WO2023109708A1 - 一种钠基双离子电池及其制备方法 - Google Patents

一种钠基双离子电池及其制备方法 Download PDF

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WO2023109708A1
WO2023109708A1 PCT/CN2022/138199 CN2022138199W WO2023109708A1 WO 2023109708 A1 WO2023109708 A1 WO 2023109708A1 CN 2022138199 W CN2022138199 W CN 2022138199W WO 2023109708 A1 WO2023109708 A1 WO 2023109708A1
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carbon
electrolyte
negative electrode
sodium
electrode material
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English (en)
French (fr)
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张帆
唐永炳
周立玉
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深圳先进技术研究院
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the technical field of batteries, in particular to a sodium-based double-ion battery and a preparation method thereof.
  • the sodium-based dual-ion battery is a kind of sodium-ion battery.
  • the positive electrode uses anion-intercalated graphite-like carbon materials, and the negative electrode uses sodium-ion battery negative electrode materials, so the cost can be further reduced. It has the advantages of environmental protection and easy recycling.
  • the Chinese patent with the publication number of CN108172816A in the prior art discloses a sodium-based dual-ion battery and its preparation method. Since the negative electrode is an adsorption mechanism, it solves the serious volume expansion or dusting of the traditional sodium-electrode negative electrode active material due to the insertion and extraction of sodium ions.
  • the capacity of this adsorption type material is low, so that the energy density of the battery is low;
  • the Chinese patent with the publication number CN107565158A discloses an electrolyte for a sodium ion battery,
  • the preparation method and the sodium-ion battery comprising the electrolyte for the sodium-ion battery have low price, high safety, low sensitivity to moisture and low environmental requirements for the battery, but the negative electrode material and the electrolyte are not tested.
  • Pre-sodiumization treatment for sodium ion storage cannot reduce the irreversible capacity loss in the early cycle.
  • the present invention provides a sodium-based double-ion battery and a preparation method thereof to solve the problems raised in the above-mentioned background technology.
  • a sodium-based dual-ion battery including a negative electrode, a positive electrode, a diaphragm and an electrolyte;
  • the negative electrode includes a negative electrode current collector and a negative electrode material, and the negative electrode material contains a sodium salt additive;
  • the electrolyte includes a sodium salt electrolyte, an organic solvent and an additive, and the additive in the electrolyte is a sodium salt additive and an organic solvent additive The combination; the concentration of the electrolyte is above 3mol/L;
  • the sodium salt additive in the negative electrode and electrolyte is selected from NaNO 3 , NaBOB, NaDFOB, DTPA-5Na, NaN 3 , Na 3 P, Na 2 CO 3 , NaNO 2 , EDTA-4Na, Na 3 Sb, Na2C 2 O 4.
  • NaB(CN) 4 NaPO 2 F 2 , Na 2 SO 3 , NaOCH 3 , NaOC 2 H 5 ;
  • the organic solvent additive in the electrolyte is selected from the group consisting of fluorobenzene, succinonitrile, fluorosulfonyloxybenzene, tris(trimethylsilane) phosphite, tripropargyl phosphate, suberonitrile, methanedi Methylene sulfonate, biphenyl, N-methylpyrrole, thiophene, 3,4-ethylenedioxythiophene, methyl ethyl sulfone, 3-fluoro-1,3-propane sultone, 1,3-propanediol sulfone , triphenylphosphine oxide, tris(pentafluorophenyl)phosphine, trimethyl borate, tris(pentafluorophenyl)boron, 4-aminobenzoic acid, benzotriazole, terthiophene, 1,3-propanesulfonate Acid lactone, 2-fluorobi
  • the concentration of the electrolyte is the concentration of the sodium salt electrolyte in the electrolyte.
  • the sodium salt electrolyte is a sodium salt that can dissociate into sodium ions and anions, preferably NaPF 6 , NaTFSI, NaFSI, NaBF 4 , NaClO 4 , NaSO 3 C 6 H 5 , NaCF 3 SO 3 , NBSB, NBDSB , NaFAB, NaTDI, NaPDI, NaTOP, NaMOB, NaFNFSI, NaFTFSI, Na 2 DFB, NaIm(BF 3 ) 2 , NaTAD, ROSO 2 Na.
  • sodium ions and anions preferably NaPF 6 , NaTFSI, NaFSI, NaBF 4 , NaClO 4 , NaSO 3 C 6 H 5 , NaCF 3 SO 3 , NBSB, NBDSB , NaFAB, NaTDI, NaPDI, NaTOP, NaMOB, NaFNFSI, NaFTFSI, Na 2 DFB, NaIm(BF 3 ) 2 , NaTAD, ROSO 2 Na.
  • the content of the sodium salt additive in the negative electrode material is 0.1-10wt%, preferably, the content of the sodium salt additive in the negative electrode material is 1-5wt%, more preferably 1-3wt%.
  • the content of the sodium salt additive in the electrolyte is 0.1-20 wt%, preferably, the content of the sodium salt additive in the electrolyte is 1-5 wt%, more preferably 1-3 wt%.
  • the organic solvent additive content in the electrolyte is 0.1-20wt%, preferably 1-5wt%, more preferably 2-4wt%.
  • concentration range of the sodium salt electrolyte in the electrolyte is 3-15mol/L.
  • the organic solvent in the electrolyte is selected from one or more of esters, sulfones, ethers, nitriles, and olefins.
  • the ester solvent of the organic solvent in the electrolyte is propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, fluorocarbonic acid Vinyl ester, methyl propionate, ethyl propionate, ethyl acetate, isobutyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, gamma-butyrolactone, delta-valerolactone, propionate Dilute carbonate, vinylene carbonate, ethyl lactate, ethyl nonanoate, triethyl phosphate, ethyl caproate, ethyl cyclohexanecarboxylate, ethyl cinnamate, ethyl pyruvate, amyl acetate species or several;
  • the sulfone solvent of the organic solvent in the electrolyte is one or more of dimethyl sulfone, ethyl methyl sulfone, tetramethyl sulfone, and methoxyethyl methyl sulfone;
  • the ether solvent of the organic solvent in the electrolyte is triethylene glycol dimethyl ether, dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and 4-methyl-1, One or more of 3-dioxolane, dimethoxymethane, 1,2-dimethoxyethane, 1,2-dimethoxypropane, diglyme;
  • the nitrile solvent of the organic solvent in the electrolyte is acetonitrile, adiponitrile, glutaronitrile, sebaconitrile, 1,3,6-hexanetricarbonitrile, 1,3,5-pentanetricarbonitrile, p- One or more of fluorobenzonitrile and p-methylbenzonitrile.
  • the negative electrode material comprises a composite of negative electrode material active material and sodium salt additive, and the negative electrode active material is hard carbon or soft carbon material; preferably, the negative electrode material active material is resin carbon, organic polymer pyrolysis carbon, glucose-based hard carbon, phenolic resin-based hard carbon, sucrose-based hard carbon materials, hollow carbon nanowires, carbon nanofibers, flower-like mesoporous carbon, three-dimensional sodium polyacrylate pyrolysis hard carbon, nanotubular hard carbon, rice starch hard carbon Carbon, nutshell hard carbon, orange peel hard carbon, reed straw hard carbon, corncob hard carbon, pitch-based hard carbon, oxygen-sulfur co-doped hard carbon, carbon black or petroleum coke, needle coke, metallurgical coke, P Doped soft carbon, carbon fiber, carbon microspheres, pitch-based derived carbon, pitch-based porous soft carbon, pitch-based disordered carbon, mesoporous soft carbon, hexaphenylbenzene pyrolytic soft carbon, carbon
  • the negative electrode material also includes a conductive agent and a binder.
