WO2017113234A1 - 一种新型钠离子电池及其制备方法 - Google Patents

一种新型钠离子电池及其制备方法 Download PDF

Info

Publication number
WO2017113234A1
WO2017113234A1 PCT/CN2015/099967 CN2015099967W WO2017113234A1 WO 2017113234 A1 WO2017113234 A1 WO 2017113234A1 CN 2015099967 W CN2015099967 W CN 2015099967W WO 2017113234 A1 WO2017113234 A1 WO 2017113234A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
positive electrode
electrolyte
ion battery
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2015/099967
Other languages
English (en)
French (fr)
Inventor
唐永炳
张小龙
张帆
李振声
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Institute of Advanced Technology of CAS
Original Assignee
Shenzhen Institute of Advanced Technology of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Institute of Advanced Technology of CAS
Priority to PCT/CN2015/099967 priority Critical patent/WO2017113234A1/zh
Priority to CN201580001257.1A priority patent/CN107148697A/zh
Publication of WO2017113234A1 publication Critical patent/WO2017113234A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 invention belongs to the technical field of secondary batteries, and in particular relates to a novel sodium ion battery and a preparation method thereof.
  • a secondary battery also called a rechargeable battery, is a battery that can be repeatedly charged and discharged and used multiple times. Compared with a non-reusable primary battery, the secondary battery has the advantages of low cost of use and low environmental pollution.
  • the main secondary battery technologies are lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, and lithium-ion batteries. Among them, lithium ion batteries are the most widely used. However, lithium-ion batteries face the disadvantages of limited lithium resource reserves and high cost.
  • sodium-ion batteries have received increasing attention in recent years. The operation of sodium ion batteries is similar to that of lithium ions, but the storage of charge in the battery is achieved by the migration of sodium ions.
  • the core component of the sodium ion battery comprises a positive electrode, a negative electrode and an electrolyte, which realizes electrical energy storage and release by a redox reaction in which ion transport and electron transport phase separation occurs at the interface between the positive electrode, the negative electrode and the electrolyte.
  • a common sodium ion battery is a transition metal oxide (NaVO 2 , NaNiMnCoO 2 ) or a polyanionic metal compound (Na 3 V 2 (PO 4 ) 3 ) or the like as a positive electrode active material, and a carbon material as a negative electrode active material.
  • the positive active material contains a transition metal element, which increases the cost of preparing the material, and on the other hand, increases the potential environmental hazard after the battery is discarded.
  • the industry is actively developing new secondary battery technologies that are environmentally friendly and have high energy density.
  • One of the two carbon batteries is of particular concern.
  • the battery uses graphite or carbon as the active material for the positive and negative electrodes and is completely free of transition metal elements.
  • the anion in the electrolyte is embedded in the cathode graphite material, and the electrolyte cation is embedded in the anode carbon material; when discharging, the anion is removed from the cathode active material, and the cation is released from the anode active material.
  • Read and Xu of the US Army Laboratory Energy Environ. Sci.
  • the graphite material has a limited embedding capacity for anions, so the battery capacity cannot be comparable to that of a conventional secondary battery;
  • fluorinated modified ester electrolyte and ionic liquid electrolysis The cost of preparing the liquid is very high, thus reducing the cost advantage of the dual carbon battery.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a novel sodium ion battery and a preparation method thereof.
  • the novel sodium ion battery uses a material capable of intercalating an anion constituting a sodium salt as a positive electrode active material, and does not contain a negative electrode active material, and can solve the defects of high manufacturing cost and low energy density of the existing secondary battery.
  • the present invention firstly provides a novel sodium ion battery comprising: a positive electrode, a negative electrode, and an electrolyte between the positive electrode and the negative electrode, wherein
  • the positive electrode includes a positive active material layer containing a positive active material
  • the negative electrode includes a negative electrode current collector, excluding the negative electrode active material
  • the positive active material includes a carbon material and a carbon material composite, a sulfide and a sulfide composite, a nitride and a nitride composite, an oxide and an oxide composite, a carbide, and the like, which are capable of allowing an anion to be composed of a sodium salt.
  • the novel sodium ion battery further includes a separator between the positive electrode and the negative electrode for isolating the positive electrode from the negative electrode.
  • the novel sodium ion battery further includes a battery case for encapsulating the positive electrode, the negative electrode, the electrolyte, and the separator.
  • the anode current collector of the anode is a conductive material
  • the conductive material includes one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or the like, or these materials.
  • the composite material may be a composite material which is compounded with a reinforcing material by using one or more of the above metals as a base material.
  • the reinforcing material may be a reinforcing material conventional in the art, and the amount thereof may be conventionally adjusted by those skilled in the art.
  • These reinforcing materials may include one or a combination of carbon fibers, boron fibers, silicon carbide fibers, wires, and hard fine particles.
  • the electrolytic solution includes a mixed liquid containing an electrolyte, an additive, and a solvent.
  • the electrolyte in the electrolyte may be a sodium salt
  • the sodium salt includes sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, twelve Sodium alkylbenzene sulfonate, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, Sodium silicate, sodium lignosulfonate, sodium hexafluorophosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexa
  • the additive in the electrolyte may include one or a combination of organic additives such as esters, sulfones, ethers, nitriles, and olefins, such esters, sulfones, ethers, nitriles, and olefins.
  • organic additives such as esters, sulfones, ethers, nitriles, and olefins, such esters, sulfones, ethers, nitriles, and olefins.
  • Organic additives include vinylene carbonate, ethylene sulfite, propylene sulfite, vinyl chlorocarbonate, methyl chloroformate, anisole, acetamide, dinitro(benzene) benzene, m-diaza ( hetero) benzene, crown ether 12-crown--4,18- -6, (C 6 H 3 F ) O 2 B (C 6 H 3 F 2), (C 6 F 4) O 2 (C 6 F 5 ), 4-fluoroanisole, fluoro-chain ether (C 4 F 9 OCH 3 ), monofluoromethyl ethylene carbonate (CH 2 F-EC), difluoromethyl ethylene carbonate (CHF 2 ) -EC), trifluoromethyl ethylene carbonate (CF 3 -EC), phosphate, phosphite, phosphazene, ethanolamine, dimethylamine, aluminum oxide, magnesium oxide, cerium oxide, sodium carbonate, a combination of one or more of calcium carbonate, ethylene s
  • the solvent in the electrolyte may include one or a combination of organic solvents such as esters, sulfones, and ethers, and the organic solvents including esters, sulfones, and ethers include propylene carbonate (PC) and carbonic acid.
  • organic solvents such as esters, sulfones, and ethers
  • the organic solvents including esters, sulfones, and ethers include propylene carbonate (PC) and carbonic acid.
  • the positive electrode further includes a positive electrode current collector, and the positive electrode active material layer containing the positive electrode active material is formed on a surface of the positive electrode current collector;
  • the positive electrode current collector is a conductive material
  • the conductive material includes one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or the like, or an alloy formed of several of these materials, or a composite material containing one or more of these materials.
  • the composite material may be a composite material which is compounded with a reinforcing material by using one or more of the above metals as a base material.
  • the reinforcing material may be a reinforcing material conventional in the art, and the amount thereof may be conventionally adjusted by those skilled in the art.
  • These reinforcing materials may include one or a combination of carbon fibers, boron fibers, silicon carbide fibers, wires, and hard fine particles.
  • the carbon material and the carbon material composite include carbon fiber, mesocarbon microbead graphite, natural graphite, glassy carbon, carbon-carbon composite material, hard carbon, porous carbon, high orientation.
