WO2025218178A1 - 二次电池和装置 - Google Patents

二次电池和装置

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Publication number
WO2025218178A1
WO2025218178A1 PCT/CN2024/135180 CN2024135180W WO2025218178A1 WO 2025218178 A1 WO2025218178 A1 WO 2025218178A1 CN 2024135180 W CN2024135180 W CN 2024135180W WO 2025218178 A1 WO2025218178 A1 WO 2025218178A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
lithium
silicon
battery according
negative electrode
Prior art date
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Pending
Application number
PCT/CN2024/135180
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English (en)
French (fr)
Inventor
马娟
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NIO Technology Anhui Co Ltd
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NIO Technology Anhui Co Ltd
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Publication date
Application filed by NIO Technology Anhui Co Ltd filed Critical NIO Technology Anhui Co Ltd
Publication of WO2025218178A1 publication Critical patent/WO2025218178A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 secondary batteries have been increasingly used in mobile phones, computers, energy storage, power tools, and electric vehicles.
  • Faster charging speeds have long been a goal for lithium-ion secondary batteries, and the development of fast-charging technology can alleviate the anxiety of electric vehicle users about recharging.
  • Lithium-ion transmission speed is an important reference indicator for fast-charging performance.
  • the electrolyte is one of the key factors affecting the transmission speed of lithium-ion charging and discharging. This is because the electrolyte is an important medium connecting the positive and negative electrodes and is a key location for lithium-ion transmission. Therefore, the research on fast-charging electrolytes is an important development direction for fast-charging batteries.
  • electrolyte additives will form a solid electrolyte interface film at the interface of the positive and negative electrodes.
  • This interface film is one of the greater resistances in the lithium ion transfer process, thereby affecting the fast charging performance of the secondary battery.
  • the electrolyte body is an important place for lithium ion transmission, and the type and content of its electrolyte additives will also affect the fast charging speed of the battery.
  • the present application provides a secondary battery and a device to solve the technical problem of slow charging speed in the prior art.
  • the secondary battery includes a fast-charging electrolyte, wherein the fast-charging electrolyte includes nitrogen-containing additives, silicon-containing and phosphorus-containing additives, thereby enabling lithium ions to be quickly transmitted in the electrolyte body, and a special solid electrolyte interface film with less resistance can be formed at the interface of the negative electrode plate, so that lithium ions can also be quickly transmitted in the interface film, thereby significantly improving the fast charging speed of the battery.
  • the fast-charging electrolyte includes nitrogen-containing additives, silicon-containing and phosphorus-containing additives, thereby enabling lithium ions to be quickly transmitted in the electrolyte body, and a special solid electrolyte interface film with less resistance can be formed at the interface of the negative electrode plate, so that lithium ions can also be quickly transmitted in the interface film, thereby significantly improving the fast charging speed of the battery.
  • the present application provides a secondary battery, which includes a positive electrode plate, a negative electrode plate and an electrolyte; the electrolyte includes a nitrogen-containing additive, a silicon-containing additive and a phosphorus-containing additive; the negative electrode plate includes a negative electrode active material layer and a solid electrolyte interface film located on the surface of the negative electrode active material layer; using an X-ray photoelectron spectrometer to test at a sputtering etching time of 0 seconds, the mass percentage content of nitrogen in the solid electrolyte interface film is a%, the mass percentage content of silicon in the solid electrolyte interface film is b%, and the mass percentage content of phosphorus in the solid electrolyte interface film is c%; wherein 6 ⁇ 0.25a+b+0.5c ⁇ 10.
  • Another aspect of the present application provides a device, which includes the secondary battery described above.
  • the secondary battery of the present application adds nitrogen-containing additives, silicon-containing and phosphorus-containing additives to the electrolyte, and controls the content of nitrogen, silicon and phosphorus in the solid electrolyte interface film (SEI film) on the surface of the negative electrode active material layer.
  • SEI film solid electrolyte interface film
  • the fast-charging electrolyte can enable lithium ions to be quickly transmitted in the electrolyte, thereby improving the fast-charging speed;
  • the control of the content of nitrogen, silicon and phosphorus in the above-mentioned SEI film improves the inorganic component ratio and structural uniformity of the SEI film, significantly reduces the transfer resistance of the SEI film to lithium ions, and thus significantly reduces the impedance of the SEI film, achieving rapid transmission of lithium ions in the SEI film, thereby significantly improving the fast-charging speed of the battery and improving the rate performance of the battery.
  • the secondary battery of the present application has at least one of the following advantages: excellent cycle performance, fast-charging performance and rate performance.
  • FIG1 is a peak spectrum of nitrogen elements in an XPS spectrum of a SEI film of a negative electrode according to one embodiment of the present application.
  • FIG2 is a peak spectrum of silicon element in the XPS spectrum of the SEI film of the negative electrode according to one embodiment of the present application.
  • FIG3 is a peak spectrum of phosphorus element in the XPS spectrum of the SEI film of the negative electrode according to one embodiment of the present application.
  • any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range.
  • each individually disclosed point or single value may itself serve as a lower limit or upper limit and be combined with any other point or single value, or with other lower limits or upper limits, to form an unspecified range.
  • a list of items connected by the terms “at least one of,” “at least one of,” “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.
  • C1-C3 alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, and the like.
  • C3-C6 alkylsilyl refers to a silicon group having 3 to 6 carbon atoms, including but not limited to trimethylsilyl and the like.
  • C2-C3 alkenyl includes, but is not limited to, ethenyl, propenyl, and the like.
  • C6-C12 aryl includes, but is not limited to, phenyl or naphthyl.
  • substituted or unsubstituted means that the functional group described after the term may or may not have a substituent.
  • substituted or unsubstituted C1-C3 alkyl refers to a C1-C3 alkyl group with a substituent or an unsubstituted C1-C3 alkyl group.
  • the number of substituents may be 1 or more, and the substituents include at least one of a halogen (e.g., fluorine), an alkyl group, or an aryl group. It should be understood that when the number of substituents is greater than 1, the substituents may be the same or different.
  • the secondary battery provided in the present application includes a positive electrode plate, a negative electrode plate and an electrolyte; the electrolyte includes a nitrogen-containing additive, a silicon-containing additive and a phosphorus-containing additive; the negative electrode plate includes a negative electrode active material layer and a solid electrolyte interface film located on the surface of the negative electrode active material layer; using an X-ray photoelectron spectrometer to test at a sputtering etching time of 0 seconds, the mass percentage content of nitrogen element in the solid electrolyte interface film is a%, the mass percentage content of silicon element in the solid electrolyte interface film is b%, and the mass percentage content of phosphorus element in the solid electrolyte interface film is c%; wherein, 6 ⁇ 0.25a+b+0.5c ⁇ 10.
