thickness expansion rate was calculated as: (b-a)/a ⁇ 100%.
  • the lithium-ion battery was discharged to 2.5V at a current of 0.1C, and the lithium-ion battery was disassembled in a glove box filled with argon to obtain the electrode sheet.
  • the obtained negative electrode sheet was cut into a test sample of 8mm ⁇ 8mm size, and soaked and cleaned with a low-boiling dimethyl carbonate (DMC) solvent for half an hour. After it was completely dried, it was pasted on the XPS sample stage, with the surface of the negative electrode active material layer facing away from the current collector facing upward, and the measurement was performed without exposure to the atmosphere.
  • DMC dimethyl carbonate
  • the negative electrode preparation steps are as follows: negative electrode active material silicon oxide (SiO x , 0.5 ⁇ x ⁇ 1.5)-graphite composite (the mass ratio of silicon oxide to graphite in the composite is 14:86), conductive agent acetylene black, binder styrene butadiene rubber SBR, thickener carboxymethyl fiber Sodium CMCNa and polyacrylic acid PAA are fully slurried in deionized water at a weight ratio of 96:2:1.5:1:0.5, and then coated on the surface of a 8 ⁇ m thick copper current collector. After drying, rolling and slitting, the negative electrode sheet is obtained.
  • silicon oxide SiO x , 0.5 ⁇ x ⁇ 1.5
  • SBR binder styrene butadiene rubber
  • PAA thickener carboxymethyl fiber
  • PAA polyacrylic acid
  • Diaphragm PP/PE/PP three-layer composite diaphragm.
  • Preparation of lithium-ion battery stack the prepared positive electrode sheet, separator and negative electrode sheet in order, make the separator between the positive and negative electrode sheets, and wind to obtain a bare battery cell; place the bare battery cell in an aluminum-plastic film outer package, inject the prepared lithium-ion battery electrolyte after sufficient drying, and the battery is left at 45°C for 48h, formed in a high-temperature fixture (formation conditions are: temperature 45°C, pressure 210kgf, 0.05C current charged to 4.2V and left to stand for 60min, then 0.1C charged to 4.2V, then 0.2C discharged to 3.0V, and so on, repeated twice) and secondary sealing, and then conventional capacity division is carried out to finally obtain a lithium-ion battery with a rated capacity of ⁇ 4Ah.
  • Examples 2 to 16 and Comparative Examples 1 to 8 are achieved on the basis of Example 1 by adjusting the type and content of additives in the electrolyte, the compaction density and single-sided surface density of the negative electrode sheet (wherein the compaction density of the negative electrode sheet is adjusted by controlling the negative electrode roller pressing pressure, and the single-sided surface density of the negative electrode sheet is adjusted by controlling the coating knife surface thickness). Specific adjustment measures and detailed data are shown in Table 1.
  • Example 17 is based on Example 6, except that the lithium salt is adjusted by replacing 1M LiPF6 lithium salt with a combined lithium salt of 0.3M LiPF6 and 0.7M LiFSI.
  • Table 2 * Indicates that the battery capacity retention rate is less than 60% at a cycle before 400 cycles.