  • the sulfide and sulfide composite includes one of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, manganese sulfide, and the like. Or a composite of several or one or more of these sulfides;
  • the nitride and nitride composites include one or more of hexagonal boron nitride, carbon doped hexagonal boron nitride, or the like or a composite containing one or more of these nitrides;
  • the oxide and oxide composites include one or more of or include or include molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, manganese oxide, and the like. a complex of one or more of these oxides;
  • the carbide and carbide composite includes one or more of titanium carbide, tantalum carbide, molybdenum carbide, silicon carbide, or the like or a composite containing one or more of these carbides;
  • the material having a layered crystal structure and a composite thereof include one or more of mica, expanded vermiculite, tungsten selenide, zinc selenide, antimony selenide, cobalt selenide, antimony telluride, etc. or contain these A composite of one or more of materials having a layered crystal structure.
  • the positive electrode active material layer of the positive electrode further includes a conductive agent and/or a binder based on the total weight of the positive electrode active material layer, wherein the positive electrode active material
  • the content is 50-90%, the content of the conductive agent is 0.1-30%, and the content of the binder is 0.1-10%.
  • the conductive agent in the positive electrode active material layer includes conductive carbon black, Super P conductive carbon ball, conductive graphite KS6, carbon nanotube, conductive carbon fiber, graphene, reduced graphite oxide. a combination of one or more of alkene and the like.
  • the binder in the positive electrode active material layer includes polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber (SBR).
  • SBR styrene-butadiene rubber
  • the separator comprises an insulating porous polymer film and/or an inorganic porous film. More preferably, the separator comprises one or a combination of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a nonwoven fabric, a glass fiber paper, a porous ceramic separator, and the like.
  • the separator may have a single layer structure or a multilayer structure.
  • the present invention also provides a method for preparing the above novel sodium ion battery, comprising the steps of:
  • the prepared negative electrode, electrolyte solution, and positive electrode were used to assemble the battery to obtain the novel sodium ion battery.
  • the above preparation method further comprises the steps of: preparing a separator, and assembling the prepared separator together with the anode, the electrolyte, and the cathode to obtain the novel sodium. Ion battery.
  • the novel sodium ion battery provided by the invention has a carbon material and a carbon material capable of allowing an anion to be composed of a sodium salt.
  • a composite, a sulfide and a sulfide composite, a nitride and a nitride composite, an oxide and an oxide composite, a carbide and a carbide composite, a material having a layered crystal structure, and a composite thereof As a positive electrode active material, it is environmentally friendly and low in cost.
  • the novel sodium ion battery of the present invention does not require the use of a negative active material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.
  • the electrolyte in the novel sodium ion battery of the present invention may also employ an optimized choice of solvent species, optimized electrolyte concentration selection, and optimized additive species and concentration selection. Therefore, the novel sodium ion battery of the present invention solves the defects of the existing secondary battery, such as large environmental pollution, high manufacturing cost, and low energy density.
  • FIG. 1 is a schematic structural view of a novel sodium ion battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing the working principle of a novel sodium ion battery using a carbon material as a positive electrode active material and containing no negative electrode active material according to an embodiment of the present invention
  • Example 3 is a charge and discharge curve of a novel sodium ion battery prepared according to Example 1 of the present invention at a 5 C rate;
  • Example 4 is a charge and discharge curve of a novel sodium ion battery prepared in Example 2 of the present invention at a 5 C rate.
  • FIG. 1 is a schematic structural view of a novel sodium ion battery according to an embodiment of the present invention.
  • the novel sodium ion battery includes: a negative electrode current collector 1, an electrolyte 2, a separator 3, a positive electrode active material layer 4, a positive electrode current collector 5, and a battery case 6; the positive electrode active material layer 4 is formed on a surface of the positive electrode current collector 5, the electrolyte solution 2 and the separator 3 are located between the negative electrode current collector 1 and the positive electrode active material layer 4, and the battery case 6 is used to encapsulate the negative electrode set Fluid 1, electrolyte 2, separator 3, positive electrode active material layer 4, and positive electrode current collector 5.
  • the negative electrode of the novel sodium ion battery of the present invention does not include the negative electrode active material, and only includes the negative electrode current collector 1, which is a conductive material, and the conductive material includes aluminum, copper, iron, tin, zinc, nickel, titanium. One of manganese, or the like, or an alloy formed by several of these materials or a composite material containing one or more of these materials.
  • the electrolyte 2 includes a mixture containing an electrolyte, an additive, and a solvent;
  • the electrolyte may be a sodium salt
  • the sodium salt includes sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, sodium dodecylbenzenesulfonate.
  • the additive may include one or a combination of organic additives such as esters, sulfones, ethers, nitriles, and olefins, and the organic additives such as esters, sulfones, ethers, nitriles, and olefins include carbonates.
  • organic additives such as esters, sulfones, ethers, nitriles, and olefins
  • the organic additives such as esters, sulfones, ethers, nitriles, and olefins include carbonates.
  • Vinyl ester ethylene sulfite, propylene sulfite, vinyl chlorocarbonate, methyl chloroformate, anisole, acetamide, dinitro(benzene)benzene, m-diaza(hetero)benzene, 12- -4,18- crown ether-crown -6, (C 6 H 3 F ) O 2 B (C 6 H 3 F 2), (C 6 F 4) O 2 (C 6 F 5), 4- fluorobenzene Methyl ether, fluorinated chain ether (C 4 F 9 OCH 3 ), monofluoromethyl ethylene carbonate (CH 2 F-EC), difluoromethyl ethylene carbonate (CHF 2 -EC), trifluoro Vinyl ethylene carbonate (CF 3 -EC), phosphate, phosphite, phosphazene, ethanolamine, dimethylamine, aluminum oxide, magnesium oxide, cerium oxide, sodium carbonate, calcium carbonate, ethylene sulfate a combination of one or more
  • the solvent may include one or a combination of organic solvents such as esters, sulfones, and ethers, and the ester, sulfone, and ether organic solvents include propylene carbonate (PC), ethylene carbonate (EC), Diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA) , fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-A Tetrahydrofuran (2MeTHF), 1,3-dioxocyclopentane (DOL), 4-methyl-1,3-dioxocyclopentane (4MeDOL), dimethoxymethane (DMM),
  • the separator 3 includes an insulating porous polymer film and/or an inorganic porous film, and may be one selected from the group consisting of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a nonwoven fabric, a glass fiber paper, and a porous ceramic separator. Or a combination of several.
  • the positive electrode active material layer 4 includes a positive electrode active material, a conductive agent, and a binder, based on the total weight of the positive electrode active material layer 4, wherein the content of the positive electrode active material is 50-90%, and the content of the conductive agent is 0.1-30. %, the content of the binder is 0.1-10%;
  • the positive active material includes a carbon material and a carbon material composite, a sulfide and a sulfide composite, a nitride and a nitride composite, an oxide and an oxide composite, a carbide, and the like, which are capable of allowing an anion to be composed of a sodium salt. a combination of one or more of a carbide composite, a material having a layered crystal structure, a composite thereof, and the like;
  • the carbon material and carbon material composite comprises carbon fiber, mesophase carbon microsphere graphite, natural graphite, glassy carbon, carbon-carbon composite material, hard carbon, porous carbon, high-oriented graphite, carbon black, carbon nanotube, graphite One or more of the olefins or the like or a composite containing one or more of these carbon materials;
  • the sulfide and sulfide composite includes one of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, manganese sulfide, and the like. Or a composite of several or one or more of these sulfides;
  • the nitride and nitride composites include one or more of hexagonal boron nitride, carbon doped hexagonal boron nitride, or the like or a composite containing one or more of these nitrides;
  • the oxide and oxide composites include one or more of or include or include molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, manganese oxide, and the like. a complex of one or more of these oxides;
  • the carbide and carbide composite includes one or more of titanium carbide, tantalum carbide, molybdenum carbide, silicon carbide, or the like or a composite containing one or more of these carbides;
  • the material having a layered crystal structure and a composite thereof include one or more of mica, expanded vermiculite, tungsten selenide, zinc selenide, antimony selenide, cobalt selenide, antimony telluride, etc. or contain these a composite of one or more of materials having a layered crystal structure;
  • the conductive agent comprises one or a combination of conductive carbon black, Super P conductive carbon sphere, conductive graphite KS6, carbon nanotube, conductive carbon fiber, graphene, reduced graphene oxide, and the like;
  • the binder includes one or a combination of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber (SBR), polyolefin-based binder, and the like.