  • the positive electrode includes a positive electrode current collector and a positive electrode material
  • the positive electrode material includes a positive electrode material active material
  • the positive electrode material active material is a graphite-like carbon material
  • the active material of the positive electrode material is artificial graphite, natural graphite, expanded graphite, mesocarbon microspheres, spherical graphite, highly oriented graphite, three-dimensional graphite, carbon-carbon composite material, flake graphite, ultrafine flake graphite, massive One or more of graphite, hollow graphite, high-purity graphite, isostatic graphite, fluorinated graphite, colloidal graphite, and graphene.
  • the negative electrode material includes 65-95wt% negative electrode material active material, 0.1-60wt% conductive agent, 0.1-20wt% sodium salt additive and 1-50wt% binder;
  • the positive electrode material includes 65 - 95wt% positive electrode material active material, 0.1-60wt% conductive agent and 1-50wt% binder.
  • Another aspect of the present invention provides a preparation method of a sodium-based double-ion battery, the preparation method comprising the following steps:
  • Preparing the positive electrode mixing the active material of the positive electrode material, the conductive agent, the binder, and the solvent to form a slurry; then coating the positive electrode material slurry on the surface of the positive electrode current collector, and cutting into pieces after drying to obtain a positive electrode of the desired size ;
  • steps S1-S4) can be performed simultaneously or in any sequence.
  • beneficial effect of the present invention is:
  • the present invention uses a high-concentration organic electrolyte containing sodium salt, and the concentration of the electrolyte is 3-15mol/L, thereby increasing the concentration of active ions and reducing the amount of electrolyte, thereby increasing the capacity and capacity of the sodium-based dual-ion battery.
  • high-concentration electrolyte is conducive to improving the high-voltage stability of the electrolyte, increasing the electrochemical window and improving the coulombic efficiency of the battery; the anions in the high-concentration electrolyte are easily reduced to become the main component of the SEI film, making the SEI film stable; Significantly reduce the volatility of the electrolyte, improve thermodynamic stability, and improve battery safety performance; increase the migration number of sodium ions, and have a larger migration number of sodium ions during charge transfer; improve rate performance; prevent graphite peeling; increase energy density;
  • a small amount of sodium salt is added to the negative electrode material and electrolyte of the sodium-based dual-ion battery to compensate for the loss of active sodium ions in the electrolyte caused by the formation of an irreversible SEI film at the negative electrode, and to supplement sodium, thereby greatly reducing sodium Irreversible capacity loss of ion batteries during early cycling, improving capacity, rate performance, cycle stability, Coulombic efficiency and energy density of sodium-ion batteries;
  • a small amount of organic solvent additive is added to the electrolyte of the sodium-based dual-ion battery, and the organic solvent additive is preferentially decomposed at the electrode interface, so that the electrolyte exhibits high oxidation stability under high pressure conditions, and can prevent the electrolyte from being deposited on the surface of the positive electrode. Oxidation and decomposition to produce gas are helpful to the formation of SEI films on the positive and negative electrodes, improving Coulombic efficiency, cycle stability under high pressure, and rate performance.
  • Fig. 1 is the structural representation of sodium-based double-ion battery of the present invention
  • Positive electrode current collector As shown in the figure: 1. Positive electrode current collector; 2. Positive electrode active material; 3. Electrolyte; 4. Diaphragm; 5. Negative electrode active material; 6. Negative electrode current collector.
  • the positive electrode of the sodium-based dual-ion battery includes a positive electrode current collector and a positive electrode material.
  • the positive electrode material includes an active material of the positive electrode material, and the active material of the positive electrode material is a graphite-like carbon material.
  • the active material of the positive electrode material is artificial graphite, natural graphite, expanded graphite, mesophase carbon microspheres, spherical graphite, highly oriented graphite, three-dimensional graphite, carbon-carbon composite material, flake graphite, ultrafine flake graphite, block graphite, hollow graphite, One or more of graphite-like carbon materials such as high-purity graphite, isostatic graphite, fluorinated graphite, colloidal graphite, and graphene.
  • the positive electrode material active material is artificial graphite.
  • the positive current collector of the positive electrode of the sodium-based dual-ion battery is a metal conductive material, which includes but is not limited to one of aluminum, copper, tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium Or several metals, alloys and composite materials.
  • the positive electrode current collector of the sodium-based dual-ion battery is preferably carbon-coated aluminum foil.
  • the positive electrode material further includes a conductive agent and a binder.
  • the positive electrode material includes 65-95wt% positive electrode active material, 1-60wt% conductive agent, and 1-50wt% binder.
  • the active material mass fraction of the positive electrode material is 80wt%.
  • the mass fraction of the conductive agent is 10wt%.
  • the mass fraction of the binder substance is 10wt%.
  • weight percentage is based on the negative electrode material.
  • the comprehensive performance of the positive electrode material obtained by adopting the active material of the positive electrode material, the conductive agent and the binder with a specific percentage content is good, and the effect of the positive electrode material in the battery can be well played.
  • the conductive agent and binder in the positive electrode material are not particularly limited, and commonly used conductive agents and binders in the art can be used.
  • the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, carbon fibers or graphene.
  • the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins (polybutadiene, polyvinyl chloride, poly One or more of isoprene, etc.).
  • the negative electrode of the sodium-based double-ion battery of the present invention includes a negative electrode current collector and a negative electrode material, and the negative electrode material contains a compound of an active material of the negative electrode material and a sodium salt additive.
  • the active material of the negative electrode material is selected from hard carbon or soft carbon, such as resin carbon, organic polymer pyrolytic carbon, glucose-based hard carbon, phenolic resin-based hard carbon, sucrose-based hard carbon materials, hollow carbon nanowires, carbon nanofibers , flower-like mesoporous carbon, three-dimensional sodium polyacrylate pyrolysis hard carbon, nano-tubular hard carbon, rice starch hard carbon, nut shell hard carbon, orange peel hard carbon, reed straw hard carbon, corncob hard carbon, pitch-based hard carbon, Hard carbon materials such as oxygen-sulfur co-doped hard carbon and carbon black or petroleum coke, needle coke, metallurgical coke, P-doped soft carbon, carbon fiber, carbon microspheres, pitch-based derived carbon, pitch-
  • the hard carbon is resin carbon, phenolic resin-based hard carbon, hollow carbon nanowire, orange peel hard carbon, oxygen-sulfur co-doped hard carbon;
  • the soft carbon is carbon microspheres, metallurgical coke, pitch-based derived carbon, mesoporous soft carbon, and nitrogen-sulfur double-doped porous soft carbon nanosheets.
  • the negative electrode material is prepared by ball milling or grinding the negative electrode active material and the sodium salt additive, or adding the sodium salt additive when the negative electrode is stirred.
  • the negative current collector of the negative electrode of the sodium-based dual-ion battery includes but is not limited to one or more metals, alloys and composites of aluminum, copper, tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium. Material.
  • the negative electrode current collector is carbon-coated aluminum foil.
  • the negative electrode material includes 65-95wt% negative electrode active material, 1-60wt% conductive agent, 1-50wt% binder and 1-20wt% sodium salt additive.
  • the active material mass fraction of the negative electrode material is 78.4wt%.
  • the mass fraction of the conductive agent is 9.8wt%.
  • the mass fraction of the binder substance is 9.8wt%.