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Abstract

一种二次电池和装置，所述的二次电池包括正极、负极和电解液，其中，所述电解液包括含硫添加剂和含磷添加剂；所述负极包括负极活性材料层以及位于所述负极活性材料层表面的固体电解质界面膜，采用X射线光电子能谱仪测试，所述固体电解质界面膜中硫的原子百分含量为S％，磷的原子百分含量为P％，其中，2.5≤2S+P/5≤10。所述的二次电池通过控制负极活性材料层表面形成的固体电解质界面膜中硫原子和磷原子的含量，在兼顾二次电池低阻抗的同时提高了其高温下的循环性能、存储性能和安全性能。

Description

二次电池和装置
本申请要求2023年06月12日提交的、发明名称为“二次电池和装置”的中国专利申请202310687392.2的优先权，上述中国专利申请的全部内容通过引用并入本申请中。
技术领域
本申请涉及储能领域。具体地，本申请涉及一种二次电池和装置。
背景技术
锂离子电池已经广泛地应用在我们日常生活及高科技领域。为了满足人们的需求，锂离子电池需要朝着更高能量密度、更安全、更长寿命的方向研发发展。然而，在电池循环过程中，电池正负极易与电解液发生副反应，一方面会导致电池容量的衰减、循环寿命的大幅降低，另一方面会导致气体的产生、电池体积的膨胀，从而使得电池的安全性降低。
发明内容
针对目前锂离子电池存在的问题，本申请提供了一种二次电池以及相关的装置。本申请的二次电池通过控制负极活性材料层表面形成的固体电解质界面膜(SEI膜)中磷原子和硫原子的含量，在兼顾二次电池低阻抗的同时提高了其高温下的循环性能、存储性能和安全性能。
本申请的第一方面提供了一种二次电池，其包括正极、负极和电解液，其中，所述电解液包括含硫添加剂和含磷添加剂；所述负极包括负极活性材料层以及位于所述负极活性材料层表面的固体电解质界面膜，采用X射线光电子能谱仪测试，所述固体电解质界面膜中硫的原子百分含量为S％，磷的原子百分含量为P％，其中，2.5≤2S+P/5≤10。
本申请的第二方面提供了一种装置，所述装置包括第一方面所述的二次电池。
本申请的有益效果为：
本申请的二次电池通过控制负极活性材料层表面形成的固体电解质界面膜SEI中硫原子和磷原子的含量，使得SEI膜更加致密和稳定，可以有效减缓电解液对电极材料的侵蚀，提高界面锂离子传输能力，降低界面阻抗，进而降低二次电池的阻抗，同时，特定硫原子 和磷原子含量配合的SEI膜可以改善锂离子二次电池的循环性能和安全性能，特别是高温下的循环性能和存储性能。
具体实施方式
为了简明，本申请仅具体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，每个单独公开的点或单个数值自身可以作为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。
除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测量方法进行测量(例如，可以按照在本申请的实施例中给出的方法进行测试)。
术语“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一种”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一种”意味着仅A；或仅B；仅C；A及B(排除C)；A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个组分或多个组分。项目B可包含单个组分或多个组分。项目C可包含单个组分或多个组分。
下面结合具体实施方式，进一步阐述本申请。应理解，这些具体实施方式仅用于说明本申请而不用于限制本申请的范围。
一、二次电池
本申请提供的二次电池包括正极、负极和电解液，其中，所述电解液包括含硫添加剂和含磷添加剂；所述负极包括负极活性材料层以及位于所述负极活性材料层表面的固体电解质界面膜，采用X射线光电子能谱仪测试，所述固体电解质界面膜中硫的原子百分含量为S％，磷的原子百分含量为P％，其中，2.5≤2S+P/5≤10。负极固体电解质界面膜SEI中来自含硫添加剂的硫原子(如Li2S、Li2SO3、烷基亚磺酸锂盐RSO2Li等中的硫原子)可以改善SEI膜的高温稳定性，从而有利于改善负极的高温存储性能和高温循环性能，但是由于硫是锂离子和电子的不良导体，其含量较多时，会影响电池阻抗的升高，增大电池极化，加速电池在循环过程中容量的衰减。SEI中来自含磷添加剂的磷原子(如LiPxFy、LixPOyFz 等中的磷原子)可以改善锂离子和电子的导电性，降低界面阻抗，进而降低二次电池的阻抗，但是含磷添加剂的高温性能欠佳。