  • the cathode current collector 5 is a conductive material including one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or the like, or an alloy formed by several of these materials or one of these materials. Or several composite materials.
  • the battery case 6 can be a battery case conventionally used in the art, such as a battery case made of SUS or the like.
  • the shape of the novel sodium ion battery provided by the present invention is not particularly limited, and may be a coin type (ie, a button type), a flat type, a cylindrical type, and an angle type.
  • FIG. 2 is a schematic view showing the working principle of a novel sodium ion battery using a carbon material as a positive electrode active material and no negative electrode active material according to an embodiment of the present invention.
  • the working principle of the novel sodium ion battery provided by the present invention is completely different from that of the conventional sodium ion battery.
  • sodium ions (Na + ) in the electrolyte 2 are deposited on the surface of the anode current collector 1 , and the anions in the electrolyte 2 are embedded in the cathode active material layer 4 composed of a carbon material or the like; At the time of discharge, the sodium deposited on the anode current collector 1 is returned to the electrolytic solution 2, and the anion embedded in the positive electrode active material layer 4 is also released and returned to the electrolytic solution 2.
  • the negative electrode active material is an essential component
  • the present invention first proposes a novel sodium ion battery which does not require the use of the negative electrode active material.
  • the advantages of the sodium ion battery that does not require the use of the negative active material include: the weight and volume of the battery can be significantly reduced, thereby increasing the weight energy density and the volume energy density of the battery; in addition, the manufacturing cost of the battery can also be reduced;
  • the novel sodium ion battery of the invention can achieve a technical effect comparable to or better than that of a conventional sodium ion battery using a negative active material.
  • the positive electrode active material in the sodium ion battery of the present invention is completely different from the positive electrode active material in the conventional sodium ion battery, and specifically, the positive electrode active material of the present invention passes through the intercalation/extraction of anions in the electrolyte. Charge/discharge is achieved, and the positive active material of the conventional sodium ion battery is charged/discharged by cation deintercalation/embedding.
  • the novel sodium ion battery of the present invention is obtained by at least the above-mentioned improvement of the negative electrode (i.e., the negative electrode does not include the negative electrode active material) and the positive electrode (that is, the positive electrode active material is a material which is capable of allowing an anion to constitute a sodium salt).
  • the above improvement of the negative electrode or the positive electrode did not provide a battery equivalent to the performance and technical effects of the novel sodium ion battery of the present invention.
  • the novel sodium ion battery provided by the present invention has a material capable of allowing an anion embedded in a sodium salt to be used as a positive electrode active material, and is environmentally friendly and low in cost.
  • the novel sodium ion battery of the present invention does not require the use of a negative active material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.
  • the button type analog battery prepared by the invention has been tested by the battery system to show that the reversible charge and discharge can be realized, and the battery preparation process is significantly simplified, the material cost can be reduced by more than 40%, the self-weight of the battery active component is reduced by more than 50%, and the capacity can be compared with ordinary.
  • Sodium ion battery
  • the method for preparing the novel sodium ion battery may include the following steps:
  • the negative electrode comprises a negative electrode current collector, excluding the negative electrode active material
  • the preparation process is to cut a metal foil such as aluminum, copper, iron, tin, zinc, nickel, titanium or manganese (preferably copper, iron, tin or aluminum) into a desired size, and clean the surface for use.
  • a metal foil such as aluminum, copper, iron, tin, zinc, nickel, titanium or manganese (preferably copper, iron, tin or aluminum) into a desired size, and clean the surface for use.
  • porous polymer film or the inorganic porous film is cut into a desired size, cleaned and used.
  • the positive electrode includes a positive electrode active material layer and a positive electrode current collector.
  • the preparation process is: weighing the positive electrode active material, the conductive agent, and the binder in a certain ratio, and adding a suitable solvent (the solvent will completely volatilize in the subsequent drying process, and finally the solvent is not contained in the positive electrode active material layer) It is ground into a uniform slurry and then uniformly coated on the surface of the positive electrode current collector, that is, a positive electrode active material layer is formed on the surface of the positive electrode current collector; after the slurry is completely dried, it is cut to obtain a positive electrode of a desired size.
  • a suitable solvent the solvent will completely volatilize in the subsequent drying process, and finally the solvent is not contained in the positive electrode active material layer
  • steps 1-4 describe the operation of the preparation method of the present invention in a specific order, it is not required or implied that these operations must be performed in this particular order.
  • the preparation of steps 1-4 can be carried out simultaneously or in any order.
  • Step 5 Using a negative electrode, an electrolyte, a separator, and a positive electrode to assemble a new type of sodium ion battery:
  • the battery is assembled in an inert gas or waterless environment, and the prepared negative electrode, separator, and positive electrode are sequentially closely packed, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the battery case to complete battery assembly.
  • the invention adopts the optimized solvent type selection, the optimized electrolyte concentration selection and the optimized additive type and concentration selection in the preparation of the novel sodium ion battery, and the electrolyte can further adopt the additive modified high concentration ester electrolyte formula.
  • the present invention also provides a structure of a positive electrode of a battery, comprising a positive electrode current collector and a positive electrode active material layer formed on the surface of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material capable of allowing an anion embedded in the sodium salt composition. , conductive agent and binder.
  • the present invention selects a negative current collector that matches the electrolyte and the positive electrode of the battery.
  • Preparation of battery negative electrode Take a copper foil with a thickness of 0.5 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the Celgard 2400 porous polymer film was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 0.8 g of artificial graphite, 0.1 g of carbon black, 0.1 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil (ie, The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed as a battery positive Extremely spare.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • the prepared sodium ion battery was charged and discharged at a rate of 5 C.
  • the charge and discharge curve is shown in Fig. 3.
  • the overall energy density of the battery was 110 Wh/kg, and the discharge median voltage was 4.2V.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 0.7 g of hard carbon, 0.2 g of carbon black, 0.1 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil (ie, The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • the prepared sodium ion battery was charged and discharged at a rate of 5 C.
  • the charge and discharge curve is shown in Fig. 4.
  • the overall energy density of the battery was 98 Wh/kg, and the discharge median voltage was 3.9V.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • the vinylidene carbonate having a total weight of 3 wt% of the liquid was used as an additive, and the mixture was sufficiently stirred and then used as an electrolyte.
  • Preparation of battery positive electrode 0.8g carbon microspheres, 0.15g carbon black, 0.05g polyvinylidene fluoride was added to 2mL nitromethylpyrrolidone solution, fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil (ie The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take an iron piece with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of titanium carbide, 0.15 g of carbon black, 0.05 g of polytetrafluoroethylene was added to 2 mL of a solution of nitromethylpyrrolidone, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the zinc foil (ie, The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take a copper foil with a thickness of 0.3 mm, cut into a disk having a diameter of 12 mm, clean the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the porous polypropylene film was cut into a 16 mm-diameter wafer, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of molybdenum disulfide, 0.15 g of graphene, 0.05 g of polyvinylidene fluoride was added to 2 mL of nitrogen In the solution of the pyrrolidone, the slurry is sufficiently ground to obtain a uniform slurry; then the slurry is uniformly coated on the surface of the aluminum foil (ie, the positive electrode current collector) and vacuum dried; the electrode sheet obtained by drying is cut into a disk having a diameter of 10 mm, and after pressing Used as a battery anode.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the porous polypropylene film was cut into a 16 mm-diameter wafer, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of molybdenum disulfide, 0.15 g of Super P conductive carbon spheres, 0.05 g of polyvinyl alcohol was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the copper foil.