  • the secondary battery of the present application adds nitrogen-containing additives, silicon-containing and phosphorus-containing additives to the electrolyte, and controls the content of nitrogen, silicon and phosphorus in the solid electrolyte interface film (SEI film) on the surface of the negative electrode active material layer.
  • SEI film solid electrolyte interface film
  • the fast-charging electrolyte can enable lithium ions to be quickly transmitted in the electrolyte, thereby improving the fast-charging speed;
  • the control of the content of nitrogen, silicon and phosphorus in the above-mentioned SEI film improves the inorganic component ratio and structural uniformity of the SEI film, significantly reduces the transfer resistance of the SEI film to lithium ions, and thus significantly reduces the impedance of the SEI film, achieving rapid transmission of lithium ions in the SEI film, thereby significantly improving the fast-charging speed of the battery and improving the rate performance of the battery.
  • the secondary battery of the present application has at least one of the following advantages: excellent cycle performance, fast-charging performance and rate performance.
  • the mass percentage content of nitrogen in the solid electrolyte interface film is a%
  • the mass percentage content of silicon in the solid electrolyte interface film is b%
  • the mass percentage content of phosphorus in the solid electrolyte interface film is c%; wherein, 6 ⁇ 0.25a+b+0.5c ⁇ 10.
  • 0.25a+b+0.5c is 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, or any value therebetween.
  • the proportions of organic and inorganic components in the SEI film can be reasonable, and while ensuring the stability of the mechanical strength of the SEI film, the SEI film can have a loose and porous structure, allowing lithium ions to quickly transport through the interface, thereby achieving rapid lithium ion transport in the SEI film.
  • the value of 0.25a+b+0.5c is too large, it will make it difficult for the SEI film to maintain a stable state, causing the electrolyte to continue to undergo side reactions, and large solid byproducts to accumulate at the SEI film interface, increasing the transmission resistance of lithium ions and thus reducing fast charging performance.
  • the value of 0.25a+b+0.5c is too small, the SEI film will be denser, and the transmission resistance of lithium ions will also increase, which will also reduce fast charging performance.
  • the mass percentage content of nitrogen element in the solid electrolyte interface film is a%, 2 ⁇ a ⁇ 13.
  • a is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or any value therebetween.
  • 4 ⁇ a ⁇ 8 is a loose, porous and stable SEI membrane interface structure.
  • a value is too large (for example, more LiFSI)
  • it will induce more side reactions in the current collector, forming by-product accumulation, which hinders the transfer of lithium ions.
  • the a value is too small (for example, less LiFSI)
  • the transmission resistance of lithium ions in the electrolyte body will increase, reducing the fast charging speed.
  • the mass percentage content of silicon element in the solid electrolyte interface film is b%, and 0.01 ⁇ b ⁇ 4.
  • b is 0.01, 0.1, 0.5, 1, 2, 3, 4 or any value therebetween.
  • the mass percentage content of phosphorus element in the solid electrolyte interface membrane is c%, and 0.01 ⁇ c ⁇ 15.
  • c is 0.01, 0.1, 0.5, 1, 2, 3, 4, 6, 8, 10, 12, 15 or any value therebetween.
  • the nitrogen-containing additive includes a fluorinated lithium sulfonyl imide
  • the fluorinated lithium sulfonyl imide includes at least one of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium (fluorosulfonyl)(trifluoromethylsulfonyl)imide, lithium (fluorosulfonyl)(perfluorobutylsulfonyl)imide, lithium (trifluoromethylsulfonyl)(perfluorobutylsulfonyl)imide (LiFNFSI), and lithium bis(pentafluoroethylsulfonyl)imide (LiBETI).
  • the fluorinated lithium sulfonyl imide is a lithium imide salt with nitrogen as the central atom, which can improve the fast charging performance
  • the nitrogen-containing additive includes lithium bis(fluorosulfonyl)imide (LiFSI). Due to the large anionic radius of LiFSI, it is easier to dissociate into lithium ions, which can significantly improve the conductivity of the battery, thereby improving the fast charging performance of the battery, and at the same time, it can also improve the rate performance, safety, and high-temperature cycling stability of the secondary battery.
  • LiFSI lithium bis(fluorosulfonyl)imide
  • the weight percentage of the nitrogen-containing additive is 3% to 15% based on the weight of the electrolyte. In some embodiments, the weight percentage of the nitrogen-containing additive is 3%, 4%, 5%, 7%, 9%, 10%, 12%, 15%, or any value therebetween. In some embodiments, the weight percentage of the nitrogen-containing additive is 5% to 10%.
  • the silicon-containing and phosphorus-containing additives include at least one of the compounds represented by Formula I and Formula II:
  • R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C3-C6 alkylsilyl group, a substituted or unsubstituted C2-C3 alkenyl group, or a substituted or unsubstituted C6-C12 aryl group; wherein Formula I contains at least one substituted or unsubstituted C3-C6 alkylsilyl group, and Formula II contains at least one substituted or unsubstituted C3-C6 alkylsilyl group, and the substituents are each independently selected from fluorine.
  • Formula I represents a silicon-containing phosphate additive
  • Formula II represents a silicon-containing phosphite additive.
  • the phosphorus-containing additive can reduce the interfacial impedance between the positive and negative electrodes, thereby improving battery power performance.
  • using a nitrogen-containing additive in conjunction with the silicon- and phosphorus-containing additives can further enhance the stability of the SEI film, improving the cycle performance and rate capability of the secondary battery.
  • the silicon- and phosphorus-containing additive includes at least one of tris(trimethylsilyl)phosphate (TMSP) and tris(trimethylsilyl)phosphite (TMSPi). In some embodiments, the silicon- and phosphorus-containing additive includes tris(trimethylsilyl)phosphate (TMSP). This can further enhance the stability of the SEI film and improve the cycling performance of the battery.
  • TMSP tris(trimethylsilyl)phosphate
  • TMSPi tris(trimethylsilyl)phosphite
  • the weight percentage of the silicon-containing and phosphorus-containing additives is 0.01% to 2% based on the weight of the electrolyte. In some embodiments, the weight percentage of the silicon-containing and phosphorus-containing additives is 0.01%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, 2%, or any value therebetween. In some embodiments, the weight percentage of the phosphorus-containing additive is 0.5% to 2%.
  • the solid electrolyte interface film is a non-artificial film.
  • the solid electrolyte interface film (SEI film) is formed by a solid product generated by a reaction of specific components in the electrolyte at a specific voltage.