本申请中，硫的原子百分含量是指固体电解质膜中硫原子占除氢原子以外所有原子的摩尔百分含量。磷的原子百分含量是指固体电解质膜中磷原子占除氢原子以外所有原子的摩尔百分含量。
在一些实施方式中，2S+P/5为2.5、2.8、3、3.2、3.5、3.8、4、4.2、4.5、4.8、5、5.2、5.5、5.8、6、6.2、6.5、6.8、7、7.2、7.5、7.8、8、8.2、8.5、8.8、9、9.2、9.5、9.8、10或这些值中任意两者组成的范围。在一些实施方式中，3≤2S+P/5≤10。当2S+P/5过高时，SEI膜中硫元素和磷元素含量较大，使得负极表面活性位点增加，会消耗更多的锂，不能抑制电解液的持续分解，进而影响电池的循环性能。当2S+P/5过低时，负极表面活性位点太少，导致电极界面动力学变差，极化增加，进而影响电池的循环性能。
在一些实施方式中，0.1≤S≤8。在一些实施方式中，S为0.2、0.5、0.8、1、1.2、1.5、1.8、2、2.2、2.5、2.8、3、3.2、3.5、3.8、4、4.2、4.5、4.8、5、5.2、5.5、5.8、6、6.2、6.5、6.8、7、7.2、7.5、7.8、8或这些值中任意两者组成的范围。在一些实施方式中，0.5≤S≤5。在另一些实施方式中，1≤S≤4。
在一些实施方式中，0.1≤P≤15。在一些实施方式中，P为0.2、0.5、0.8、1、1.2、1.5、1.8、2、2.2、2.5、2.8、3、3.2、3.5、3.8、4、4.2、4.5、4.8、5、5.2、5.5、5.8、6、6.2、6.5、6.8、7、7.2、7.5、7.8、8、8.2、8.5、8.8、9、9.2、9.5、9.8、10、10.2、10.5、10.8、11、11.2、11.5、11.8、12、12.2、12.5、12.8、13、13.2、13.5、13.8、14、14.2、14.5、14.8、15或这些值中任意两者组成的范围。在一些实施方式中，0.5≤P≤10。在另一些实施方式中，2≤P≤10。
在一些实施方式中，所述含磷添加剂包括选自磷酸锂盐中的至少一种。上述含磷添加剂能够改善界面膜的组成及结构，降低界面阻抗，使其更有效地发挥上述效果，从而进一步改善二次电池的循环性能及存储性能。
在一些实施方式中，所述含磷添加剂包括选自二氟二草酸磷酸锂(LiDFOP)、四氟草酸磷酸锂(LiTFOP)、三草酸磷酸锂(LiTOP)、二氟磷酸锂(LiDFP)中的至少一种。在另一些实施方式中，所述含磷添加剂包括二氟二草酸磷酸锂和/或二氟磷酸锂。
在一些实施方式中，所述含硫添加剂包括选自磺酸酯、硫酸酯和亚硫酸酯中的至少一种。上述含硫添加剂能够改善界面膜的组成及结构，使其更有效地发挥上述效果，从而进一步改善二次电池的循环性能及存储性能。
在一些实施方式中，所述磺酸酯包括式I-1所示的化合物中的至少一种，
式I-1中，Q1和Q2独立地选自C1-C6亚烷基。
在一些实施方式中，Q1和Q2独立地选自C1-C4亚烷基，例如亚甲基、亚乙基或亚丙基。在一些实施方式中，所述磺酸酯包括甲基二磺酸亚甲酯(MMDS)、乙基二磺酸亚乙酯和甲基二磺酸亚丙酯中的至少一种。
在一些实施方式中，所述磺酸酯包括式I-2所示的化合物中的至少一种，
式I-2中，R1、R2独立地选自氢原子或C1-C6烷基，Q3选自C1-C6亚烷基、C2-C6亚烯基。
在一些实施方式中，式I-2中，R1、R2独立地选自氢原子或C1-C4烷基，Q3选自C1-C4亚烷基、C2-C4亚烯基。
在一些实施方式中，所述磺酸酯包括1,3-丙烷磺内酯(PS)、1-丙烯-1,3-磺酸内酯(PST)和1,4-丁烷磺内酯(BS)中的至少一种。
在一些实施方式中，所述硫酸酯包括式I-3所示的化合物中的至少一种，
式I-3中，R3、R4、R5、R6独立地选自氢原子或C1-C6烷基，Q4不存在或Q4选自C1-C6亚烷基。
在一些实施方式中，式I-3中，R3、R4、R5、R6独立地选自氢原子或C1-C4烷基，Q4不存在或Q4选自C1-C4亚烷基。
在一些实施方式中，式I-3中，R3、R4、R5、R6独立地选自氢原子、甲基、乙基、正丙基或异丙基，Q4不存在。
在一些实施方式中，所述硫酸酯包括硫酸乙烯酯(DTD)、4-甲基硫酸亚乙酯(PCS)、4-乙基硫酸亚乙酯(PES)、4-丙基硫酸亚乙酯(PEGLST)和硫酸丙烯酯(TS)中的至少一种。
在一些实施方式中，所述亚硫酸酯包括式I-4所示的化合物中的至少一种，
式I-4中，R7、R8、R9、R10独立地选自氢原子或C1-C6烷基，Q5不存在或Q5选自C1-C6亚烷基。