  • the surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the porous polyethylene film was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 0.8 g of hard carbon, 0.1 g of carbon black, 0.1 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil (ie, The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • Preparation of battery negative electrode Take a zinc foil with a thickness of 0.3 mm, cut into a disk having a diameter of 12 mm, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the porous polypropylene film was cut into a 16 mm-diameter wafer, washed with acetone, dried and used as a separator.
  • Formulation of electrolyte Weigh 3g of sodium sulfate into 5mL of ethylene carbonate solution, stir until sodium sulfate is completely dissolved, then add 1wt% of ethylene sulfite and total weight of the electrolyte. 1 wt% of ethylene carbonate was used as an additive, and it was sufficiently stirred and then used as an electrolyte.
  • Preparation of battery positive electrode 0.8 g of hexagonal boron nitride, 0.1 g of graphene, 0.1 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil ( That is, the surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • Preparation of battery negative electrode Take a titanium foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the porous polycomposite polymer film was cut into a 16 mm-diameter wafer, washed with acetone, and dried to serve as a separator.
  • Formulation of electrolyte Weigh 3g of sodium phosphate and add it to 5mL of dimethyl sulfone solution, stir until sodium phosphate is completely dissolved, then add 1wt% of phosphate ester based on the total weight of the electrolyte and 1wt% of the total weight of the electrolyte As an additive, ethylene carbonate is sufficiently stirred and used as an electrolyte.
  • Preparation of battery positive electrode 0.8 g of titanium oxide, 0.1 g of conductive carbon fiber, 0.1 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on aluminum foil (ie, The surface of the positive electrode current collector was vacuum dried; the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and pressed to serve as a positive electrode of the battery.
  • Preparation of battery negative electrode Take a tin foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the non-woven fabric was cut into a 16 mm-diameter disc, washed with acetone, and dried to serve as a separator.
  • Formulation of electrolyte Weigh 3g of sodium borate and add it to 5mL of dimethyl sulfite solution, stir until sodium borate is completely dissolved, then add 1wt% of ethylene sulfite and the electrolyte accounted for the total weight of the electrolyte. A total weight of 1% by weight of aluminum oxide is used as an additive, and the mixture is sufficiently stirred and used as an electrolyte.
  • Preparation of battery positive electrode 0.8g zinc selenide, 0.1g carbon black, 0.1g polyvinylidene fluoride was added to 2mL nitromethylpyrene In the solution of the rotary solvent, the slurry is sufficiently ground to obtain a uniform slurry; then the slurry is uniformly coated on the surface of the copper foil (ie, the positive electrode current collector) and vacuum dried; the electrode sheet obtained by drying is cut into a disk having a diameter of 10 mm, and pressed. After the death, it is used as a battery anode.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • the present invention provides a sodium ion battery of the prior art, the specific structure and preparation method of which is the same as that of Example 1 disclosed in CN104966813A (Application No.: 201510231704.4, Application Date: 2015.05.08), the negative electrode activity of the battery
  • the material was graphite, the positive active material was Na 3 V 2 (PO 4 ) 3 , and the electrolyte was 1 mol/L NaPF 6 /DEGDME solution. Based on the overall energy density of the battery was 86 Wh / kg, the discharge median voltage was 2.7V.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

本发明公开了一种新型钠离子电池及其制备方法。该新型钠离子电池包括：正极、负极以及电解液；其中，正极包括含有正极活性材料的正极活性材料层；负极包括负极集流体，不包括负极活性材料；该正极活性材料包括能容许组成钠盐的阴离子嵌入的碳材料及碳材料复合物、硫化物及硫化物复合物、氮化物及氮化物复合物、氧化物及氧化物复合物、碳化物及碳化物复合物、具有层状晶体结构的材料及其复合物中的一种或几种的组合。该新型钠离子电池的制备方法主要包括以下步骤：制备负极；配制电解液；制备正极；采用制备得到的负极、电解液、正极进行电池的组装。本发明提供的新型钠离子电池采用能容许组成钠盐的阴离子嵌入的材料作为正极活性材料，且不含负极活性材料；因此环境友好且成本低，并显著降低了电池自重和成本，提升了电池能量密度。