  • the sodium salt additive mass fraction is 2wt%
  • the conductive agent and binder in the negative electrode material are not particularly limited, and commonly used conductive agents and binders in the art can be used.
  • the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, carbon fibers or graphene.
  • the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins (polybutadiene, polyvinyl chloride, poly One or more of isoprene, etc.).
  • the electrolyte solution of the sodium-based double-ion battery includes a sodium salt electrolyte, an organic solvent and an additive, and the additive includes a sodium salt additive and an organic solvent additive.
  • the electrolyte sodium salt includes one or more of organic sodium salts or inorganic sodium salts.
  • the sodium salt as the electrolyte is also not particularly limited as long as it can be dissociated into sodium ions and anions.
  • Carriers Na + and anions are provided by organic sodium salts and/or inorganic sodium salts.
  • the sodium salt electrolyte is NaPF 6 , NaTFSI, NaFSI, NaBF 4 , NaClO 4 , NaSO 3 C 6 H 5 , NaCF 3 SO 3 , NBSB, NBDSB, NaFAB, NaTDI, NaPDI, NaTOP, One or more of NaMOB, NaFNFSI, NaFTFSI, Na 2 DFB, NaIm(BF 3 ) 2 , NaTAD, ROSO 2 Na. Preferred is NaPF 6 .
  • the concentration of the sodium salt electrolyte in the electrolytic solution is preferably 3-15 mol/L.
  • the electrolyte solvent is not particularly limited, as long as the solvent can dissociate the electrolyte into sodium ions and anions, and the sodium ions and anions can migrate freely.
  • the solvent in the electrolyte is an organic solvent
  • the solvent in the electrolyte plays the role of dissociating sodium salt, providing Na + and anion transport medium.
  • the organic solvent includes one or more of ester, sulfone, ether, or nitrile organic solvents.
  • the ester solvent is propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, fluoroethylene carbonate, methyl propionate , ethyl propionate, ethyl acetate, isobutyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, ⁇ -butyrolactone, ⁇ -valerolactone, propylene carbonate, vinylene carbonate
  • esters ethyl lactate, ethyl nonanoate, triethyl phosphate, ethyl hexanoate, ethyl cyclohexanecarboxylate, ethyl cinnamate, ethyl pyruvate, amyl acetate;
  • the sulfone solvent is one or more of dimethylsulfone, ethylmethylsulfone, tetramethylsulfone, and methoxyethylmethylsulfone;
  • the ether solvent is triethylene glycol dimethyl ether, dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and 4-methyl-1,3-diox One or more of cyclopentane, dimethoxymethane, 1,2-dimethoxyethane, 1,2-dimethoxypropane and diglyme;
  • the nitrile solvent is acetonitrile, adiponitrile, glutaronitrile, sebaconitrile, 1,3,6-hexanetricarbonitrile, 1,3,5-pentanetricarbonitrile, p-fluorobenzonitrile , one or more of p-methylbenzonitrile;
  • the electrolyte also includes additives; the additives include sodium salt additives and organic solvent additives; the mass fraction of sodium salt additives in the electrolyte is 1-20%, and the mass fraction of the organic solvent additives in the electrolyte The mass fraction is 0.1-20%.
  • Additives can further improve one or several performances of sodium-based double-ion batteries.
  • Sodium salt additives include NaNO 3 , NaBOB, NaDFOB, DTPA-5Na, NaN 3 , Na 3 P, Na 2 CO 3 , NaNO 2 , EDTA-4Na, Na 3 Sb, Na 2 C 2 O 4 , Na 2 C 3 O 5.
  • the organic solvent additives in the electrolyte include fluorobenzene, succinonitrile, fluorosulfonyloxybenzene, tris(trimethylsilane) phosphite, tripropargyl phosphate, suberonitrile, methanedisulfonate Acid methylene ester, biphenyl, N-methylpyrrole, thiophene, 3,4-ethylenedioxythiophene, methyl ethyl sulfone, 3-fluoro-1,3-propane sultone, 1,3-propanediol ring sulfone, Triphenylphosphine oxide, tris(pentafluorophenyl)phosphine, trimethyl borate, tris(pentafluorophenyl)boron, 4-aminobenzoic acid, benzotriazole, terthiophene, 1,3-propanesulfonic acid Lactone, 2-fluorobiphenyl,
  • separator is not particularly limited, and a common separator in the art can be used.
  • the separator includes, but is not limited to, an insulating porous polymer film or an inorganic porous film.
  • the diaphragm includes but not limited to one or more of porous polypropylene film, porous polyethylene film, porous composite polymer film, non-woven fabric, glass fiber paper or porous ceramic diaphragm.
  • the sodium-based double-ion battery further includes a casing or an outer package for packaging.
  • Any outer package can be properly selected without limitation as long as it is stable to the electrolyte and has sufficient sealing performance.
  • the shape of the sodium-based double-ion battery involved in the present invention is not limited to the button type, and can also be designed into flat, cylindrical, or laminated shapes according to the core components.
  • Embodiment 1 A sodium-based dual-ion battery, including a negative electrode, a separator, an electrolyte and a positive electrode.
  • negative electrode 0.784g resin carbon and 0.02g sodium difluorooxalate borate (NaDFOB) were ball milled or ground, 0.098g conductive carbon black, 0.098g polytetrafluoroethylene were added to 1mL nitrogen methyl pyrrolidone solution, fully ground to obtain uniform slurry; then the slurry is uniformly coated on the surface of the carbon-coated aluminum foil and dried in vacuum.
  • the electrode sheet obtained by drying was cut into discs with a diameter of 12 mm, which were compacted and used as negative electrodes for future use.
  • Preparation of the diaphragm cut the glass fiber diaphragm into a disc with a diameter of 16 mm, and use it as a diaphragm after drying.
  • Preparation of positive electrode Add 0.24g artificial graphite, 0.03g carbon black, and 0.03g polyvinylidene fluoride to 0.5mL nitrogen methyl pyrrolidone solution, grind thoroughly to obtain a uniform slurry; then evenly coat the slurry on the surface of copper foil and Vacuum dry.
  • the electrode sheet obtained by drying was cut into a disc with a diameter of 10 mm, and was used as a positive electrode after compaction.
  • Example 2-4 is the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the selection of positive electrode active materials, see Table 1 for details.
  • Examples 5-7 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the selection of the negative electrode active material, see Table 2 for details.
  • Examples 8-10 are the same as Example 1 in the preparation process of the sodium-based double-ion battery, the difference is only in the electrolyte salt, see Table 3 for details.
  • Examples 11-13 are the same as Example 1 in the preparation process of the sodium-based double-ion battery, the difference is only in the electrolyte salt concentration, see Table 4 for details.
  • Examples 14-16 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the sodium salt additive, see Table 5 for details.
  • Examples 17-19 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the content of the sodium salt additive in the electrolyte, see Table 6 for details.
  • Examples 20-22 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the organic solvent additive, see Table 7 for details.
  • Examples 23-25 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the content of organic solvent additives in the electrolyte, see Table 8 for details.
  • Examples 26-28 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the content of the negative electrode sodium salt additive, see Table 9 for details.
  • Examples 29-49 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the type of solvent in the electrolyte, see Table 10 for details.
  • Examples 50-51 are the same as Example 1 in the preparation process of the sodium-based double-ion battery, the difference is only in the type of separator, see Table 11 for details.
  • Examples 52-55 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, the difference is only in the active material, conductive agent, binder type, and mass percentage in the positive electrode material, see Table 12 for details .
  • Examples 56-59 are the same as Example 1 in the preparation process of the sodium-based dual-ion battery, except for the active material, conductive agent, binder type, and mass percentage in the negative electrode material. See Table 13 for details.