在一些实施方式中，式I-4中，R7、R8、R9、R10独立地选自氢原子或C1-C4烷基，Q5不存在或Q5选自C1-C4亚烷基。
在一些实施方式中，所述亚硫酸酯包括亚硫酸亚乙酯(DTO)。
在一些实施方式中，所述亚硫酸酯包括式I-5所示的化合物中的至少一种，
式I-5中，R11和R12独立地选自C1-C6烷基。
在一些实施方式中，式I-5中，R11和R12独立地选自C1-C4烷基。在一些实施方式中，所述亚硫酸酯包括二甲基亚硫酸酯(DMS)和二乙基亚硫酸酯(DES)中的至少一种。
在一些实施方式中，相对于每100g负极活性材料，所述含磷添加剂的含量为0.01-4.5g。在一些实施方式中，相对于每100g负极活性材料，所述含磷添加剂的含量为0.1g、0.3g、0.5g、0.7g、0.9g、1g、1.2g、1.4g、1.6g、1.8g、2g、2.2g、2.4g、2.6g、2.8g、3.2g、3.5g、3.8g、4g、4.2g、4.5g或这些值中任意两者组成的范围。在一些实施方式中，相对于每100g负极活性材料，所述含磷添加剂的含量为0.05-4g。在一些实施方式中，相对于每100g负极活性材料，所述含磷添加剂的含量为0.1-3g。
在一些实施方式中，相对于每100g负极活性材料，所述含硫添加剂的含量为0.1-6g。在一些实施方式中，相对于每100g负极活性材料，所述含硫添加剂的含量为0.2g、0.4g、0.6g、0.8g、1g、1.2g、1.4g、1.6g、1.8g、2g、2.2g、2.4g、2.6g、2.8g、3.2g、3.5g、3.8g、4g、4.2g、4.5g、4.8g、5g、5.2g、5.5g、5.8g、6g或这些值中任意两者组成的范围。在一些实施方式中，相对于每100g负极活性材料，所述含硫添加剂的含量为0.1-5g。在一些实施方式中，相对于每100g负极活性材料，所述含硫添加剂的含量为0.2-4g。
在一些实施方式中，所述电解液还包括其他添加剂，所述其他添加剂包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、三(三甲基硅烷)磷酸酯、三(三甲基硅烷)硼酸酯、氟代碳酸乙烯酯、二氟代碳酸乙烯酯、三氟代碳酸丙烯酯、2,2,2-三氟代碳酸甲乙酯、2,2,2-三氟代碳酸二乙酯、三(三氟乙基)磷酸酯和1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚中的至少一种。
在一些实施方式中，所述电解液还包括电解质锂盐，所述锂盐选自六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、三氟甲基磺酰锂(LiOTf)、双(氟磺酰)亚胺锂(LiFSI)、(三氟甲基磺酰)(全氟丁基磺酰)亚胺锂(LiFNFSI)、双三氟甲基磺酰亚胺锂(LiTFSI)、双(五氟乙基磺酸)亚胺锂(LiBETI)、双草酸硼酸锂(LiBOB)、双(氟代丙二酸)硼酸锂(LiBFMB)、4,5-二氰基-2-(三氟甲基)咪唑锂(LiTDI)和二氟草酸硼酸锂(LiDFOB)中的至少一种。
在一些实施方式中，所述锂盐包括六氟磷酸锂。在一些实施方式中，所述六氟磷酸锂的浓度为0.3-1.2mol/L。其中，浓度表示单位体积电解液中所含六氟磷酸锂的摩尔数。
在一些实施方式中，所述电解液还包括溶剂。在一些实施方式中，所述溶剂包括链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。
在一些实施方式中，所述链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯和氟代链状碳酸酯中的至少一种。在一些实施方式中，所述环状碳酸酯包括碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯中的至少一种。在一些实施方式中，所述羧酸酯选自甲酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、γ-丁内酯和氟代羧酸酯中的至少一种。
在一些实施方式中，所述溶剂包括链状碳酸酯和/或环状碳酸酯，基于所述溶剂的质量，所述链状碳酸酯和/或环状碳酸酯的质量含量在90％以上，例如95％以上、98％以上。在一些实施方式中，所述溶剂不包括羧酸酯。在一些实施方式中，所述溶剂不包括醚。
在一些实施方式中，所述负极包括负极活性材料层，所述负极活性材料包括硅基材料。所述硅基材料包括硅、硅合金、硅氧化合物和硅碳化合物中的至少一种。在一些实施方式 中，所述硅基材料为硅氧化合物和/或硅碳化合物。本申请中的“硅氧化合物”可以是单一物质，也可以是混合物，只要其平均化学通式符合SiOx，x＝0.5-1.5，即可。