  • the nitrogen in the solid electrolyte interface film comes from a nitrogen-containing additive, and the silicon and phosphorus in the solid electrolyte interface film come from silicon- and phosphorus-containing additives.
  • the mass percentage contents of nitrogen, silicon, and phosphorus in the solid electrolyte interface film refer to the mass percentage contents of the corresponding elements measured on the surface of the negative electrode active material layer using an X-ray photoelectron spectrometer at a sputtering etching time of 0 seconds.
  • the electrolyte further comprises a first additive comprising at least one of a cyclic carbonate containing a carbon-carbon double bond, a fluorine-containing cyclic carbonate, a fluorine-containing phosphate, and an oxalate borate.
  • the first additive comprises at least one of vinylene carbonate (VC), fluoroethylene carbonate (FEC), lithium difluorophosphate (LiDFP), lithium difluorooxalatoborate (LiDFOB), and lithium dioxalatoborate (LiBOB).
  • the weight percentage of the first additive is 0.05% to 10% based on the weight of the electrolyte. In some embodiments, the weight percentage of the first additive is 0.05%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, or any value therebetween. In some embodiments, the weight percentage of the first additive is 0.1% to 5%.
  • the electrolyte further includes a lithium salt
  • the lithium salt includes at least one of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluorosulfonyl (LiTf), and lithium bis(fluoromalonate)borate (LiBFMB).
  • the weight percentage content of the lithium salt is 0.05% to 20% based on the weight of the electrolyte. In some embodiments, the weight percentage content of the lithium salt is 0.05%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any value therebetween. In some embodiments, the weight percentage content of the lithium salt is 1% to 15%.
  • the electrolyte further includes a solvent
  • the solvent includes at least one of a linear carbonate, a cyclic carbonate, and a carboxylate.
  • the linear carbonate is selected from at least one of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate and fluorinated linear carbonate.
  • the cyclic carbonate includes at least one of ethylene carbonate (EC), propylene carbonate and butylene carbonate.
  • the carboxylate is selected from at least one of methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolactone and fluorinated carboxylate.
  • the mass percentage content of the solvent is 0.05% to 80% based on the mass of the electrolyte. In some embodiments, the mass percentage content of the solvent is 0.05%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any value therebetween. In some embodiments, the mass percentage content of the solvent is 20% to 70%.
  • the positive electrode sheet includes a positive electrode active material layer, the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material includes lithium nickel transition metal oxide.
  • the lithium nickel transition metal oxide includes at least one of LiNi x M 1-x O 2 , where M includes at least one of cobalt, manganese, iron, chromium, titanium, zinc, vanadium, aluminum, zirconium, cerium, magnesium, calcium, molybdenum, strontium, tungsten, yttrium, lanthanum, silver, niobium, copper, and barium, and 0.7 ⁇ x ⁇ 0.98.
  • all transition metal elements in the positive electrode active material include transition element nickel (Ni) and other transition elements M.
  • the molar percentage content of nickel is based on the total molar amount of all transition metal elements (including transition element Ni and other transition elements M) in the positive electrode active material.
  • x is 0.7, 0.72, 0.74, 0.76, 0.78, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98, or any value therebetween.
  • the positive electrode active material includes at least one of lithium nickel oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese cobalt magnesium oxide, and lithium nickel manganese oxide.
  • the positive electrode active material layer further includes a binder, and optionally a conductive material.
  • the binder improves the bonding between the positive electrode active material particles and also improves the bonding between the positive electrode active material and the current collector.
  • the binder includes: polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyacrylic acid (PAA), polymethyl methacrylate (PMMA), polyimide (PI), polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1,1-difluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin or nylon, etc.
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PAA polyacrylic acid
  • PMMA polymethyl methacrylate
  • PI polyimide
  • polyvinyl alcohol hydroxypropyl cellulose
  • the conductive material includes: a carbon-based material, a metal-based material, a conductive polymer, 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 sheet further includes a positive electrode current collector, which can be a metal foil or a composite current collector.
  • a positive electrode current collector can be a metal foil or a composite current collector.
  • aluminum foil can be used.
  • the composite current collector can be obtained by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a polymer substrate.
  • the negative electrode sheet includes a negative electrode active material layer and a solid electrolyte interface film located on a surface of the negative electrode active material layer.
  • the negative electrode active material layer includes a negative electrode active material
  • the negative electrode active material includes a mixture of a silicon-based material and at least one material selected from a carbon-based material, a tin-based material, a phosphorus-based material, and metallic lithium.
  • the silicon-based material comprises at least one of silicon, a silicon alloy, a silicon oxide, and a silicon carbon compound.
  • 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, a tin oxide, and a tin alloy.
  • the phosphorus-based material comprises phosphorus and/or a phosphorus complex.
  • the mass percentage of the silicon-based material is 3% to 40% based on the mass of the negative electrode active material. In some embodiments, the mass percentage of the silicon-based material is 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, or any value therebetween.
  • the negative electrode active material layer further comprises a binder and a conductive agent.
  • the binder comprises styrene-butadiene rubber (SBR), sodium carboxymethyl cellulose (CMC), polyacrylic acid (PAA), 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, acrylated styrene-butadiene rubber, epoxy resin, or nylon.
  • SBR styrene-butadiene rubber
  • CMC sodium carboxymethyl cellulose
  • PAA polyacrylic acid
  • polyvinyl alcohol hydroxypropyl cellulose
  • diacetyl cellulose polyvinyl chloride
  • the conductive agent includes: a carbon-based material, a metal-based material, a conductive polymer, 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 plate 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.
  • a separator is provided between the positive and negative electrode plates to prevent short circuits.
  • the material and shape of the separator that can be used in the embodiments of the present application are not particularly limited and can be any known prior art material.
  • the separator comprises a polymer or inorganic material that is stable with the electrolyte of the present application.
  • the separator may include a substrate layer and a surface treatment layer.
  • the substrate layer is a non-woven fabric, film, or composite film having a porous structure
  • the material of the substrate layer includes at least one of polyethylene, polypropylene, polyethylene terephthalate, or polyimide.
  • polypropylene porous film, polyethylene porous film, polypropylene non-woven fabric, polyethylene non-woven fabric, or polypropylene-polyethylene-polypropylene porous composite film can be used.
  • a surface treatment layer is provided 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 includes a polymer, 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 method for preparing the secondary battery includes providing an electrode assembly, injecting liquid, packaging, and forming.
  • the forming temperature is 40° C. to 50° C., for example, 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., or 49° C.