Description

一种新型钠离子电池及其制备方法 技术领域
本发明属于二次电池技术领域，具体涉及一种新型钠离子电池及其制备方法。
背景技术
二次电池也称为可充电电池，是一种可重复充放电、使用多次的电池。相比于不可重复使用的一次电池，二次电池具有使用成本低、对环境污染小的优点。目前主要的二次电池技术有铅酸电池、镍铬电池、镍氢电池、锂离子电池。其中尤其以锂离子电池应用最为广泛。但是锂离子电池面临着锂资源储量有限、成本高的缺点。作为潜在取代锂离子电池的储能技术，钠离子电池在近几年日益受到关注。钠离子电池的工作原理与锂离子类似，但是电池中电荷的储存于释放是通过钠离子的迁移实现。钠离子电池的核心组成部件包含正极、负极和电解液，它通过发生在正极、负极与电解液界面上的离子传输与电子传输相分离的氧化还原反应来实现电能存储与释放。充电时，钠离子从正极活性材料中脱出，嵌入负极活性材料；放电时，钠离子从负极活性材料脱出而嵌入到正极活性材料中。
常见的钠离子电池是以过渡金属氧化物(NaVO2、NaNiMnCoO2)或聚阴离子型金属化合物(Na3V2(PO4)3)等为正极活性材料，以碳材料为负极活性材料。正极活性材料中包含过渡金属元素，这一方面使得材料的制备成本增加，另一方面也使得电池废弃后对环境的潜在危害加大。
当前业内正在积极研发环境友好、能量密度高的新型二次电池技术。其中一种双碳电池尤其值得关注，这种电池以石墨或碳材料作为正极和负极活性材料，完全不含过渡金属元素。充电时，电解液中的阴离子嵌入正极石墨材料中，电解质阳离子则嵌入负极碳材料中；放电时，阴离子从正极活性材料脱出，阳离子从负极活性材料脱出。例如，美国陆军实验室的Read和Xu等(Energy Environ.Sci.2014,7,617)开发了一种双石墨二次电池，其以石墨材料同时作为负极和正极活性材料，以氟化改性酯类作为电解液溶剂，实现了该电池体系的可逆充放电实验。德国明斯特大学的Rothermel和Placke等(Energy Environ.Sci.2014,7,3412)研发了一种基于离子液体电解液的双石墨电池，亦实现了双石墨电池体系的可逆充放电。
但是，上述两项研究工作还面临如下问题：(1)石墨材料对阴离子的嵌入容量有限，因此电池容量无法与常规二次电池媲美；(2)氟化改性酯类电解液和离子液体电解液的制备成本非常高，因而削弱了双碳电池的成本优势。
发明内容
本发明的目的在于克服现有技术的不足，提供一种新型钠离子电池及其制备方法。该新型钠离子电池采用能容许组成钠盐的阴离子嵌入的材料作为正极活性材料，且不含负极活性材料，能够解决现有二次电池存在的制造成本高、能量密度低等缺陷。
为达到上述目的，本发明首先提供了一种新型钠离子电池，其包括：正极、负极、以及位于正极与负极之间的电解液，其中，
所述正极包括含有正极活性材料的正极活性材料层；
所述负极包括负极集流体，不包括负极活性材料；
所述正极活性材料包括能容许组成钠盐的阴离子嵌入的碳材料及碳材料复合物、硫化物及硫化物复合物、氮化物及氮化物复合物、氧化物及氧化物复合物、碳化物及碳化物复合物、具有层状晶体结构的材料及其复合物等中的一种或几种的组合。
根据本发明的具体实施方式，优选地，上述的新型钠离子电池还包括：隔膜，其位于所述正极与所述负极之间，用于隔离正极与负极。
根据本发明的具体实施方式，优选地，上述的新型钠离子电池还包括：电池壳体，用于封装所述正极、负极、电解液及隔膜。
在上述的新型钠离子电池中，优选地，所述负极的负极集流体为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰等中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。需说明的是，该复合材料可以是以上述金属中的一种或几种作为基体材料，与增强材料复合而成的复合材料。该增强材料可以采用本领域常规的增强材料，其添加量也可以由本领域技术人员进行常规的调整。这些增强材料可以包括碳纤维、硼纤维、碳化硅纤维、金属丝和硬质细粒等一种或几种的组合。
在上述的新型钠离子电池中，优选地，所述电解液包括含有电解质、添加剂和溶剂的混合液。其中，所述电解液中的电解质可以为钠盐，该钠盐包括氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠(NaTFSI)等中的一种或几种的组合，且所述电解质在所述电解液中的浓度范围为0.1-10mol/L。
所述电解液中的添加剂可以包括酯类、砜类、醚类、腈类和烯烃类等有机添加剂中的一种或几种的组合，该酯类、砜类、醚类、腈类和烯烃类有机添加剂包括碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、氯代碳酸乙烯酯、氯代甲酸甲脂、苯甲醚、乙酰胺、 二氮(杂)苯、间二氮(杂)苯、12-冠醚-4、18-冠醚-6、(C6H3F)O2B(C6H3F2)、(C6F4)O2(C6F5)、4-氟苯甲醚、氟代链状醚(C4F9OCH3)、一氟代甲基碳酸乙烯酯(CH2F-EC)、二氟代甲基碳酸乙烯酯(CHF2-EC)、三氟代甲基碳酸乙烯酯(CF3-EC)、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、硫酸亚乙酯、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃等中的一种或几种的组合，且以所述电解液的总重量为基准，所述添加剂在所述电解液中的含量为0.1-40％。
所述电解液中的溶剂可以包括酯类、砜类和醚类等有机溶剂中的一种或几种的组合，该酯类、砜类和醚类有机溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)，丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(例如12-冠醚-4)等中的一种或几种的组合。
在上述的新型钠离子电池中，优选地，所述正极还包括正极集流体，所述含有正极活性材料的正极活性材料层形成于所述正极集流体的表面；该正极集流体为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰等中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。需说明的是，该复合材料可以是以上述金属中的一种或几种作为基体材料，与增强材料复合而成的复合材料。该增强材料可以采用本领域常规的增强材料，其添加量也可以由本领域技术人员进行常规的调整。这些增强材料可以包括碳纤维、硼纤维、碳化硅纤维、金属丝和硬质细粒等中的一种或几种的组合。
在上述的新型钠离子电池中，优选地，所述碳材料及碳材料复合物包括碳纤维、中间相碳微球石墨、天然石墨、玻璃碳、碳碳复合材料、硬碳、多孔炭、高取向石墨、炭黑、碳纳米管、石墨烯等中的一种或几种或含有这些碳材料中的一种或几种的复合物；
所述硫化物及硫化物复合物包括二硫化钼、二硫化钨、二硫化钒、二硫化钛、二硫化铁、硫化亚铁、硫化镍、硫化锌、硫化钴、硫化锰等中的一种或几种或含有这些硫化物中的一种或几种的复合物；
所述氮化物及氮化物复合物包括六方氮化硼、碳掺杂六方氮化硼等中的一种或几种或含有这些氮化物中的一种或几种的复合物；
所述氧化物及氧化物复合物包括三氧化钼、三氧化钨、五氧化二钒、二氧化钒、二氧化钛、氧化锌、氧化铜、氧化镍、氧化锰等中的一种或几种或含有这些氧化物中的一种或几种的复合物；
所述碳化物及碳化物复合物包括碳化钛、碳化钽、碳化钼、碳化硅等中的一种或几种或含有这些碳化物中的一种或几种的复合物；
所述具有层状晶体结构的材料及其复合物包括云母、膨胀蛭石、硒化钨、硒化锌、硒化铋、硒化钴、碲化铋等中的一种或几种或含有这些具有层状晶体结构的材料中的一种或几种的复合物。
在上述的新型钠离子电池中，优选地，所述正极的正极活性材料层还包括导电剂和/或粘结剂，以所述正极活性材料层的总重量为基准，其中的正极活性材料的含量为50-90％，导电剂的含量为0.1-30％，粘结剂的含量为0.1-10％。
在上述的新型钠离子电池中，优选地，所述正极活性材料层中的导电剂包括导电炭黑、Super P导电碳球、导电石墨KS6、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯等中的一种或几种的组合。
在上述的新型钠离子电池中，优选地，所述正极活性材料层中的粘结剂包括聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶(SBR)、聚烯烃类粘结剂等中的一种或几种的组合。
在上述的新型钠离子电池中，优选地，所述隔膜包括绝缘的多孔聚合物薄膜和/或无机多孔薄膜。更优选地，所述隔膜包括多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、无纺布、玻璃纤维纸、多孔陶瓷隔膜等中的一种或几种的组合。该隔膜可以为单层结构，也可以为多层结构。
另一方面，本发明还提供了一种上述的新型钠离子电池的制备方法，其包括以下步骤：
制备负极；
配制电解液；
制备正极；
采用制备得到的负极、电解液、正极进行电池的组装，得到所述的新型钠离子电池。
根据本发明的具体实施方式，优选地，上述的制备方法还包括以下步骤：制备隔膜，并且使制备得到的隔膜与所述负极、电解液、正极一起进行电池的组装，得到所述的新型钠离子电池。