在一些实施方式中，所述负极活性材料还包括碳基材料、锡基材料、磷基材料、金属锂中的至少一种材料的混合物。所述碳基材料包括石墨、软碳、硬碳、碳纳米管和石墨烯中的至少一种。所述锡基材料包括锡、锡氧化物和锡合金中的至少一种。所述磷基材料包括磷和/或磷复合物。
在一些实施方式中，基于所述负极活性材料的质量，所述硅基材料的质量含量g％满足：10≤g≤100。在一些实施方式中，g为11、13、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95或这些值中任意两者组成的范围。在一些实施方式中，10≤g≤50。在另一些实施方式中，12≤g≤35。
在一些实施方式中，所述负极活性材料层还包括粘结剂和导电剂。在一些实施方式中，粘结剂包括，但不限于：聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1，1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙等。
在一些实施方式中，导电剂包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，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，基于金属的材料选自金属粉、金属纤维、铜、镍、铝或银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施方式中，所述负极还包括负极集流体，所述负极集流体包括：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或其任意组合。
在一些实施方式中，所述负极的极片压实密度为1.5-1.8g/cm3。在一些实施方式中，所述负极的极片压实密度为1.5g/cm3、1.55g/cm3、1.6g/cm3、1.65g/cm3、1.7g/cm3、1.75g/cm3、1.8g/cm3或这些值中任意两者组成的范围。本申请中，极片压实密度可根据所选择的活性物质特性，通过本领域常规技术手段调整，例如控制极片辊压压力、辊压温度、辊压速度和辊压次数。
在一些实施方式中，所述负极的极片单面面密度为6-10mg/cm2。在一些实施方式中，所述负极的极片单面面密度为6mg/cm2、6.5mg/cm2、7mg/cm2、7.5mg/cm2、8mg/cm2、8.5mg/cm2、9mg/cm2、9.5mg/cm2、10mg/cm2或这些值中任意两者组成的范围。在一些实施 方式中，所述负极的极片单面面密度为7-10mg/cm2。本申请中，极片单面面密度可根据所选择的活性物质特性，通过本领域常规技术手段调整，例如涂布刀表厚度、涂布温度、涂布速度。
在一些实施方式中，所述正极包括正极活性材料层，所述正极活性材料包括选自锂镍过渡金属氧化物中的至少一种。在一些实施方式中，所述锂镍过渡金属氧化物的化学式如式LiNimConA(1-m-n)O2所示，其中，A选自锰、铝、镁、铬、钙、锆、钼、银或铌中的至少一种，0.5≤m≤1，0≤n≤0.5，m+n≤1。
在一些实施方式中，m为0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95或这些值中任意两者组成的范围。在一些实施方式中，n为0.05、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45或这些值中任意两者组成的范围。
在一些实施方式中，所述锂镍过渡金属氧化物包括NCA、NCM111、NCM523、NCM622、NCM811、Ni90、Ni92或Ni95中的至少一种。
在一些实施方式中，所述正极活性材料也可包括磷酸盐系化合物中的至少一种，所述磷酸盐系化合物的化学式如式LiMnkB(1-k)PO4所示，其中，0≤k≤1，B元素选自铁、钴、镁、钙、锌、铬或铅中的至少一种。在一些实施方式中，k为0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95或这些值中任意两者组成的范围。在一些实施方式中，所述磷酸盐系化合物包括磷酸铁锂、LiMn0.6Fe0.4PO4或LiMn0.8Fe0.2PO4中的至少一种。
在一些实施方式中，正极活性材料层还包括粘结剂，并且可选地包括导电剂。粘结剂提高正极活性材料颗粒彼此间的结合，并且还提高正极活性材料与集流体的结合。