  • the formation comprises: charging to 4.25V at 0.05C current and standing for 60min, then charging to 4.25V at 0.1C current, and then discharging to 3.0V at 0.2C current under the conditions of a temperature of 40°C-50°C, for example, 45°C, and a pressure of 150kgf-250kgf, for example, 210kgf.
  • the secondary battery is formed.
  • the solid electrolyte interface membrane is formed after the secondary battery is formed.
  • nitrogen-containing additives, silicon-containing additives, and phosphorus-containing additives are reduced on the surface of the negative electrode active material to form an SEI film.
  • the absolute content of nitrogen, silicon, and phosphorus in the SEI film will be different from the absolute content of nitrogen, silicon, and phosphorus in the SEI film after formation, but the relative content, that is, the mass percentage of nitrogen, silicon, and phosphorus in the SEI film, will still be between 2% and 12%, between 0.01% and 4%, and between 0.01% and 15%, respectively.
  • the secondary battery is a lithium secondary battery or a sodium secondary battery.
  • the lithium secondary battery includes: 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 packaging, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging 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 also provides a battery module.
  • the battery module includes the aforementioned secondary battery.
  • the battery module of the present application utilizes the aforementioned secondary battery and therefore has at least the same advantages as the aforementioned secondary battery.
  • the battery module of the present application may include multiple secondary batteries, the specific number of which can be adjusted based on the application and capacity of the battery module.
  • the present application further provides a battery pack comprising the above-mentioned battery module.
  • the number of battery modules contained 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 the secondary battery.
  • the device includes an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, a power storage system, etc.
  • a battery pack or battery module may be used.
  • the device may be a mobile phone, a tablet computer, a laptop computer, etc.
  • the device is generally required to be lightweight and thin, and may use a secondary battery as a power source.
  • conductive agent acetylene black binder styrene-butadiene rubber SBR
  • thickener sodium carboxymethyl cellulose CMCNa thickener sodium carboxymethyl cellulose CMCNa
  • PAA polyacryl
  • Diaphragm PP/PE/PP (polypropylene/polyethylene/polypropylene) three-layer composite diaphragm.
  • Preparation of lithium-ion secondary batteries The positive electrode sheet, separator (PP/PE/PP three-layer composite film), and negative electrode sheet prepared above are overlapped in sequence, with the separator located between the positive electrode sheet and the negative electrode sheet, and wound to obtain a bare cell. After the bare cell is fully dried, it is placed in a cylindrical (e.g., 18650 cylindrical) steel shell, and then the electrolyte prepared above is injected and sealed.
  • a cylindrical e.g., 18650 cylindrical
  • the battery undergoes pre-charging, high-temperature infiltration, formation (formation conditions are: temperature 45°C, 0.05C current charging to 3V and then standing for 5 minutes, then 0.1C charging to 3.5V and standing for 5 minutes, and then 0.33C charging to 4.0V) and high-temperature aging, and then regular capacity distribution is performed.
  • Examples 2 to 7 and Comparative Examples 1 to 3 are achieved by adjusting the types and contents of lithium salts, solvents, and additives in the electrolyte on the basis of Example 1. Specific adjustment measures and detailed data are shown in Table 1.
  • XPS X-ray photoelectron spectrometer
  • the lithium-ion battery was discharged at a current of 0.1C to 2.5V.
  • the battery was then disassembled in an argon-filled glove box to obtain the electrode sheets.
  • the resulting electrode sheets were cut into 8mm x 8mm test samples and soaked and cleaned in a low-boiling-point dimethyl carbonate (DMC) solvent for half an hour. After complete drying, they were attached to the XPS sample stage with the surface of the negative electrode active material layer facing away from the current collector facing upward. Measurements were performed without exposure to the atmosphere.
  • DMC dimethyl carbonate
  • the mass percentage content of nitrogen, silicon, and phosphorus in the negative electrode SEI film can be obtained by the above-mentioned test method. More specifically, Figures 1 to 3 are the XPS spectra of nitrogen, silicon, and phosphorus obtained by testing the negative electrode SEI film in Example 1. The peak areas in the spectra are integrated to obtain the peak area of each element, and the mass percentage content of the corresponding element is obtained by normalizing the peak area of each element.
  • this fast-charging electrolyte enables rapid lithium ion transport within the electrolyte, thereby increasing the fast-charging speed. Furthermore, by controlling the content of nitrogen, silicon, and phosphorus in the SEI film, the inorganic component ratio and structural uniformity of the SEI film are increased, significantly reducing the SEI film's resistance to lithium ion transfer, and thus significantly reducing the SEI film's impedance, enabling rapid lithium ion transport within the SEI film, thereby significantly increasing the battery's fast-charging speed and improving the battery's rate performance. Based on the above improvements, the secondary battery of the present application has at least one of the following advantages: excellent fast-charging performance and rate performance.