  • Table 14 Electrochemical performance test of the sodium-based double-ion battery provided in Example 1 of the present invention
  • Table 14 Compared with the performance of traditional sodium-based dual-ion batteries, the results and comparisons are shown in Table 14. As can be seen from Table 14, compared with the traditional sodium-based dual-ion battery in the pre-sodiumized sodium-based dual-ion battery of Example 1 of the present invention, the specific capacity of the battery is improved by adding sodium salt additives and organic solvent additives to the negative electrode and electrolyte. , energy density, higher first Coulombic efficiency, and better cycle stability.

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Abstract

本发明涉及一种钠基双离子电池，包括负极、正极、隔膜和电解液；所述负极包括负极集流体和负极材料，所述负极材料为负极材料活性物质与钠盐添加剂的复合物，所述负极材料活性物质为硬碳类或软碳材料；所述正极包括正极集流体和正极材料，所述正极材料包括正极材料活性物质，所述正极材料活性物质为石墨类碳材料；所述电解液包括钠盐电解质、有机溶剂及添加剂，所述电解液中的添加剂包括钠盐添加剂和有机溶剂添加剂，所述电解液中的有机溶剂包括酯类、砜类、醚类、腈类、烯烃类有机溶剂中的一种或几种。本发明具有如下优点：提高钠离子电池的容量、倍率性能、循环稳定性、库伦效率和能量密度。

Description

一种钠基双离子电池及其制备方法 技术领域
本发明涉及电池技术领域，特别是涉及一种钠基双离子电池及其制备方法。
背景技术
由于钠资源储量丰富、廉价，在地壳中分布均匀，并且与锂有着相似的物理化学性质，可代替目前造价昂贵的锂离子电池，降低成本，从而使得钠离子电池在规模化储能领域具有广泛的市场应用前景。钠基双离子电池是钠离子电池中的一种，正极采用阴离子插层型的石墨类碳材料，负极采用钠离子电池负极材料，因此成本可进一步降低。具有环保、易回收的优势。然而，由于双离子电池中电解液中的阴阳离子均为活性物质，而电解液浓度较低，造成电解液用量大，电池能量密度低。另一方面，常见的改善钠离子电池性能的添加剂包括成膜添加剂、过充电保护添加剂、稳定剂、改善高低温性能的添加剂、导电添加剂或阻燃添加剂等。由于这些添加剂不含有钠元素，目前报道的基于这些添加剂的钠离子电池存在早期充放电容量不可逆，钠离子损失，导致电池库伦效率和能量密度降低；另外，由于这些添加剂无法抑制电解液发生氧化分解，无法在正负极界面形成SEI膜，导致电池在高压下循环稳定性不强，库伦效率低，倍率性能差。
现有技术中公开号为CN108172816A的中国专利公开了钠基双离子电池及其制备方法，由于负极是吸附机理，解决了传统钠电负极活性材料由于钠离子嵌入和脱出导致的严重体积膨胀或粉化所引起的循环稳定性衰减和电池容量降低的技术问题，然而这种吸附型材料的容量较低，使得电池能量密度较低；公开号为CN107565158A的中国专利公开了钠离子电池用电解液、制备方法及包含该钠离子电池用电解液的钠离子电池，其电解液价格低廉、安全性高、对水分敏感程度低并且对电池制成环境要求低，但是并没有对负极材料和电解液进行预钠化处理，进行钠离子储备，无法降低早期周期不可逆容量损失。
发明内容
为了克服上述现有技术的不足，本发明提供了一种钠基双离子电池及其制备方法，以解决上述背景技术中提出的问题。
为达到上述目的，本发明提供的技术方案为：一种钠基双离子电池，包括负极、正极、隔膜和电解液；
所述负极包括负极集流体和负极材料，所述负极材料中含有钠盐添加剂；所述电解液包括钠盐电解质、有机溶剂及添加剂，所述电解液中的添加剂为钠盐添加剂和有机溶剂添加剂的组合；所述电解液的浓度为3mol/L以上；
所述负极和电解液中的钠盐添加剂选自NaNO 3、NaBOB、NaDFOB、DTPA-5Na、NaN 3、Na 3P、Na 2CO 3、NaNO 2、EDTA-4Na、Na 3Sb、Na2C 2O 4、Na2C 3O 5、Na 2C 6O 6、Na 3C 6H 5O 7、NaCrO 2、Na 2NiO 2、NaPO2F 2、Na 2NiPO 4、NaCoPO 4、NaDFOP、NaPCPI、NaTCP、NaTIM、NaB(CN) 4、NaPO 2F 2、Na 2SO 3、NaOCH 3、NaOC 2H 5中的一种或几种；
所述电解液中的有机溶剂添加剂选自氟代苯、丁二腈、氟磺酰基氧基苯、三(三甲基硅烷)亚磷酸酯、三炔丙基磷酸酯、辛二腈、甲烷二磺酸亚甲酯、联苯、N-甲基吡咯、噻吩、3，4-乙烯二氧噻吩、甲乙砜、3-氟-1，3-丙磺酸内酯、1，3-丙二醇环砜、三苯基氧化膦、三(五氟苯基)膦、硼酸三甲酯、三(五氟苯基)硼、4-氨基苯甲酸、苯并三唑、三联噻吩、1，3-丙磺酸内酯、2-氟联苯、磷酸三甲酯、磷酸甲苯二苯酯、亚磷酸三苯酯、呋喃、乙烯二羟基噻吩、三异丙基乙磺酰(五氟苯基)膦、三磷酸六氟异丙基酯中的一种或几种。
进一步地，所述电解液的浓度为钠盐电解质在电解液中的浓度。