在一些实施方式中，粘结剂包括，但不限于：聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙等。
在一些实施方式中，导电剂包括，但不限于：基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，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，基于金属的材料选自金属粉、金属纤维、铜、镍、铝或银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
在一些实施方式中，所述正极还包括正极集流体，所述正极集流体可以采用金属箔片或复合集流体。例如，可以使用铝箔。复合集流体可以通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子基材上的工艺所制得。
在一些实施方式中，正极与负极之间设有隔离膜以防止短路。可用于本申请的实施例的隔离膜的材料和形状没有特别限制，其可为任何现有技术中公开的技术。在一些实施方式中，隔离膜包括由对本申请的电解液稳定的材料形成的聚合物或无机物等。
例如，隔离膜可包括基材层和表面处理层。基材层为具有多孔结构的无纺布、膜或复合膜，基材层的材料包括聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯或聚酰亚胺中的至少一种。具体地，可选用聚丙烯多孔膜、聚乙烯多孔膜、聚丙烯无纺布、聚乙烯无纺布或聚丙烯-聚乙烯-聚丙烯多孔复合膜。
基材层的至少一个表面上设置有表面处理层，表面处理层可以是聚合物层或无机物层，也可以是混合聚合物与无机物所形成的层。
无机物层包括无机颗粒和粘结剂，无机颗粒包括氧化铝、氧化硅、氧化镁、氧化钛、二氧化铪、氧化锡、二氧化铈、氧化镍、氧化锌、氧化钙、氧化锆、氧化钇、碳化硅、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。粘结剂包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。
聚合物层中包含聚合物，聚合物的材料包括聚酰胺、聚丙烯腈、丙烯酸酯聚合物、聚丙烯酸、聚丙烯酸盐、聚乙烯呲咯烷酮、聚乙烯醚、聚偏氟乙烯或聚(偏氟乙烯-六氟丙烯)中的至少一种。
在一些实施方式中，所述二次电池的制备方法包括提供电极组件、注液、封装和化成。在一些实施方式中，所述化成的温度为40℃至50℃，例如41℃、42℃、43℃、44℃、45℃、46℃、47℃、48℃或49℃。在一些实施方式中，所述化成的压力为150kgf至250kgf，例如160kgf、170kgf、180kgf、190kgf、200kgf、210kgf、220kgf、230kgf或240kgf。在一些实施方式中，所述化成的充电电流为0.05C-0.1C，所述化成的放电电流为0.1C-0.3C。
在一些实施方式中，所述化成包括：在温度为40℃-50℃例如45℃、压力为150kgf-250kgf例如200kgf的条件下，0.05C电流充电至4.2V静置60min，随后0.1C充电至4.2V，然后0.2C放电至3.0V。
在一些实施方式中，所述二次电池为锂二次电池或钠二次电池。在一些实施例中，锂二次电池包括，但不限于：锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
在一些实施方式中，二次电池可包括外包装，所述外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，如聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)、聚丁二酸丁二醇酯(PBS)等中的一种或几种。
在一些实施方式中，所述二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。
在一些实施方式中，本申请还提供了一种电池模块。该电池模块包括上述的二次电池。本申请的电池模块采用了上述二次电池，因此至少具有与所述二次电池相同的优势。本申请的电池模块所含二次电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
在一些实施方式中，本申请还提供了一种电池包，其包括上述电池模块。所述电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
二、装置