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Abstract

本申请涉及二次电池和装置。本申请的二次电池包括正极极片、负极极片和电解液；电解液包括含氮添加剂、含硅和含磷添加剂；负极极片包括负极活性材料层以及位于负极活性材料层表面的固体电解质界面膜；采用X射线光电子能谱仪在溅射刻蚀时间0秒下测试，固体电解质界面膜中氮元素的质量百分比含量为a％，固体电解质界面膜中硅元素的质量百分比含量为b％，固体电解质界面膜中磷元素的质量百分比含量为c％；其中，5.5≤0.25a+b+0.5c≤10。由此，本申请的二次电池具有优异的循环性能、快充性能和倍率性能。

Description

二次电池和装置
本申请要求2024年04月18日提交的，名称为“二次电池和装置”的中国专利申请CN202410467777.2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
近年来，锂离子二次电池在手机、电脑、储能、电动工具、电动汽车领域的应用越来越广泛。锂离子二次电池在使用过程中，拥有更快的充电速度一直是人们追求的目标之一，而快充技术的发展也能够缓解电动汽车用户的补能焦虑。锂离子传输速度是快充性能的重要参考指标，从锂离子传输路径来看，电解液是锂离子充放电过程中影响其传输速度的重要因素之一，这是因为电解液是联系正负极的重要介质，是锂离子传输的重要场所，由此，快充型电解液的研究是快充电池的重要发展方向。
然而，目前的二次电池和装置仍有待改进。
发明内容
发明人发现，电解液添加剂会在正负极界面形成固体电解质界面膜，这层界面膜是锂离子传递过程中的较大阻力之一，进而影响二次电池的快充性能。此外，电解液本体是锂离子传输的重要场所，其电解液添加剂的类别及含量也会影响电池的快充速度。为了缓解或解决上述提及问题中至少一个，本申请提供了一种二次电池和装置，用以解决现有技术中充电速度慢的技术问题，该二次电池包括快充型电解液，其中，快充型电解液包括含氮添加剂、含硅和含磷添加剂，由此，能够使锂离子在电解液本体快速传输，且能在负极极片界面处形成阻力较小的特殊固体电解质界面膜，使锂离子在界面膜也能实现快速传输，从而显著提升电池的快充速度。
本申请一方面提供了一种二次电池，该二次电池包括正极极片、负极极片和电解液；所述电解液包括含氮添加剂、含硅和含磷添加剂；所述负极极片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射线光电子能谱仪在溅射刻蚀时间0秒下测试，所述固体电解质界面膜中氮元素的质量百分比含量为a％，所述固体电解质界面膜中硅元素的质量百分比含量为b％，所述固体电解质界面膜中磷元素的质量百分比含量为c％；其中，6≤0.25a+b+0.5c≤10。
本申请另一方面提供了一种装置，所述装置包括前面所述的二次电池。
本申请的有益效果为：
本申请的二次电池通过在电解液中添加含氮添加剂、含硅和含磷添加剂，并控制负极活性材料层表面的固体电解质界面膜(SEI膜)中氮元素、硅元素、磷元素的含量，一方面，该快充型电解液能够使锂离子在电解液中快速传输，进而提升快充速度；另一方面，上述SEI膜中氮元素、硅元素、磷元素的含量的控制，提升了SEI膜的无机成分占比和结构均匀性，显著减小了SEI膜对锂离子的传递阻力，进而显著降低了SEI膜的阻抗，实现锂离子在SEI膜中的快速传输，从而显著提升电池的快充速度，改善电池的倍率性能。基于以上改善，本申请的二次电池具有以下优点的至少之一：优异的循环性能、快充性能和倍率性能。
附图说明：
图1为根据本申请一种实施方式的负极极片SEI膜的XPS图谱中氮元素的分峰图谱。
图2为根据本申请一种实施方式的负极极片SEI膜的XPS图谱中硅元素的分峰图谱。
图3为根据本申请一种实施方式的负极极片SEI膜的XPS图谱中磷元素的分峰图谱。
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“中的至少一者”、“中的至少一个”、“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中的至少一者”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中的至少一者”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。
术语“C1-C3烷基”包括但不限于：甲基、乙基、正丙基、异丙基、环丙基等。
术语“C3-C6烷基硅基”指具有3-6个碳原子的硅基，包括但不限于：三甲基硅基等。
术语“C2-C3烯基”包括但不限于：乙烯基、丙烯基等。
术语“C6-C12芳基”包括但不限于：苯基或萘基等。
术语“取代或未取代的”指在该术语后面记载的官能团可以具有或不具有取代基。例如，“取代或未取代的C1-C3烷基”是指具有取代基的C1-C3烷基或者非取代的C1-C3烷基。其中，取代基的个数可以是1个或2个以上，取代基包括卤素(例如氟)、烷基或芳基中的至少一种。应当理解地是，当取代基的个数大于1时，各取代基可以相同或不同。
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极片、负极极片和电解液；所述电解液包括含氮添加剂、含硅和含磷添加剂；所述负极极片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射线光电子能谱仪在溅射刻蚀时间0秒下测试，所述固体电解质界面膜中氮元素的质量百分比含量为a％，所述固体电解质界面膜中硅元素的质量百分比含量为b％，所述固体电解质界面膜中磷元素的质量百分比含量为c％；其中，6≤0.25a+b+0.5c≤10。
由此，本申请的二次电池通过在电解液中添加含氮添加剂、含硅和含磷添加剂，并控制负极活性材料层表面的固体电解质界面膜(SEI膜)中氮元素、硅元素、磷元素的含量，一方面，该快充型电解液能够使锂离子在电解液中快速传输，进而提升快充速度；另一方面，上述SEI膜中氮元素、硅元素、磷元素的含量的控制，提升了SEI膜的无机成分占比和结构均匀性，显著减小了SEI膜对锂离子的传递阻力，进而显著降低了SEI膜的阻抗，实现锂离子在SEI膜中的快速传输，从而显著提升电池的快充速度，改善电池的倍率性能。基于以上改善，本申请的二次电池具有以下优点的至少之一：优异的循环性能、快充性能和倍率性能。
在一些实施方式中，采用X射线光电子能谱仪在溅射刻蚀时间0秒下测试，所述固体电解质界面膜中氮元素的质量百分比含量为a％，所述固体电解质界面膜中硅元素的质量百分比含量为b％，所述固体电解质界面膜中磷元素的质量百分比含量为c％；其中，6≤0.25a+b+0.5c≤10。在一些实施方式中，0.25a+b+0.5c为6、6.5、7、7.5、8、8.5、9、9.5、10或它们之间的任意值。在一些实施方式中，7≤0.25a+b+0.5c≤9。由此，能够使得SEI膜中的有机、无机成分占比合理，能在保证SEI膜机械强度维持稳定的同时，使得SEI膜具有性能疏松多孔的结构，使锂离子能快速传输通过界面，实现锂离子在SEI膜中的快速传输。当0.25a+b+0.5c值过大，会造成SEI膜难以维持稳定状态，使电解液持续发生副反应，SEI膜界面堆积较大的固态副产物，增加锂离子的传输阻力，进而降低快充性能。当0.25a+b+0.5c值过小，会造成SEI膜较致密，锂离子的传输阻力也会增加，也会降低快充性能。