本发明提供的新型钠离子电池以能容许组成钠盐的阴离子嵌入的碳材料及碳材料 复合物、硫化物及硫化物复合物、氮化物及氮化物复合物、氧化物及氧化物复合物、碳化物及碳化物复合物、具有层状晶体结构的材料及其复合物等中的一种或几种的组合作为正极活性材料，环境友好且成本低。同时，本发明的新型钠离子电池无需使用负极活性材料，因而显著降低了电池自重和成本，提升了电池能量密度。此外，本发明的新型钠离子电池中的电解液还可以采用优化的溶剂种类的选择、优化的电解质浓度的选择和优化的添加剂种类与浓度的选择。因此，本发明的新型钠离子电池解决了现有二次电池存在的环境污染大、制造成本高、能量密度低等缺陷。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本发明的一部分，并不构成对本发明的限定。在附图中：
图1为本发明一具体实施方式提供的新型钠离子电池的结构示意图；
图2为本发明一具体实施方式提供的以碳材料作为正极活性材料且不含负极活性材料的新型钠离子电池的工作原理示意图；
图3为本发明实施例1制备的新型钠离子电池在5C倍率下的充放电曲线；
图4为本发明实施例2制备的新型钠离子电池在5C倍率下的充放电曲线。
具体实施方式
以下配合图示及本发明的一些具体实施例，进一步阐述本发明为达成所欲发明目的所采取的技术手段。
图1为本发明一具体实施方式提供的新型钠离子电池的结构示意图。如图1所示，该新型钠离子电池包括：负极集流体1、电解液2、隔膜3、正极活性材料层4、正极集流体5以及电池壳体6；所述正极活性材料层4形成于所述正极集流体5的表面，所述电解液2及所述隔膜3位于所述负极集流体1与所述正极活性材料层4之间，所述电池壳体6用于封装所述负极集流体1、电解液2、隔膜3、正极活性材料层4以及正极集流体5。
其中，本发明的新型钠离子电池的负极不包括负极活性材料，仅包括负极集流体1，该负极集流体1为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰等中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。
电解液2包括含有电解质、添加剂和溶剂的混合液；
其中，电解质可以为钠盐，该钠盐包括氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三 钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠(NaTFSI)等中的一种或几种的组合，且所述电解质在所述电解液中的浓度范围为0.1-10mol/L；
添加剂可以包括酯类、砜类、醚类、腈类和烯烃类等有机添加剂中的一种或几种的组合，该酯类、砜类、醚类、腈类和烯烃类有机添加剂包括碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、氯代碳酸乙烯酯、氯代甲酸甲脂、苯甲醚、乙酰胺、二氮(杂)苯、间二氮(杂)苯、12-冠醚-4、18-冠醚-6、(C6H3F)O2B(C6H3F2)、(C6F4)O2(C6F5)、4-氟苯甲醚、氟代链状醚(C4F9OCH3)、一氟代甲基碳酸乙烯酯(CH2F-EC)、二氟代甲基碳酸乙烯酯(CHF2-EC)、三氟代甲基碳酸乙烯酯(CF3-EC)、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、硫酸亚乙酯、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃等中的一种或几种的组合，且以所述电解液的总重量为基准，所述添加剂在所述电解液中的含量为0.1-40％；
溶剂可以包括酯类、砜类和醚类等有机溶剂中的一种或几种的组合，该酯类、砜类和醚类有机溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)，丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(例如12-冠醚-4)等中的一种或几种的组合。
隔膜3包括绝缘的多孔聚合物薄膜和/或无机多孔薄膜，可以选用多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、无纺布、玻璃纤维纸、多孔陶瓷隔膜等中的一种或几种的组合。
正极活性材料层4包括正极活性材料、导电剂和粘结剂，以正极活性材料层4的总重量为基准，其中的正极活性材料的含量为50-90％，导电剂的含量为0.1-30％，粘结剂的含量为0.1-10％；
所述正极活性材料包括能容许组成钠盐的阴离子嵌入的碳材料及碳材料复合物、硫化物及硫化物复合物、氮化物及氮化物复合物、氧化物及氧化物复合物、碳化物及碳化物复合物、具有层状晶体结构的材料及其复合物等中的一种或几种的组合；
其中，所述碳材料及碳材料复合物包括碳纤维、中间相碳微球石墨、天然石墨、玻璃碳、碳碳复合材料、硬碳、多孔炭、高取向石墨、炭黑、碳纳米管、石墨烯等中的一种或几种或含有这些碳材料中的一种或几种的复合物；
所述硫化物及硫化物复合物包括二硫化钼、二硫化钨、二硫化钒、二硫化钛、二硫化铁、硫化亚铁、硫化镍、硫化锌、硫化钴、硫化锰等中的一种或几种或含有这些硫化物中的一种或几种的复合物；
所述氮化物及氮化物复合物包括六方氮化硼、碳掺杂六方氮化硼等中的一种或几种或含有这些氮化物中的一种或几种的复合物；
所述氧化物及氧化物复合物包括三氧化钼、三氧化钨、五氧化二钒、二氧化钒、二氧化钛、氧化锌、氧化铜、氧化镍、氧化锰等中的一种或几种或含有这些氧化物中的一种或几种的复合物；
所述碳化物及碳化物复合物包括碳化钛、碳化钽、碳化钼、碳化硅等中的一种或几种或含有这些碳化物中的一种或几种的复合物；
所述具有层状晶体结构的材料及其复合物包括云母、膨胀蛭石、硒化钨、硒化锌、硒化铋、硒化钴、碲化铋等中的一种或几种或含有这些具有层状晶体结构的材料中的一种或几种的复合物；
导电剂包括导电炭黑、Super P导电碳球、导电石墨KS6、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯等中的一种或几种的组合；
粘结剂包括聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶(SBR)、聚烯烃类粘结剂等中的一种或几种的组合。
正极集流体5为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰等中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。
电池壳体6可以采用本领域常规使用的电池壳体，例如SUS制电池壳体等。
本发明提供的新型钠离子电池的形状没有特殊限制，可以为硬币型(即扣型)、平板型、圆筒型以及角型等。
图2为本发明一具体实施方式提供的以碳材料作为正极活性材料且不含负极活性材料的新型钠离子电池的工作原理示意图。如图2所示，本发明提供的新型钠离子电池的工作原理与传统的钠离子电池完全不同。传统的钠离子电池充电时，钠离子从正极活性材料中脱出，然后嵌入负极活性材料中；放电时，钠离子则从负极活性材料中脱出，嵌入正极活性材料中。本发明的新型钠离子电池充电时，电解液2中的钠离子(Na+)沉积到负极集流体1表面，同时电解液2中的阴离子则嵌入碳材料等组成的正极活性材料 层4中；放电时，负极集流体1上沉积的钠回到电解液2中，嵌入正极活性材料层4中的阴离子也脱出，回到电解液2中。
在传统的钠离子电池中，负极活性材料是必须的组分，而本发明首次提出无需使用负极活性材料的新型钠离子电池。这种无需使用负极活性材料的钠离子电池所具备的优点包括：电池重量、体积可显著降低，进而使得电池重量能量密度和体积能量密度获得提升；此外，电池制造成本也可获得降低；并且本发明的新型钠离子电池可以获得与使用负极活性材料的传统钠离子电池相当或更好的技术效果。此外，本发明的钠离子电池中的正极活性材料与传统钠离子电池中的正极活性材料在工作原理上完全不同，具体地说，本发明的正极活性材料通过电解液中阴离子的嵌入/脱出而实现充/放电，而传统钠离子电池的正极活性材料则是通过阳离子的脱出/嵌入来实现充/放电。本发明的新型钠离子电池是至少通过上述对于负极(即负极不包括负极活性材料)和正极(即正极活性材料采用能容许组成钠盐的阴离子嵌入的材料)的同时改进而得到的，单独对负极或正极进行上述改进，无法得到与本发明的新型钠离子电池的性能及技术效果相当的电池。
相比于现有的二次电池技术，本发明提供的新型钠离子电池以能容许组成钠盐的阴离子嵌入的材料作为正极活性材料，环境友好且成本低。同时，本发明的新型钠离子电池无需使用负极活性材料，因而显著降低了电池自重和成本，提升了电池能量密度。
本发明已制备出的扣式模拟电池，通过电池系统测试表明能够实现可逆充放电，且电池制备过程显著简化，材料成本可降低40％以上，电池活性成分自重降低50％以上，容量可比拟普通钠离子电池。
在本发明一具体实施方式中，该新型钠离子电池的制备方法可以包括以下步骤：
步骤1、制备负极：
其中，负极包括负极集流体，不包括负极活性材料；
具体地，制备过程是将铝、铜、铁、锡、锌、镍、钛或锰(优选铜、铁、锡或铝)等金属箔片裁切成所需尺寸，将表面清洗干净备用。
步骤2、配制电解液：
称取适量电解质(即钠盐)加入到一定体积的溶剂中，充分搅拌溶解后，再加入一定量的添加剂，搅拌均匀后备用。
步骤3、制备隔膜：
将多孔聚合物薄膜或无机多孔薄膜裁切成所需尺寸，清洗干净后备用。
步骤4、制备正极：
其中，正极包括正极活性材料层及正极集流体。
具体地，制备过程是按一定比例称取正极活性材料、导电剂、粘结剂，加入适当溶剂(该溶剂会在后续干燥过程中完全挥发，最终正极活性材料层中不包含该溶剂)中充分研磨成均匀浆料，然后均匀涂覆于正极集流体表面，即在正极集流体表面形成了正极活性材料层；待浆料完全干燥后进行裁切，得到所需尺寸的正极。
尽管上述步骤1-4是以特定顺序描述了本发明制备方法的操作，但是，这并非要求或者暗示必须按照该特定顺序来执行这些操作。步骤1-4的制备可以同时或者任意先后执行。
步骤5、利用负极、电解液、隔膜、正极进行新型钠离子电池的组装：
在惰性气体或无水环境下组装电池，将上述制备好的负极、隔膜、正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入电池壳体，完成电池组装。