进一步地，所述钠盐电解质为能够离解成钠离子和阴离子的钠盐，优选为NaPF 6、NaTFSI、NaFSI、NaBF 4、NaClO 4、NaSO 3C 6H 5、NaCF 3SO 3、NBSB、NBDSB、NaFAB、NaTDI、NaPDI、NaTOP、NaMOB、NaFNFSI、NaFTFSI、Na 2DFB、NaIm(BF 3) 2、NaTAD、ROSO 2Na中的一种或几种。
进一步地，所述负极材料中的钠盐添加剂含量为0.1-10wt％，优选地，负极材料中的钠盐添加剂含量为1-5wt％，更优选为1-3wt％。
进一步地，所述电解液中的钠盐添加剂含量为0.1-20wt％，优选地，电解液中的钠盐添加剂含量为1-5wt％，更优选为1-3wt％。
进一步地，所述电解液中的有机溶剂添加剂含量为0.1-20wt％，优选地，为1-5wt％，更优选为2-4wt％。
进一步地，所述电解液的中钠盐电解质的浓度范围为3-15mol/L。
进一步地，所述电解液中的有机溶剂选自酯类、砜类、醚类、腈类、烯烃类有机溶剂中的一种或几种。
优选的，所述电解液中的有机溶剂的酯类溶剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、甲酸甲酯、乙酸甲酯、氟代碳酸乙烯酯、丙酸甲酯、丙酸乙酯、乙酸乙酯、乙酸异丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、γ-丁内酯、δ-戊内酯、丙稀碳酸酯、碳酸亚乙烯酯、乳酸乙酯、壬酸乙酯、磷酸三乙酯、己酸乙酯、环己甲酸乙酯、肉桂酸乙酯、丙酮酸乙酯、乙酸戊酯中的一种或几种；
所述电解液中的有机溶剂的砜类溶剂为二甲基砜、乙基甲基砜、四甲基砜、甲氧基乙基甲基砜中的一种或几种；
所述电解液中的有机溶剂的醚类溶剂为三乙二醇二甲醚、二甲醚、四氢呋喃、2-甲基四氢呋喃、1，3-二氧环戊烷和4-甲基-1，3-二氧环戊烷、二甲氧甲烷、1，2-二甲氧乙烷、1，2-二甲氧丙烷、二甘醇二甲醚中的一种或几种；
所述电解液中的有机溶剂的腈类溶剂为乙腈、己二腈、戊二腈、癸二腈、1,3,6-己烷三甲腈、1,3,5-戊烷三甲腈、对氟苯甲腈、对甲基苯甲腈中的一种或几种。
进一步地，所述负极材料包含负极材料活性物质和钠盐添加剂的复合物，所述负极活性物质为硬碳类或软碳材料；优选的，负极材料活性物质为树脂碳、有机聚合物热解碳、葡萄糖基硬碳、酚醛树脂基硬碳、蔗糖基硬炭材料、中空碳纳米线、碳纳米纤维、花状介孔炭、三维聚丙烯酸钠裂解硬碳、纳米管状硬碳、大米淀粉硬碳、坚果壳硬碳、桔皮硬碳、芦苇秸秆硬碳、玉米芯硬碳、沥青基硬碳、氧硫共掺杂硬碳、炭黑或为石油焦、针状焦、冶金焦炭、P掺杂软碳、碳纤维、碳微球、沥青基衍生炭、沥青基多孔软炭、沥青基无序碳、介孔软炭、六苯基苯热解软碳、碳纳米片、苝-3,4,9,10-四羧酸二酐热解三维多孔软碳、中孔软碳、多晶半空心微米棒软碳、氮掺杂碳纳米纤维、氮硫双掺杂多孔软碳纳米片中的一种或几种。
进一步地，所述负极材料还包含导电剂、粘结剂。
进一步地，所述正极包括正极集流体和正极材料，所述正极材料包括正极材料活性物质，所述正极材料活性物质为石墨类碳材料。
优选的，所述正极材料活性物质为人造石墨、天然石墨、膨胀石墨、中间相碳微球、球形石墨、高取向石墨、三维石墨、碳碳复合材料、鳞片石墨、超细鳞片石墨、块状石墨、中空石墨、高纯石墨、等静压石墨、氟化石墨、胶体石墨、石墨烯中的一种或几种。
优选的，所述负极材料包括65-95wt％的负极材料活性物质、0.1-60wt％的导电剂，0.1-20wt％的钠盐添加剂和1-50wt％的粘结剂；所述正极材料包括65-95wt％的正极材料活性物质、0.1-60wt％的导电剂和1-50wt％的粘结剂。
本发明另一个方面提供了一种钠基双离子电池的制备方法，所述制备方法包括以下步骤：
S1)制备负极：将负极材料活性物质、导电剂、钠盐添加剂和粘结剂及溶剂混合制成浆料或将负极材料活性物质与钠盐添加剂混合后，再与导电剂、和粘结剂及溶剂混合制成浆料；再将负极材料浆料涂覆于负极集流体表面，干燥后裁片，得到所需尺寸的负极；
S2)配制电解液：将钠盐电解质、钠盐添加剂和有机溶剂添加剂溶于有机溶剂中，充分搅拌得到电解液；
S3)制备隔膜：将隔膜裁切成所需尺寸备用；
S4)制备正极：将正极材料活性物质、导电剂和粘结剂及溶剂混合制成浆料；再将正极材料浆料涂覆于正极集流体表面，干燥后裁片，得到所需尺寸的正极；
S5)组装：将步骤a)得到的负极、步骤b)得到的电解液、步骤c)得到的隔膜以及步骤d)得到的正极进行组装，得到钠基双离子电池。
进一步地，步骤S1-S4)可以同时或者任意先后执行.
采用上述技术方案后，本发明的有益效果为：
1、首先，本发明使用含钠盐的高浓度有机电解液，电解液浓度为3-15mol/L，从而提高活性离子的浓度，并减少电解液用量，从而提高钠基双离子电池的容量和能量密度；此外，高浓度电解液有利于提高电解液高电压稳定性，增大电化学窗口并提高电池库伦效率；高浓度电解液中阴离子容易被还原成为SEI膜主要成分，使SEI膜稳定；大幅度降低电解液的挥发性，提高热力学稳定性，改善电池安全性能；钠离子迁移数增加，电荷传输过程中具有较大的钠离子迁移数；改善倍率性能；防止石墨剥落；提高能量密度；
2、本发明在钠基双离子电池负极材料和电解液中加入少量钠盐，弥补负极处不可逆的SEI膜形成对电解液中活性钠离子的损失，进行钠补充，从而极大的降低了钠离子电池在早期循环过程中的不可逆容量损失，提高钠离子电池的容量、倍率性能、循环稳定性、库伦效率和能量密度；
3、本发明在钠基双离子电池电解液中加入少量有机溶剂添加剂，有机溶剂添加剂在电极界面优先发生分解，使电解液在高压条件下表现出高氧化稳定性，可防止电解液在正极表面发生氧化分解产气，有助于正极和负极上SEI膜的形成，提高库伦效率、高压下循环稳定性和倍率性能。
附图说明
图1是本发明钠基双离子电池的结构示意图；
如图所示：1、正极集流体；2、正极活性材料；3、电解液；4、隔膜；5、负极活性材料；6、负极集流体。
具体实施方式
下面结合如图1所示结构示意图详细描述本发明基双离子电池的各部件结构组成。
[正极]
钠基双离子电池的正极包括正极集流体、正极材料，正极材料包括正极材料活性物质，正极材料活性物质为石墨类碳材料。