本申请还提供了一种装置，所述装置包括上述二次电池、电池模块或电池包中的至少一种。
在一些实施方式中，所述装置包括，但不限于：电动车辆、混合动力电动车辆、插电式混合动力电动车辆、蓄电系统等。为了满足该装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
在另一些实施方中，所述装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
测试方法
1.电池阻抗测试
将锂离子电池在25±2℃下以1C恒流放电至2.5V，再以0.5C恒流充电至4.25V，4.25V下恒压充电至0.05C，然后再1C恒流放电至50％SOC，静置60min，记录静置结束后的电 压U1，再以2C恒流放电10s，记录放电结束后电压U2，2C电流记为I，静置60min。按公式DCR＝(U1-U2)/I，计算电池在50％SOC下的放电DCR。
2.电池高温循环性能测试
在45℃条件下，将锂离子电池以0.5C恒流充电至4.25V，再4.25V下恒压充电至0.05C，之后再1C恒流放电至2.5V。充放电400个循环后，按以下公式计算45℃、第400次循环后的容量保持率：第400次循环后放电容量/首次循环放电容量×100％。
3.电池60℃存储厚度变化率测试
将锂离子电池在25℃下以1C恒流放电至2.5V，再以0.5C恒流充电至4.25V，之后再4.25V下恒压充电至0.05C，使用PPG软包电池测厚仪测试此时电池的厚度记为a。将电池放置到烘箱当中，在60℃存储条件下恒压4.25V存储30天，测试30天之后的厚度记为b，厚度膨胀率的计算公式：(b-a)/a×100％。
4.SEI膜硫和磷的原子百分含量的测试
将锂离子电池以0.1C的电流下放电至2.5V，在充满氩气的手套箱中进行锂离子电池拆卸得到电极极片。将得到的负极极片裁剪成8mm×8mm大小的测试样品，并用低沸点的碳酸二甲酯(DMC)溶剂进行浸泡清洗半小时，待完全干燥后，粘贴于XPS的样品台上，使负极活性材料层的背离集流体的表面朝上，在没有暴露于大气中的条件下进行测量。具体测试条件和步骤如下：
使用单晶体光谱AlKα射线，至于X射线点，使用输出为10KV和22mA的1000×1750μm的椭圆形式，选择溅射刻蚀时间为0秒时的数据，对于中性碳C1s使用284.8eV，且至于数据处理例如峰值区分，使用3点光滑，峰面积测量，本底扣除和峰值合成，以计算硫和磷的原子百分含量。
实施例1
正极制备步骤为：将正极活性材料LiNi0.9Co0.05Mn0.05O2、导电剂碳纳米管/乙炔黑、粘结剂聚偏氟乙烯PVDF，按重量比例LiNi0.9Co0.05Mn0.05O2﹕CNT/Super-P﹕PVDF＝95﹕2.0/1.0﹕2在N-甲基吡咯烷酮NMP溶剂体系中充分匀浆后，涂布于12μm厚的涂铝集流体上烘干、辊压，得到正极极片。
负极制备步骤为：将负极活性材料硅氧(SiOx，0.5≤x≤1.5)-石墨复合物(复合物中硅氧与石墨的质量比为14﹕86)、导电剂乙炔黑、粘结剂丁苯橡胶SBR、增稠剂羧甲基纤维 素钠CMCNa、聚丙烯酸PAA按重量比例96﹕2﹕1.5﹕1﹕0.5在去离子水中充分匀浆后，涂布于8μm厚铜集流体表面，烘干、辊压、分条后得到负极极片。
隔膜：采用PP/PE/PP三层复合隔膜。
电解液的配制：在充满氩气的手套箱(H2O＜0.1ppm，O2＜0.1ppm)中，将锂盐LiPF6和溶剂EC/DEC/EMC＝25/20/55按照一定的比例混合均匀，配置成1M的溶液，最后按照负极活性材料的质量加入表1用量的含硫添加剂(相对于100g负极活性材料添加0.435gDTD)和含磷添加剂(相对于100g负极活性材料添加0.435gLiDFP)，搅拌均匀后得到实施例1的锂离子电池电解液。
锂离子电池的制备：将制得的正极极片、隔膜、负极极片按顺序叠好，使隔膜处于正负极极片中间，卷绕得到裸电芯；将裸电芯置于铝塑膜外包装中，经过充分干燥后注入配制好的锂离子电池电解液，电池经过45℃搁置48h、高温夹具化成(化成条件是：温度45℃、压力210kgf、0.05C电流充电至4.2V静置60min，随后0.1C充电至4.2V，然后0.2C放电至3.0V，如此，重复两次)和二次封口后，进行常规分容，最后得到额定容量～4Ah的锂离子电池。
实施例2至实施例16以及对比例1至对比例8
实施例2至实施例16以及对比例1至对比例8是在实施例1的基础上通过调整电解液中添加剂的种类和含量、负极极片的压实密度和单面面密度(其中负极片压实密度通过控制负极辊压压力来调整、负极片单面面密度通过控制涂布刀表厚度来调整)来实现的，具体调整措施和详细数据见表1。