本发明在制备新型钠离子电池时，采用优化的溶剂种类的选择、优化的电解质浓度的选择和优化的添加剂种类与浓度的选择，电解液更可以采用添加剂改性的高浓度酯类电解液配方。并且，本发明还提出了一种电池正极的结构，包括正极集流体以及形成于该正极集流体表面的正极活性材料层，且正极活性材料层包括能容许组成钠盐的阴离子嵌入的正极活性材料、导电剂和粘结剂。同时，本发明选择了与该电解液和该电池正极相匹配的负极集流体。
为了对本发明提供的新型钠离子电池进行更为清楚地阐述，下面结合一些具体的实施例来进行说明，然而值得注意的是这些实施例仅是为了更好地说明本发明，并不构成对本发明不当的限定。
实施例1
制备电池负极：取厚度为0.5mm的铜箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将Celgard2400多孔聚合物薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸钠加入到5mL碳酸甲乙酯中，搅拌至六氟磷酸钠完全溶解，然后加入占所述电解液总重量2wt％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g人造石墨、0.1g碳黑、0.1g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正 极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
将制备得到的新型钠离子电池以5C倍率进行充放电，充放电曲线如图3所示，基于该电池的整体能量密度达到110Wh/kg，放电中值电压为4.2V。
实施例2
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸钠加入到5mL碳酸丙烯酯/碳酸乙烯酯(体积比＝1:1)的混合溶液中，搅拌至六氟磷酸钠完全溶解，然后加入占所述电解液总重量3wt％的亚硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.7g硬碳、0.2g碳黑、0.1g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
将制备得到的新型钠离子电池以5C倍率进行充放电，充放电曲线如图4所示，基于该电池的整体能量密度达到98Wh/kg，放电中值电压为3.9V。
实施例3
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取2g四氟硼酸钠加入到5mL碳酸乙烯酯/碳酸二甲酯(体积比＝1:1)的混合溶液中，搅拌至四氟硼酸钠完全溶解，然后加入占所述电解液总重量3wt％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g碳微球、0.15g碳黑、0.05g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
实施例4
制备电池负极：取厚度为0.3mm的铁片，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g高氯酸钠加入到5mL碳酸乙烯酯/二甲醚(重量比＝1:1)的混合溶液中，搅拌至高氯酸钠完全溶解，然后加入占所述电解液总重量2wt％的硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g碳化钛、0.15g碳黑、0.05g聚四氟乙烯加入到2mL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锌箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
实施例5
制备电池负极：取厚度为0.3mm的铜箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚丙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g高氯酸钠加入到5mL碳酸乙烯酯/碳酸二乙酯(体积比＝1:1)的混合溶液中，搅拌至高氯酸钠完全溶解，然后加入占所述电解液总重量2wt％的环丁基砜作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g二硫化钼、0.15g石墨烯、0.05g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
实施例6
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚丙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g三氟甲烷磺酰亚胺钠加入到5mL碳酸丙烯酯/碳酸甲乙酯(重量比＝1:1)的混合溶液中，搅拌至三氟甲烷磺酰亚胺钠完全溶解，然后加入占所述电解液总重量2wt％的亚硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g二硫化钼、0.15g Super P导电碳球、0.05g聚乙烯醇加入到2mL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(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
实施例7
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚乙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g高氯酸钠加入到5mL碳酸乙烯酯/碳酸甲乙酯(体积比＝1:1)的混合溶液中，搅拌至高氯酸钠完全溶解，然后加入占所述电解液总重量2wt％的碳酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g硬碳、0.1g碳黑、0.1g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
实施例8
制备电池负极：取厚度为0.3mm的锌箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚丙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g硫酸钠加入到5mL碳酸乙烯酯溶液中，搅拌至硫酸钠完全溶解，然后加入占所述电解液总重量1wt％的亚硫酸亚乙酯和占所述电解液总重量1wt％的碳酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g六方氮化硼、0.1g石墨烯、0.1g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
实施例9
制备电池负极：取厚度为0.3mm的钛箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚复合聚合物薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g磷酸钠加入到5mL二甲基砜溶液中，搅拌至磷酸钠完全溶解，然后加入占所述电解液总重量1wt％的磷酸酯和占所述电解液总重量1wt％的碳酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g氧化钛、0.1g导电碳纤维、0.1g聚偏氟乙烯加入到2mL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铝箔(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
实施例10
制备电池负极：取厚度为0.3mm的锡箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将无纺布裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g硼酸钠加入到5mL亚硫酸二甲酯溶液中，搅拌至硼酸钠完全溶解，然后加入占所述电解液总重量1wt％的亚硫酸亚乙酯和占所述电解液总重量1wt％的三氧化二铝作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g硒化锌、0.1g碳黑、0.1g聚偏氟乙烯加入到2mL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(即，正极集流体)表面并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，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电池壳体，完成电池组装。
对比例1
本对比例提供了一种现有技术中的钠离子电池，其具体结构及制备方法与CN104966813A(申请号：201510231704.4，申请日：2015.05.08)中公开的实施例1相同，该电池的负极活性材料为石墨，正极活性材料为Na3V2(PO4)3，电解液为1mol/L的NaPF6/DEGDME溶液。基于该电池的整体能量密度为86Wh/kg，放电中值电压为2.7V。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (17)

  1. 一种新型钠离子电池，其特征在于，包括：正极、负极、以及位于正极与负极之间的电解液，其中，
    所述正极包括含有正极活性材料的正极活性材料层；
    所述负极包括负极集流体，不包括负极活性材料；