在一些实施方式中，所述固体电解质界面膜中氮元素的质量百分比含量为a％，2≤a≤13。在一些实施方式中，a为2、3、4、5、6、7、8、9、10、11、12、13或它们之间的任意值。在一些实施方式中，4≤a≤8。由此，能够形成疏松多孔且稳定的SEI膜界面结构，有利于锂离子快速通过。当a值过大(例如，LiFSI较多)，会诱发集流体发生较多副反应，形成副产物堆积，阻碍锂离子传递。当a值过小(例如，LiFSI较少)，锂离子在电解液本体的传输阻力将增大，降低快充速度。
在一些实施方式中，所述固体电解质界面膜中硅元素的质量百分比含量为b％，0.01≤b≤4。在一些实施方式中，b为0.01、0.1、0.5、1、2、3、4或它们之间的任意值。在一些实施方式中，1≤b≤3。由此，能够形成疏松多孔且稳定的SEI膜界面结构，有利于锂离子快速通过。当b值过大，会造成SEI膜不稳定，新增的颗粒表面会诱发电解液持续发生副反应，SEI膜界面堆积较大的固态副产物，增加锂离子的传输阻力，进而降低快充性能。当b值过小，会造成SEI膜较致密，锂离子的传输阻力也会增加，也会降低快充性能。
在一些实施方式中，所述固体电解质界面膜中磷元素的质量百分比含量为c％，0.01≤c≤15。在一些实施方式中，c为0.01、0.1、0.5、1、2、3、4、6、8、10、12、15或它们之间的任意值。在一些实施方式中，3≤c≤10。由此，能够形成疏松多孔且稳定的SEI膜界面结构，有利于锂离子快速通过。当c值过大，会造成SEI膜不稳定，新增的颗粒表面会诱发电解液持续发生副反应，SEI膜界面堆积较大的固态副产物，增加锂离子的传输阻力，进而降低快充性能。当c值过小，会造成SEI膜较致密，锂离子的传输阻力也会增加，也会降低快充性能。
在一些实施方式中，所述含氮添加剂包括含氟磺酰亚胺锂，所述含氟磺酰亚胺锂包括双氟磺酰亚胺锂(LiFSI)、双三氟甲基磺酰亚胺锂(LiTFSI)、(氟磺酰)(三氟甲基磺酰)亚胺锂、(氟磺酰)(全氟丁基磺酰)亚胺锂、(三氟甲基磺酰)(全氟丁基磺酰)亚胺锂(LiFNFSI)和双(五氟乙基磺酰)亚胺锂(LiBETI)中的至少一种。由此，含氟磺酰亚胺锂是以氮为中心原子的亚胺锂盐，能够提升电池的快充性能，显著改善电池倍率性能。
在一些实施方式中，所述含氮添加剂包括双氟磺酰亚胺锂(LiFSI)。由于LiFSI的阴离子半径较大，较易于解离出锂离子，进而能够显著提高电池的电导率，从而提升电池的快充性能，同时，还能够提升二次电池的倍率性能、安全性、高温循环稳定性。
在一些实施方式中，基于所述电解液的质量，所述含氮添加剂的质量百分比含量为3％～15％。在一些实施方式中，所述含氮添加剂的质量百分比含量为3％、4％、5％、7％、9％、10％、12％、15％或它们之间的任意值。在一些实施方式中，所述含氮添加剂的质量百分比含量为5％～10％。
在一些实施方式中，所述含硅和含磷添加剂包括式I和式II所示的化合物中的至少一种：
其中，式I和式II中，R3、R4、R5、R6、R7、R8各自独立地选自取代或未取代的C1-C3烷基、取代或未取代的C3-C6烷基硅基、取代或未取代的C2-C3烯基或者取代或未取代的C6-C12芳基；其中，式I中含有至少一个取代或未取代的C3-C6烷基硅基，式II中含有至少一个取代或未取代的C3-C6烷基硅基，所述取代基各自独立地选自氟。
在一些实施方式中，式I为含硅磷酸酯添加剂，式II为含硅亚磷酸酯添加剂。由此，上述含磷添加剂的添加剂，可以降低正负极界面阻抗，提升了电池功率性能。此外，将含氮添加剂与上述含硅和含磷添加剂共同使用，可以进一步提升SEI膜的稳定性，提升二次电池的循环性能和倍率性能。
在一些实施方式中，所述含硅和含磷添加剂包括三(三甲基硅基)磷酸酯(TMSP)和三(三甲基硅基)亚磷酸酯(TMSPi)中的至少一种。在一些实施方式中，所述含硅和含磷添加剂包括三(三甲基硅基)磷酸酯(TMSP)。由此，可以进一步提升SEI膜的稳定性，提高电池的循环性能。
在一些实施方式中，基于所述电解液的质量，所述含硅和含磷添加剂的质量百分比含量为0.01％～2％。在一些实施方式中，所述含硅和含磷添加剂的质量百分比含量为0.01％、0.1％、0.3％、0.5％、0.7％、0.9％、1％、1.1％、1.3％、1.5％、1.7％、1.9％、2％或它们之间的任意值。在一些实施方式中，所述含磷添加剂的质量百分比含量为0.5％～2％。
在一些实施方式中，所述固体电解质界面膜为非人造膜。在一些实施方式中，所述固体电解质界面膜(SEI膜)由所述电解液中的特定成分在特定电压下发生反应生成的固态产物形成。在一些实施方式中，所述固态电解质界面膜中的氮元素来含氮添加剂，所述固态电解质界面膜中的硅元素和磷元素来自含硅和含磷添加剂。
在一些实施方式中，固体电解质界面膜中氮元素、硅元素和磷元素的质量百分比含量是指负极活性材料层表面采用X射线光电子能谱仪在溅射刻蚀时间0秒下测试得到的对应元素的质量百分比含量。
在一些实施方式中，所述电解液还包括第一添加剂，所述第一添加剂包括含碳碳双键的环状碳酸酯、含氟的环状碳酸酯、含氟磷酸盐和草酸硼酸盐中的至少一种。在一些实施方式中，所述第一添加剂包括碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、二氟磷酸锂(LiDFP)、二氟草酸硼酸锂(LiDFOB)和二草酸硼酸锂(LiBOB)中的至少一种。
在一些实施方式中，基于所述电解液的质量，所述第一添加剂的质量百分比含量为0.05％～10％。在一些实施方式，所述第一添加剂的质量百分比含量为0.05％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、6％、7％、8％、9％、10％或它们之间的任意值。在一些实施方式，所述第一添加剂的质量百分比含量为0.1％～5％。
在一些实施方式中，所述电解液还包括锂盐，所述锂盐包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、三氟磺酰锂(LiTf)和双(氟代丙二酸)硼酸锂(LiBFMB)中的至少一种。
在一些实施方式中，基于所述电解液的质量，所述锂盐的质量百分比含量为0.05％～20％。在一些实施方式，所述锂盐的质量百分比含量为0.05％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％或它们之间的任意值。在一些实施方式，所述锂盐的质量百分比含量为1％～15％。
在一些实施方式中，所述电解液还包括溶剂，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(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯、碳酸二丙酯、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(EC)、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，基于所述电解液的质量，所述溶剂的质量百分比含量为0.05％～80％。在一些实施方式，所述溶剂的质量百分比含量为0.05％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、6％、7％、8％、9％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％或它们之间的任意值。在一些实施方式，所述溶剂的质量百分比含量为20％～70％。
在一些实施方式中，所述正极极片包括正极活性材料层，所述正极活性材料层包括正极活性材料，所述正极活性材料包括锂镍过渡金属氧化物。