实施例17
实施例17是在实施例6的基础上，调整了锂盐，将1M的LiPF6锂盐替换成0.3M LiPF6和0.7M LiFSI的组合锂盐。
表1

实施例1-17和对比例1-7的电池性能测试结果见表2。
表2


*：表示电池在循环400圈前的某一圈容量保持率就已低于60％。
虽然已经说明和描述了本申请的一些示例性实施方式，然而本申请不限于所公开的实施方式。相反，本领域普通技术人员将认识到，在不脱离如所附权利要求中描述的本申请的精神和范围的情况下，可对所描述的实施方式进行一些修饰和改变。

Claims (11)

  1. 一种二次电池，包括正极、负极和电解液，其中，
    所述电解液包括含硫添加剂和含磷添加剂；
    所述负极包括负极活性材料层以及位于所述负极活性材料层表面的固体电解质界面膜，采用X射线光电子能谱仪测试，所述固体电解质界面膜中硫的原子百分含量为S％，磷的原子百分含量为P％，其中，2.5≤2S+P/5≤10。
  2. 根据权利要求1所述的二次电池，其特征在于，0.1≤S≤8，和/或，0.1≤P≤15。
  3. 根据权利要求1或2所述的二次电池，其特征在于，0.5≤S≤5，和/或，0.5≤P≤10。
  4. 根据权利要求1或2所述的二次电池，其特征在于，相对于每100g负极活性材料，所述含磷添加剂的含量为0.01-4.5g。
  5. 根据权利要求1或2所述的二次电池，其特征在于，相对于每100g负极活性材料，所述含硫添加剂的含量为0.1-6g。
  6. 根据权利要求1或2所述的二次电池，其特征在于，所述负极的极片压实密度为1.5-1.8g/cm3；和/或，
    所述负极的极片单面面密度为6-10mg/cm2。
  7. 根据权利要求1或2所述的二次电池，其特征在于，所述含磷添加剂包括选自磷酸锂盐中的至少一种，和/或，所述含硫添加剂包括选自磺酸酯、硫酸酯和亚硫酸酯中的至少一种，其中，
    所述磺酸酯包括式I-1和式I-2所示的化合物中的至少一种，
    式I-1中，Q1和Q2独立地选自C1-C6亚烷基，式I-2中，R1、R2独立地选自氢原子或C1-C6烷基，Q3选自C1-C6亚烷基、C2-C6亚烯基；
    所述硫酸酯包括式I-3所示的化合物中的至少一种，
    式I-3中，R3、R4、R5、R6独立地选自氢原子或C1-C6烷基，Q4不存在或Q4选自C1-C6亚烷基；
    所述亚硫酸酯包括式I-4和式I-5所示的化合物中的至少一种，
    式I-4中，R7、R8、R9、R10独立地选自氢原子或C1-C6烷基，Q5不存在或Q5选自C1-C6亚烷基，式I-5中，R11和R12独立地选自C1-C6烷基。
  8. 根据权利要求7所述的二次电池，其特征在于，所述含磷添加剂包括选自二氟二草酸磷酸锂、四氟草酸磷酸锂、三草酸磷酸锂和二氟磷酸锂中的至少一种；和/或，
    所述磺酸酯包括甲基二磺酸亚甲酯、乙基二磺酸亚乙酯、甲基二磺酸亚丙酯、1,3-丙烷磺内酯、1-丙烯-1,3-磺酸内酯和1,4-丁烷磺内酯中的至少一种，
    所述硫酸酯包括硫酸乙烯酯、4-甲基硫酸亚乙酯、4-乙基硫酸亚乙酯、4-丙基硫酸亚乙酯和硫酸丙烯酯中的至少一种，
    所述亚硫酸酯包括亚硫酸亚乙酯、二甲基亚硫酸酯和二乙基亚硫酸酯中的至少一种。
  9. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液包括锂盐，所述锂盐包括六氟磷酸锂，所述六氟磷酸锂的浓度为0.3-1.2mol/L；和/或，
    所述电解液包括溶剂，所述溶剂包括链状碳酸酯和/或环状碳酸酯，基于所述溶剂的质量，所述链状碳酸酯和/或环状碳酸酯的质量含量在90％以上。
  10. 根据权利要求1或2所述的二次电池，其特征在于，所述负极包括选自硅、硅合金、硅氧化合物和硅碳化合物中的至少一种硅基材料，基于所述负极活性材料的质量，所述硅基材料的质量含量g％满足：10≤g≤100；和/或，
    所述正极包括选自锂镍过渡金属氧化物的活性材料，所述锂镍过渡金属氧化物的化学式如式LiNimConA(1-m-n)O2所示，其中，A选自锰、铝、镁、铬、钙、锆、钼、银或铌中的至少一种，0.5≤m≤1，0≤n≤0.5，m+n≤1。
  11. 一种装置，其包括权利要求1-10中任一项所述的二次电池。
PCT/CN2024/098028 2023-06-12 2024-06-07 二次电池和装置 Ceased WO2024255699A1 (zh)

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