正极材料活性物质为人造石墨、天然石墨、膨胀石墨、中间相碳微球、球形石墨、高取向石墨、三维石墨、碳碳复合材料、鳞片石墨、超细鳞片石墨、块状石墨、中空石墨、高纯石墨、等静压石墨、氟化石墨、胶体石墨、石墨烯等石墨类碳材料中的一种或几种。优选地，在本发明技术方案的基础上，正极材料活性物质为人造石墨。
可以理解的是，钠基双离子电池正极的正极集流体为金属导电材料，该导电材料包括但不限于铝、铜、锡、锌、铅、锑、镉、金、铋或锗中的一种或几种金属、合金及复合材料。
优选地，钠基双离子电池正极集流体优选为涂炭铝箔。
在一种优选的实施方式中，正极材料还包括导电剂和粘结剂。
在一种优选的实施方式中，按重量百分比计，正极材料包括65-95wt％正极活性材料，1-60wt％导电剂，1-50wt％粘结剂。
优选地，正极材料活性物质质量分数为80wt％。
优选地，导电剂物质质量分数为10wt％。
优选地，粘结剂物质质量分数为10wt％。
其中重量百分比以负极材料为计算基准。
采用特定百分含量的正极材料活性物质、导电剂和粘结剂得到的正极材料的综合性能好，能很好地发挥正极材料在电池中的作用。
可以理解的是，正极材料中的导电剂和粘结剂也没有特别限制，可采用本领域普通常用的导电剂和粘结剂。
在一种优选的实施方式中，导电剂为导电炭黑、导电碳球、导电石墨、碳纳米管、碳纤维或石墨烯中的一种或几种。
在一种优选的实施方式中，粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃类(聚丁二烯、聚氯乙烯、聚异戊二烯等)中的一种或多种。
[负极]
本发明钠基双离子电池负极包括负极集流体和负极材料，负极材料包含负极材料活性物质和钠盐添加剂的复合物。负极材料活性物质选自硬碳或软瘫，例如可以选择树脂碳、有机聚合物热解碳、葡萄糖基硬碳、酚醛树脂基硬碳、蔗糖基硬炭材料、中空碳纳米线、碳纳米纤维、花状介孔炭、三维聚丙烯酸钠裂解硬碳、纳米管状硬碳、大米淀粉硬碳、坚果壳硬碳、桔皮硬碳、芦苇秸秆硬碳、玉米芯硬碳、沥青基硬碳、氧硫共掺杂硬碳和炭黑等硬碳类材料或为石油焦、针状焦、冶金焦炭、P掺杂软碳、碳纤维、碳微球、沥青基衍生炭、沥青基多孔软炭、沥青基无序碳、介孔软炭、六苯基苯热解软碳、碳纳米片、苝-3,4,9,10-四羧酸二酐热解三维多孔软碳、中孔软碳、多晶半空心微米棒软碳、氮掺杂碳纳米纤维、氮硫双掺杂多孔软碳纳米片等软碳类中的一种或几种；
优选地，所述硬碳为树脂碳、酚醛树脂基硬碳、中空碳纳米线、桔皮硬碳、氧硫共掺杂硬碳；
优选地，所述软碳为碳微球、冶金焦炭、沥青基衍生炭、中孔软碳、氮硫双掺杂多孔软 碳纳米片。
通过将负极活性材料与钠盐添加剂球磨或研磨或在负极搅浆时加入钠盐添加剂制成负极材料。
可以理解的是，钠基双离子电池负极的负极集流体包括但不限于铝、铜、锡、锌、铅、锑、镉、金、铋或锗中的一种或几种金属、合金及复合材料。优选地，负极集流体为涂炭铝箔。
在一种优选的实施方式中，按重量百分比计，负极材料包括65-95wt％的负极活性物质，1-60wt％导电剂、1-50wt％粘结剂和1-20wt％钠盐添加剂。
优选地，负极材料活性物质质量分数为78.4wt％。
优选地，导电剂物质质量分数为9.8wt％。
优选地，粘结剂物质质量分数为9.8wt％。
优选地，钠盐添加剂质量分数为2wt％
可以理解的是，负极材料中的导电剂和粘结剂也没有特别限制，可采用本领域普通常用的导电剂和粘结剂。
在一种优选的实施方式中，导电剂为导电炭黑、导电碳球、导电石墨、碳纳米管、碳纤维或石墨烯中的一种或几种。
在一种优选的实施方式中，粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃类(聚丁二烯、聚氯乙烯、聚异戊二烯等)中的一种或多种。
[电解液]
钠基双离子电池的电解液包括钠盐电解质、有机溶剂及添加剂，添加剂包括钠盐添加剂和有机溶剂添加剂。
在一种优选的实施方式中，电解质钠盐包括有机型钠盐或无机型钠盐中的一种或几种。作为电解质的钠盐也没有特别限制，只要可以离解成钠离子和阴离子即可。
通过有机钠盐和/或无机钠盐提供载流子Na +和阴离子。
在一种优选的实施方式中，钠盐电解质为NaPF 6、NaTFSI、NaFSI、NaBF 4、NaClO 4、NaSO 3C 6H 5、NaCF 3SO 3、NBSB、NBDSB、NaFAB、NaTDI、NaPDI、NaTOP、NaMOB、NaFNFSI、NaFTFSI、Na 2DFB、NaIm(BF 3) 2、NaTAD、ROSO 2Na中的一种或几种。优选为NaPF 6。
在电解液中钠盐电解质的浓度优选为3-15mol/L。
可以理解的是，电解液溶剂没有特别限制，只要溶剂可以使电解质离解成钠离子和阴离子，且钠离子和阴离子可以自由迁移即可。
在一种优选的实施方式中，电解液中溶剂为有机溶剂
电解液中的溶剂起到解离钠盐、提供Na +和阴离子传输介质的作用。
优选地，有机溶剂包括酯类、砜类、醚类、或腈类有机溶剂中的一种或几种。
优选地，所述酯类溶剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、甲酸甲酯、乙酸甲酯、氟代碳酸乙烯酯、丙酸甲酯、丙酸乙酯、乙酸乙酯、乙酸异丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、γ-丁内酯、δ-戊内酯、丙稀碳酸酯、碳酸亚乙烯酯、乳酸乙酯、壬酸乙酯、磷酸三乙酯、己酸乙酯、环己甲酸乙酯、肉桂酸乙酯、丙酮酸乙酯、乙酸戊酯中的一种或几种；
优选地，所述砜类溶剂为二甲基砜、乙基甲基砜、四甲基砜、甲氧基乙基甲基砜中的一种或几种；
优选地，所述醚类溶剂为三乙二醇二甲醚、二甲醚、四氢呋喃、2-甲基四氢呋喃、1，3-二氧环戊烷和4-甲基-1，3-二氧环戊烷、二甲氧甲烷、1，2-二甲氧乙烷、1，2-二甲氧丙烷和二甘醇二甲醚中的一种或几种；
优选地，所述腈类溶剂为乙腈、己二腈、戊二腈、癸二腈、1,3,6-己烷三甲腈、1,3,5-戊烷三甲腈、对氟苯甲腈、对甲基苯甲腈中的一种或几种；
在一种优选的实施方式中，电解液中还包括添加剂；添加剂包括钠盐添加剂和有机溶剂添加剂；钠盐添加剂在电解液中的质量分数为1-20％，有机溶剂添加剂在电解液中的质量分数为0.1-20％。
添加剂能够进一步改善钠基双离子电池的一种或几种性能.