在一些实施方式中，所述锂镍过渡金属氧化物包括LiNixM1-xO2中的至少一种，M包括钴、锰、铁、铬、钛、锌、钒、铝、锆、铈、镁、钙、钼、锶、钨、钇、镧、银、铌、铜和钡中的至少一种，0.7≤x≤0.98。可以理解的是，正极活性材料中所有的过渡金属元素包括过渡元素镍元素(Ni)和其他过渡元素M。镍元素的摩尔百分比含量是基于正极活性材料中所有的过渡金属元素(包括过渡元素Ni和其他过渡元素M)的摩尔总量的占比。
在一些实施方式中，x为0.7、0.72、0.74、0.76、0.78、0.8、0.82、0.84、0.86、0.88、0.9、0.92、0.94、0.96、0.98或它们之间的任意值。
在一些实施方式中，正极活性材料包括锂镍氧化物、锂镍钴铝氧化物、锂镍钴锰氧化物、锂镍锰钴镁氧化物和锂镍锰氧化物中的至少一种。
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材料。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：聚偏二氟乙烯(PVDF)、聚丙烯腈(PAN)、聚丙烯酸(PAA)、聚甲基丙烯酸甲酯(PMMA)、聚酰亚胺(PI)、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，导电材料包括：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，所述正极极片还包括正极集流体，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得到。
在一些实施方式中，所述负极极片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。
在一些实施方式中，所述负极活性材料层包括负极活性材料，所述负极活性材料包括硅基材料和选自碳基材料、锡基材料、磷基材料、金属锂中的至少一种材料的混合物。
在一些实施方式中，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。在一些实施方式中，所述锡基材料包括锡、锡氧化物和锡合金中的至少一种。在一些实施方式中，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百分比含量为3％～40％。在一些实施方式中，所述硅基材料的质量百分比含量为3％、5％、8％、10％、12％、15％、18％、20％、25％、30％、35％、40％或它们之间的任意值。
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：丁苯橡胶(SBR)、羧甲基纤维素钠(CMC)、聚丙烯酸(PAA)、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、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：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，所述负极极片还包括负极集流体，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，正极极片与负极极片之间设有隔膜以防止短路。可用于本申请的实施例的隔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℃，例如为41℃、42℃、43℃、44℃、45℃、46℃、47℃、48℃或49℃。
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210kgf的条件下、0.05C电流充电至4.25V静置60min，随后0.1C充电至4.25V，然后0.2C放电至3.0V。
在一些实施方式中，所述二次电池经过化成。在一些实施方式中，所述固体电解质界面膜通过二次电池化成后形成。在二次电池的化成过程中含氮添加剂、含硅和含磷添加剂在负极活性材料表面还原形成SEI膜。二次电池经过多次循环后，SEI膜中的氮元素、硅元素和磷元素各自的绝对含量与化成后SEI膜中氮元素、硅元素和磷元素各自的绝对含量会有不同，但是相对含量即SEI膜中氮元素、硅元素和磷元素各自的质量百分比含量仍分别在2％～12％之间、0.01％～4％之间、0.01％～15％之间。
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：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。
在一些实施方式中，所述装置包括：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。
在另一些实施方式中，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。
实施例及对比例
实施例1
正极极片的制备步骤为：将正极活性材料LiNi0.9Co0.06Mn0.04O2、CNT(导电剂碳纳米管)/乙炔黑、粘结剂聚偏氟乙烯PVDF，按重量比例LiNi0.9Co0.06Mn0.04O2：CNT/乙炔黑：PVDF＝95：(2.0/1.0)：2在N-甲基吡咯烷酮NMP中，经充分匀浆后涂布于12μm厚的铝集流体上，随后经烘干、辊压、热压等步骤得到正极极片。
负极极片的制备步骤为：将负极活性材料硅氧化物(SiOx，0.5≤x≤1.5)-石墨复合物(Si/C＝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95：2：1.5：1：0.5加入去离子水中，经充分匀浆后涂布于8μm厚铜集流体上，随后经烘干、辊压、热压等步骤得到负极极片。
电解液的制备：在充满氩气的手套箱(H2O＜0.1ppm，O2＜0.1ppm)中，将锂盐LiPF6充分溶解在EC/DMC/EMC(碳酸乙烯酯/碳酸二乙酯/碳酸甲乙酯)＝20/70/10的混合溶液，配置成锂盐LiPF6的质量百分含量为1.5％的溶液，随后加入15％的含氮添加剂双氟磺酰亚胺锂(LiFSI)和2％的含硅和含磷添加剂三(三甲基硅基)磷酸酯(TMSP)，再加入第二添加剂8％的氟代碳酸乙烯酯(FEC)和0.5％的碳酸亚乙烯酯(VC)，搅拌均匀后得到电解液。
隔膜：采用PP/PE/PP(聚丙烯/聚乙烯/聚丙烯)三层复合隔膜。
锂离子二次电池的制备：将上述制备的正极极片、隔膜(PP/PE/PP三层复合膜)、负极极片依次层层交叠，隔膜处于正极极片、负极极片中间，卷绕得到裸电芯，将裸电芯经充分干燥后置于圆柱(例如18650圆柱)钢壳中，随后注入上述制备的电解液并封口，电池经过预充、高温浸润、化成(化成条件是：温度45℃、0.05C电流充电至3V后静置5min，随后0.1C充电至3.5V后静置5min，然后0.33C充电至4.0V)和高温老化后，进行常分容。
实施例2～7以及对比例1～3
实施例2～7以及对比例1～3是在实施例1的基础上通过调整电解液中锂盐、溶剂和添加剂的种类和含量等来实现的，具体调整措施和详细数据见表1。
表1
测试方法
1、X射线光电子能谱仪(XPS)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。将得到的电极极片裁剪成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，以计算每种组分的原子。
例如，通过上述测试方法可以得到负极极片SEI膜中氮元素、硅元素、磷元素的质量百分比含量。更具体的，图1～3分别为实施例1中对负极极片SEI膜进行测试得到的氮元素、硅元素、磷元素的XPS图谱，其中，分别对图谱中的峰面积进行积分计算，可以得到每个元素的峰面积，根据每个元素的峰面积通过归一化计算得到对应元素的质量百分比含量。
2、阻抗(DCR)测试
25±2℃环境中，将锂离子二次电池静止5分钟，0.5C充电至4.2V，静止5分钟，0.5C放电至50％SOC，静止60分钟，记录末端电位为V1，2C脉冲充电10秒，记录末端电位为V2，静止5分钟，2C充电电流为A，则DCR＝(V1-V2)/A。
3、4C倍率充电容量保持率测试
25±2℃环境中，将锂离子二次电池静止5分钟，0.5C放电至2.5V，静止5分钟，0.5C充电至4.2V，静止5分钟，记录充电容量为C0；0.5C放电至2.5V，静止5分钟，4C充电至4.2V，静止5分钟，记录充电容量为C1；则4C倍率充电容量保持率A＝C1/C0。
4、电解液电导率测试
25±2℃环境中，取上述制备好的电解液，利用电导率测定仪进行测试。
测试结果
表2
由实施例1～7、对比例1～3可知，该快充型电解液能够使锂离子在电解液中快速传输，进而提升快充速度；并且，通过SEI膜中氮元素、硅元素、磷元素的含量的控制，提升了SEI膜的无机成分占比和结构均匀性，显著减小了SEI膜对锂离子的传递阻力，进而显著降低了SEI膜的阻抗，实现锂离子在SEI膜中的快速传输，从而显著提升电池的快充速度，改善电池的倍率性能。基于以上改善，本申请的二次电池具有以下优点的至少之一：优异的快充性能和倍率性能。
比较对比例1和实施例1～7，由于未加入含硅和含磷添加剂TMSP，造成SEI膜中未检测到硅元素的含量，进而0.25a+b+0.5c的值过小，则造成SEI膜较致密，锂离子的传输阻力也会增加，电池阻抗显著增大，快充性能变差，容量保持率也显著降低。
比较对比例2和实施例1～7，由于未加入含氮添加剂LiFSI，造成SEI膜中未检测到氮元素的含量，且SEI膜中磷元素含量过大，进而0.25a+b+0.5c的值过大，使得SEI膜稳定性差，其界面会堆积较大的固态副产物，增加锂离子的传输阻力，电池阻抗显著增大，且电解液电导率显著降低，快充性能变差，容量保持率也显著降低。
比较对比例3和实施例1～7，由于0.25a+b+0.5c的值过小，则造成SEI膜较致密，锂离子的传输阻力会增加，电池阻抗显著增大，快充性能变差，容量保持率也显著降低。
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 (20)

  1. 一种二次电池，其特征在于，包括正极极片、负极极片和电解液；
    所述电解液包括含氮添加剂、含硅和含磷添加剂；
    所述负极极片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射线光电子能谱仪在溅射刻蚀时间0秒下测试，所述固体电解质界面膜中氮元素的质量百分比含量为a％，所述固体电解质界面膜中硅元素的质量百分比含量为b％，所述固体电解质界面膜中磷元素的质量百分比含量为c％；
    其中，5.5≤0.25a+b+0.5c≤10。
  2. 根据权利要求1所述的二次电池，其特征在于，6≤0.25a+b+0.5c≤8。
  3. 根据权利要求1或2所述的二次电池，其特征在于，2≤a≤13。
  4. 根据权利要求1或2所述的二次电池，其特征在于，0.01≤b≤4。
  5. 根据权利要求1或2所述的二次电池，其特征在于，0.01≤c≤15。
  6. 根据权利要求3所述的二次电池，其特征在于，4≤a≤8。
  7. 根据权利要求4所述的二次电池，其特征在于，1≤b≤3。
  8. 根据权利要求5所述的二次电池，其特征在于，3≤c≤10。
  9. 根据权利要求1或2所述的二次电池，其特征在于，所述含氮添加剂包括含氟磺酰亚胺锂，所述含氟磺酰亚胺锂包括双氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂、(氟磺酰)(三氟甲基磺酰)亚胺锂、(氟磺酰)(全氟丁基磺酰)亚胺锂、(三氟甲基磺酰)(全氟丁基磺酰)亚胺锂和双(五氟乙基磺酰)亚胺锂中的至少一种。
  10. 根据权利要求1或2所述的二次电池，其特征在于，所述含硅和含磷添加剂包括式I和式II所示的化合物中的至少一种：
    其中，式I和式II中，R3、R4、R5、R6、R7、R8各自独立地选自取代或未取代的C1-C3烷基、取代或未取代的C3-C6烷基硅基、取代或未取代的C2-C3烯基或者取代或未取代的C6-C12芳基；其中，式I中含有至少一个取代或未取代的C3-C6烷基硅基，式II中含有至少一个取代或未取代的C3-C6烷基硅基，所述取代基各自独立地选自氟。
  11. 根据权利要求9所述的二次电池，其特征在于，所述含氮添加剂包括双氟磺酰亚胺锂。
  12. 根据权利要求10所述的二次电池，其特征在于，所述含硅和含磷添加剂包括三(三甲基硅基)磷酸酯和三(三甲基硅基)亚磷酸酯中的至少一种。
  13. 根据权利要求1所述的二次电池，其特征在于，所述固体电解质界面膜为非人造膜。
  14. 根据权利要求1或2所述的二次电池，其特征在于，基于所述电解液的质量，所述含氮添加剂的质量百分比含量为3％～15％；
    基于所述电解液的质量，所述含硅和含磷添加剂的质量百分比含量为0.01％～2％。
  15. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液还包括第二添加剂，所述第二添加剂包括含碳碳双键的环状碳酸酯、含氟的环状碳酸酯、含氟磷酸盐和草酸硼酸盐中的至少一种；基于所述电解液的质量，所述第二添加剂的质量百分比含量为0.05％～10％。
  16. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液还包括锂盐，所述锂盐包括六氟磷酸锂、四氟硼酸锂、三氟磺酰锂和双(氟代丙二酸)硼酸锂中的至少一种；基于所述电解液的质量，所述锂盐的质量百分比含量为0.05％～20％。
  17. 根据权利要求1或2所述的二次电池，其特征在于，所述电解液还包括溶剂，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；基于所述电解液的质量，所述溶剂的质量百分比含量为0.05％～80％。
  18. 根据权利要求1或2所述的二次电池，其特征在于，所述固体电解质界面膜由所述负极活性材料与所述电解液反应形成。
  19. 根据权利要求1或2所述的二次电池，其特征在于，所述正极极片包括正极活性材料层，所述正极活性材料层包括正极活性材料，所述正极活性材料包括锂镍过渡金属氧化物，所述锂镍过渡金属氧化物包括LiNixM1-xO2中的至少一种，M包括钴、锰、铁、铬、钛、锌、钒、铝、锆、铈、镁、钙、钼、锶、钨、钇、镧、银、铌、铜和钡中的至少一种，0.7≤x≤0.98；和/或
    所述负极活性材料层包括负极活性材料，所述负极活性材料包括硅基材料和选自碳基材料、锡基材料、磷基材料、金属锂中的至少一种材料的混合物；其中，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，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/或磷碳复合物；基于所述负极活性材料的质量，所述硅基材料的质量百分比含量为3％～40％；和/或
    所述二次电池经过化成。
  20. 一种装置，其特征在于，包括权利要求1至19中任一项所述的二次电池。
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