钠盐添加剂包括NaNO 3、NaBOB、NaDFOB、DTPA-5Na、NaN 3、Na 3P、Na 2CO 3、NaNO 2、EDTA-4Na、Na 3Sb、Na 2C 2O 4、Na 2C 3O 5、Na 2C 6O 6、Na 3C 6H 5O 7、NaCrO 2、Na 2NiO 2、NaPO 2F 2、Na 2NiPO 4、NaCoPO 4、NaDFOP、NaPCPI、NaTCP、NaTIM、NaB(CN) 4、NaPO 2F 2、Na 2SO 3、,NaOCH 3、NaOC 2H 5中的一种或几种；
所述电解液中的有机溶剂添加剂包括氟代苯、丁二腈、氟磺酰基氧基苯、三(三甲基硅烷)亚磷酸酯、三炔丙基磷酸酯、辛二腈、甲烷二磺酸亚甲酯、联苯、N-甲基吡咯、噻吩、3，4-乙烯二氧噻吩、甲乙砜、3-氟-1，3-丙磺酸内酯、1，3-丙二醇环砜、三苯基氧化膦、三(五氟苯基)膦、硼酸三甲酯、三(五氟苯基)硼、4-氨基苯甲酸、苯并三唑、三联噻吩、1，3-丙磺酸内酯、2-氟联苯、磷酸三甲酯、磷酸甲苯二苯酯、亚磷酸三苯酯、呋喃、乙烯二羟基噻吩、三异丙基乙磺酰(五氟苯基)膦、三磷酸六氟异丙基酯中的一种或几种；
[隔膜]
可以理解的是，隔膜也没有特别限制，采用本领域现有普通隔膜即可。
在一种优选的实施方式中，隔膜包括但不限于绝缘的多孔聚合物薄膜或无机多孔薄膜。
在一种优选的实施方式中，隔膜包括但不限于多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、无纺布、玻璃纤维纸或多孔陶瓷隔膜中的一种或几种。
在一种优选的实施方式中，钠基双离子电池还包括用于封装的壳体或外包装。
可以适当选择任意外包装而无限制，只要其对电解液稳定并具有足够的密封性能即可。
此外，本发明涉及的钠基双离子电池形态不局限于扣式型，也可根据核心成分设计成平板型、圆柱型或叠片型等形态。
下面结合实施例对本发明做进一步的详细说明。
实施例1：一种钠基双离子电池，包括负极、隔膜、电解液和正极。
制备负极：将0.784g树脂碳与0.02g二氟草酸硼酸钠(NaDFOB)球磨或研磨后和0.098g导电碳黑、0.098g聚四氟乙烯加入到1mL氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀的涂覆于涂炭铝箔表面并真空干燥。对干燥所得电极片裁切成直径12mm的圆片，压实后作为负极备用。
制备隔膜：将玻璃纤维隔膜切成直径16mm的圆片，干燥后作为隔膜备用。
配制电解液：称取2.52gNaPF6、0.1gNaDFOB和量取0.15mL三(三甲基硅烷)亚磷酸酯加入到5mL碳酸丙烯酯和碳酸甲乙酯的混合溶剂中(体积比为20:80)，搅拌至NaPF6完全溶解，充分搅拌均匀后作为电解液备用(电解液浓度为3M)。
制备正极：将0.24g人造石墨、0.03g碳黑、0.03g聚偏氟乙烯加入到0.5mL氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铜箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压实后作为正极备用。
组装：在惰性气体保护的手套箱中，将上述制备好的正极、隔膜、负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式壳体，完成钠基双离子电池组装。
实施例2-4：实施例2-4与例1钠基双离子电池制备过程步骤相同，区别仅在正极活性材料选材不同，具体参见表1。
表1：不同正极活性材料电池性能对比
Figure PCTCN2022138199-appb-000001
Figure PCTCN2022138199-appb-000002
从表1中可以看出，正极活性材料为人造石墨时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例5-7：实施例5-7与例1钠基双离子电池制备过程步骤相同，区别仅在负极活性材料选材不同，具体参见表2。
表2：不同负极活性材料电池性能对比
Figure PCTCN2022138199-appb-000003
从表2中可以看出，负极活性材料为树脂碳时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例8-10：实施例8-10与例1钠基双离子电池制备过程步骤相同，区别仅在电解质盐不同，具体参见表3。
表3：不同电解质盐电池性能对比
Figure PCTCN2022138199-appb-000004
从表3中可以看出，电解质为NaPF6时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例11-13：实施例11-13与例1钠基双离子电池制备过程步骤相同，区别仅在电解质 盐浓度不同，具体参见表4。
表4：不同电解质盐浓度电池性能对比
Figure PCTCN2022138199-appb-000005
从表4中可以看出，电解质浓度为3M时，电池比容量、循环稳定性、能量密度、首次库伦效率都较高。
实施例14-16：实施例14-16与例1钠基双离子电池制备过程步骤相同，区别仅在钠盐添加剂不同，具体参见表5。
表5：不同钠盐添加剂电池性能对比
Figure PCTCN2022138199-appb-000006
从表5中可以看出，钠盐添加剂为NaDFOB时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例17-19：实施例17-19与例1钠基双离子电池制备过程步骤相同，区别仅在电解液钠盐添加剂含量不同，具体参见表6。
表6：不同电解液钠盐添加剂含量电池性能对比
Figure PCTCN2022138199-appb-000007
Figure PCTCN2022138199-appb-000008
从表6中可以看出，电解液钠盐添加剂含量为2wt％时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例20-22：实施例20-22与例1钠基双离子电池制备过程步骤相同，区别仅在有机溶剂添加剂不同，具体参见表7。
表7：不同有机溶剂添加剂电池性能对比
Figure PCTCN2022138199-appb-000009
从表7中可以看出，有机添加剂为三(三甲基硅烷)亚磷酸酯时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例23-25：实施例23-25与例1钠基双离子电池制备过程步骤相同，区别仅在电解液有机溶剂添加剂含量不同，具体参见表8。
表8：不同电解液有机溶剂添加剂含量电池性能对比
Figure PCTCN2022138199-appb-000010
从表8中可以看出，电解液有机溶剂添加剂含量为3wt％时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例26-28：实施例26-28与例1钠基双离子电池制备过程步骤相同，区别仅在负极钠盐添加剂含量不同，具体参见表9。
表9：不同负极钠盐添加剂含量电池性能对比
Figure PCTCN2022138199-appb-000011
从表9中可以看出，负极钠盐添加剂含量为2wt％时，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
实施例29-49：实施例29-49与例1钠基双离子电池制备过程步骤相同，区别仅在电解液中溶剂种类不同，具体参见表10。
表10：不同电解液溶剂电池性能对比
Figure PCTCN2022138199-appb-000012
Figure PCTCN2022138199-appb-000013
从表10中可以看出，电解液溶剂为碳酸丙烯酯和碳酸甲乙酯(v/v 20:80)时，能量密度更高，循环稳定性更好。
实施例50-51：实施例50-51与例1钠基双离子电池制备过程步骤相同，区别仅在隔膜种类不同，具体参见表11。
表11：不同隔膜电池性能对比
Figure PCTCN2022138199-appb-000014
从表11可以看出，隔膜为玻璃纤维纸时，能量密度更高，循环稳定性更好。
实施例52-55：实施例52-55与例1钠基双离子电池制备过程步骤相同，区别仅在正极材料中的活性材料、导电剂、粘结剂种类、质量百分比不同，具体参见表12。
表12：不同正极材料、导电剂、粘结剂含量电池性能对比
Figure PCTCN2022138199-appb-000015
Figure PCTCN2022138199-appb-000016
实施例56-59与例1钠基双离子电池制备过程步骤相同，区别仅在负极材料中的活性材料、导电剂、粘结剂种类、质量百分比不同，具体参见表13。
表13：不同负极材料、导电剂、粘结剂含量电池性能对比
Figure PCTCN2022138199-appb-000017
表14：对本发明实施例1所提供的钠基双离子电池进行电池的电化学性能测试
Figure PCTCN2022138199-appb-000018
Figure PCTCN2022138199-appb-000019
与传统的钠基双离子电池性能进行比较，结果及对比情况如表14所示。从表14可以看出，本发明实施例1的预钠化的钠基双离子电池与传统钠基双离子电池相比，在负极及电解液中加入钠盐添加剂和有机溶剂添加剂，电池比容量、能量密度、首次库伦效率更高，循环稳定性更好。
以上对本发明及其实施方式进行了描述，这种描述没有限制性，附图中所示的也只是本发明的实施方式之一，实际的结构并不局限于此。总而言之如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的结构方式及实施例，均应属于本发明的保护范围。

Claims (10)

  1. 一种钠基双离子电池，包括负极、正极、隔膜和电解液；其特征在于，
    所述负极包括负极集流体和负极材料，所述负极材料中含有钠盐添加剂；所述电解液包括钠盐电解质、有机溶剂及添加剂，所述电解液中的添加剂为钠盐添加剂和有机溶剂添加剂的组合；所述电解液中钠盐电解质浓度为3mol/L以上；
    所述负极和电解液中的钠盐添加剂选自NaNO 3、NaBOB、NaDFOB、DTPA-5Na、NaN 3、Na 3P、Na 2CO 3、NaNO 2、EDTA-4Na、Na 3Sb、Na2C 2O 4、Na2C 3O 5、Na 2C 6O 6、Na 3C 6H 5O 7、NaCrO 2、Na 2NiO 2、NaPO2F 2、Na 2NiPO 4、NaCoPO 4、NaDFOP、NaPCPI、NaTCP、NaTIM、NaB(CN) 4、NaPO 2F 2、Na 2SO 3、NaOCH 3、NaOC 2H 5中的一种或几种；
    所述电解液中的有机溶剂添加剂选自氟代苯、丁二腈、氟磺酰基氧基苯、三(三甲基硅烷)亚磷酸酯、三炔丙基磷酸酯、辛二腈、甲烷二磺酸亚甲酯、联苯、N-甲基吡咯、噻吩、3，4-乙烯二氧噻吩、甲乙砜、3-氟-1，3-丙磺酸内酯、1，3-丙二醇环砜、三苯基氧化膦、三(五氟苯基)膦、硼酸三甲酯、三(五氟苯基)硼、4-氨基苯甲酸、苯并三唑、三联噻吩、1，3-丙磺酸内酯、2-氟联苯、磷酸三甲酯、磷酸甲苯二苯酯、亚磷酸三苯酯、呋喃、乙烯二羟基噻吩、三异丙基乙磺酰(五氟苯基)膦、三磷酸六氟异丙基酯中的一种或几种。
  2. 权利要求1所述的钠基双离子电池，其特征在于，所述钠盐电解质为能够离解成钠离子和阴离子的钠盐，优选为NaPF 6、NaTFSI、NaFSI、NaBF 4、NaClO 4、NaSO 3C 6H 5、NaCF 3SO 3、NBSB、NBDSB、NaFAB、NaTDI、NaPDI、NaTOP、NaMOB、NaFNFSI、NaFTFSI、Na 2DFB、NaIm(BF 3) 2、NaTAD、ROSO 2Na中的一种或几种。
  3. 权利要求1所述的钠基双离子电池，其特征在于，所述负极材料中的钠盐添加剂含量为0.1-10wt％，
    优选地，负极材料中的钠盐添加剂含量为1-5wt％，
    更优选为1-3wt％。
  4. 权利要求1所述的钠基双离子电池，其特征在于，所述电解液中的钠盐添加剂含量为0.1-20wt％，
    优选地，电解液中的钠盐添加剂含量为1-5wt％，
    更优选为1-3wt％。
  5. 权利要求1所述的钠基双离子电池，其特征在于，所述电解液中的有机溶剂添加剂含 量为0.1-20wt％，
    优选地，为1-5wt％，
    更优选为2-4wt％。
  6. 权利要求1所述的钠基双离子电池，其特征在于，所述电解液的中钠盐电解质的浓度范围为3-15mol/L。
  7. 权利要求1所述的钠基双离子电池，其特征在于，所述电解液中的有机溶剂选自酯类、砜类、醚类、腈类、烯烃类有机溶剂中的一种或几种。
    优选的，所述电解液中的有机溶剂的酯类溶剂选自碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、甲酸甲酯、乙酸甲酯、氟代碳酸乙烯酯、丙酸甲酯、丙酸乙酯、乙酸乙酯、乙酸异丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、γ-丁内酯、δ-戊内酯、丙稀碳酸酯、碳酸亚乙烯酯、乳酸乙酯、壬酸乙酯、磷酸三乙酯、己酸乙酯、环己甲酸乙酯、肉桂酸乙酯、丙酮酸乙酯、乙酸戊酯中的一种或几种；
    所述电解液中的有机溶剂的砜类溶剂选自二甲基砜、乙基甲基砜、四甲基砜、甲氧基乙基甲基砜中的一种或几种；
    所述电解液中的有机溶剂的醚类溶剂选自三乙二醇二甲醚、二甲醚、四氢呋喃、2-甲基四氢呋喃、1，3-二氧环戊烷和4-甲基-1，3-二氧环戊烷、二甲氧甲烷、1，2-二甲氧乙烷、1，2-二甲氧丙烷、二甘醇二甲醚中的一种或几种；
    所述电解液中的有机溶剂的腈类溶剂选自乙腈、己二腈、戊二腈、癸二腈、1,3,6-己烷三甲腈、1,3,5-戊烷三甲腈、对氟苯甲腈、对甲基苯甲腈中的一种或几种。
  8. 权利要求1所述的钠基双离子电池，其特征在于，所述负极材料包含负极材料活性物质和钠盐添加剂的复合物，所述负极活性物质为硬碳类或软碳材料；
    优选的，负极材料活性物质选自树脂碳、有机聚合物热解碳、葡萄糖基硬碳、酚醛树脂基硬碳、蔗糖基硬炭材料、中空碳纳米线、碳纳米纤维、花状介孔炭、三维聚丙烯酸钠裂解硬碳、纳米管状硬碳、大米淀粉硬碳、坚果壳硬碳、桔皮硬碳、芦苇秸秆硬碳、玉米芯硬碳、沥青基硬碳、氧硫共掺杂硬碳、炭黑或为石油焦、针状焦、冶金焦炭、P掺杂软碳、碳纤维、碳微球、沥青基衍生炭、沥青基多孔软炭、沥青基无序碳、介孔软炭、六苯基苯热解软碳、碳纳米片、苝-3,4,9,10-四羧酸二酐热解三维多孔软碳、中孔软碳、多晶半空心微米棒软碳、氮掺杂碳纳米纤维、氮硫双掺杂多孔软碳纳米片中的一种或几种；
    优选地，所述负极材料还包含导电剂、粘结剂。
  9. 权利要求1所述的钠基双离子电池，其特征在于，所述正极包括正极集流体和正极材料，所述正极材料包括正极材料活性物质，所述正极材料活性物质为石墨类碳材料；
    优选的，所述正极材料活性物质为人造石墨、天然石墨、膨胀石墨、中间相碳微球、球形石墨、高取向石墨、三维石墨、碳碳复合材料、鳞片石墨、超细鳞片石墨、块状石墨、中空石墨、高纯石墨、等静压石墨、氟化石墨、胶体石墨、石墨烯中的一种或几种；
    优选的，所述负极材料包括65-95wt％的负极材料活性物质、0.1-60wt％的导电剂，0.1-20wt％的钠盐添加剂和1-50wt％的粘结剂；所述正极材料包括65-95wt％的正极材料活性物质、0.1-60wt％的导电剂和1-50wt％的粘结剂。
  10. 权利要求1-9任一项所述的钠基双离子电池的制备方法，其特征在于，所述制备方法包括以下步骤：
    S1)制备负极：将负极材料活性物质、导电剂、钠盐添加剂和粘结剂及溶剂混合制成浆料或将负极材料活性物质与钠盐添加剂混合后，再与导电剂、和粘结剂及溶剂混合制成浆料；再将负极材料浆料涂覆于负极集流体表面，干燥后裁片，得到所需尺寸的负极；
    S2)配制电解液：将钠盐电解质、钠盐添加剂和有机溶剂添加剂溶于有机溶剂中，充分搅拌得到电解液；
    S3)制备隔膜：将隔膜裁切成所需尺寸备用；
    S4)制备正极：将正极材料活性物质、导电剂和粘结剂及溶剂混合制成浆料；再将正极材料浆料涂覆于正极集流体表面，干燥后裁片，得到所需尺寸的正极；
    S5)组装：将步骤a)得到的负极、步骤b)得到的电解液、步骤c)得到的隔膜以及步骤d)得到的正极进行组装，得到钠基双离子电池；
    优选地，步骤S1-S4)可以同时或者任意先后执行.
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