    所述正极活性材料包括能容许组成钠盐的阴离子嵌入的碳材料及碳材料复合物、硫化物及硫化物复合物、氮化物及氮化物复合物、氧化物及氧化物复合物、碳化物及碳化物复合物、具有层状晶体结构的材料及其复合物中的一种或几种的组合。
  2. 根据权利要求1所述的新型钠离子电池，其特征在于，还包括：隔膜，其位于所述正极与所述负极之间，用于隔离正极与负极。
  3. 根据权利要求2所述的新型钠离子电池，其特征在于，还包括：电池壳体，用于封装所述正极、负极、电解液及隔膜。
  4. 根据权利要求1所述的新型钠离子电池，其特征在于，所述负极的负极集流体为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。
  5. 根据权利要求1所述的新型钠离子电池，其特征在于，所述电解液包括含有电解质、添加剂和溶剂的混合液。
  6. 根据权利要求5所述的新型钠离子电池，其特征在于，所述电解液中的电解质为钠盐，该钠盐包括氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠中的一种或几种的组合，且所述电解质在所述电解液中的浓度范围为0.1-10mol/L。
  7. 根据权利要求5所述的新型钠离子电池，其特征在于，所述电解液中的添加剂包括酯类、砜类、醚类、腈类和烯烃类有机添加剂中的一种或几种的组合，该酯类、砜类、醚类、腈类和烯烃类有机添加剂包括碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、氯代碳酸乙烯酯、氯代甲酸甲脂、苯甲醚、乙酰胺、二氮(杂)苯、间二氮(杂)苯、12-冠醚-4、18-冠醚-6、(C6H3F)O2B(C6H3F2)、(C6F4)O2(C6F5)、4-氟苯甲醚、氟代链状醚、一氟代甲基碳酸乙烯酯、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、硫 酸亚乙酯、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃中的一种或几种的组合，且以所述电解液的总重量为基准，所述添加剂在所述电解液中的含量为0.1-40％。
  8. 根据权利要求5所述的新型钠离子电池，其特征在于，所述电解液中的溶剂包括酯类、砜类和醚类有机溶剂中的一种或几种的组合，该酯类、砜类和醚类有机溶剂包括碳酸丙烯酯、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、N,N-二甲基乙酰胺、氟代碳酸乙烯酯，丙酸甲酯、丙酸乙酯、乙酸乙酯、γ-丁内酯、四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、4-甲基-1,3-二氧环戊烷、二甲氧甲烷、1,2-二甲氧丙烷、三乙二醇二甲醚、二甲基砜、二甲醚、亚硫酸乙烯酯、亚硫酸丙烯脂、亚硫酸二甲脂、亚硫酸二乙脂、冠醚中的一种或几种的组合。
  9. 根据权利要求1所述的新型钠离子电池，其特征在于，所述正极还包括正极集流体，所述含有正极活性材料的正极活性材料层形成于所述正极集流体的表面；该正极集流体为导电材料，该导电材料包括铝、铜、铁、锡、锌、镍、钛、锰中的一种或这些材料中的几种形成的合金或含有这些材料中的一种或几种的复合材料。
  10. 根据权利要求1或9所述的新型钠离子电池，其特征在于，所述正极的正极活性材料层还包括导电剂和/或粘结剂，以所述正极活性材料层的总重量为基准，其中的正极活性材料的含量为50-90％，导电剂的含量为0.1-30％，粘结剂的含量为0.1-10％。
  11. 根据权利要求1所述的新型钠离子电池，其特征在于，所述碳材料及碳材料复合物包括碳纤维、中间相碳微球石墨、天然石墨、玻璃碳、碳碳复合材料、硬碳、多孔炭、高取向石墨、炭黑、碳纳米管、石墨烯中的一种或几种或含有这些碳材料中的一种或几种的复合物；
    所述硫化物及硫化物复合物包括二硫化钼、二硫化钨、二硫化钒、二硫化钛、二硫化铁、硫化亚铁、硫化镍、硫化锌、硫化钴、硫化锰中的一种或几种或含有这些硫化物中的一种或几种的复合物；
    所述氮化物及氮化物复合物包括六方氮化硼、碳掺杂六方氮化硼中的一种或两种或含有这些氮化物中的一种或两种的复合物；
    所述氧化物及氧化物复合物包括三氧化钼、三氧化钨、五氧化二钒、二氧化钒、二氧化钛、氧化锌、氧化铜、氧化镍、氧化锰中的一种或几种或含有这些氧化物中的一种或几种的复合物；
    所述碳化物及碳化物复合物包括碳化钛、碳化钽、碳化钼、碳化硅中的一种或几种或含有这些碳化物中的一种或几种的复合物；
    所述具有层状晶体结构的材料及其复合物包括云母、膨胀蛭石、硒化钨、硒化锌、 硒化铋、硒化钴、碲化铋中的一种或几种或含有这些具有层状晶体结构的材料中的一种或几种的复合物。
  12. 根据权利要求10所述的新型钠离子电池，其特征在于，所述导电剂包括导电炭黑、Super P导电碳球、导电石墨KS6、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯中的一种或几种的组合。
  13. 根据权利要求10所述的新型钠离子电池，其特征在于，所述粘结剂包括聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶、聚烯烃类粘结剂中的一种或几种的组合。
  14. 根据权利要求2所述的新型钠离子电池，其特征在于，所述隔膜包括绝缘的多孔聚合物薄膜和/或无机多孔薄膜。
  15. 根据权利要求2或14所述的新型钠离子电池，其特征在于，所述隔膜包括多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、无纺布、玻璃纤维纸、多孔陶瓷隔膜中的一种或几种的组合。
  16. 一种权利要求1-15中任一项所述的新型钠离子电池的制备方法，其特征在于，包括以下步骤：
    制备负极；
    配制电解液；
    制备正极；
    采用制备得到的负极、电解液、正极进行电池的组装，得到所述的新型钠离子电池。
  17. 根据权利要求16所述的制备方法，其特征在于，还包括以下步骤：制备隔膜，并且使制备得到的隔膜与所述负极、电解液、正极一起进行电池的组装，得到所述的新型钠离子电池。
PCT/CN2015/099967 2015-12-30 2015-12-30 一种新型钠离子电池及其制备方法 Ceased WO2017113234A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2015/099967 WO2017113234A1 (zh) 2015-12-30 2015-12-30 一种新型钠离子电池及其制备方法
CN201580001257.1A CN107148697A (zh) 2015-12-30 2015-12-30 一种新型钠离子电池及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/099967 WO2017113234A1 (zh) 2015-12-30 2015-12-30 一种新型钠离子电池及其制备方法

Publications (1)

Publication Number Publication Date
WO2017113234A1 true WO2017113234A1 (zh) 2017-07-06

Family

ID=59224100

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/099967 Ceased WO2017113234A1 (zh) 2015-12-30 2015-12-30 一种新型钠离子电池及其制备方法

Country Status (2)

Country Link
CN (1) CN107148697A (zh)
WO (1) WO2017113234A1 (zh)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108172903A (zh) * 2017-12-26 2018-06-15 深圳先进技术研究院 电解液、钠离子二次电池及其制备方法
CN108242560A (zh) * 2017-12-26 2018-07-03 深圳先进技术研究院 锌基双离子电池及其制备方法
CN108470908A (zh) * 2017-02-23 2018-08-31 深圳先进技术研究院 一种二次电池及其制备方法
CN111321477A (zh) * 2018-12-17 2020-06-23 深圳先进技术研究院 SnX2纳米纤维材料、制备方法、负极活性材料、负极、二次电池或电容器及其制备方法
CN111453759A (zh) * 2020-03-25 2020-07-28 陕西科技大学 一种钠离子电池用铜箔原位生长三维硫化铜负极材料、制备方法及应用
CN111542960A (zh) * 2017-10-11 2020-08-14 法国国家科学研究中心 包括特定的添加剂的组合的电解质组合物、其作为非水性液态电解质在Na-离子电池中的用途以及包括这种电解质组合物的Na-离子电池
CN113437276A (zh) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 正极活性材料、电化学装置与电子设备
CN113474931A (zh) * 2019-02-28 2021-10-01 三菱化学株式会社 钠离子二次电池用非水系电解液和钠离子二次电池
CN113540446A (zh) * 2021-07-05 2021-10-22 武汉钜能科技有限责任公司 一种锂离子电池负极材料及其制备方法
CN114050246A (zh) * 2021-11-16 2022-02-15 郑州大学 微米级多孔硫酸亚铁钠/碳复合正极材料及其制备的钠离子电池或钠电池
CN114142027A (zh) * 2021-12-09 2022-03-04 广东工业大学 一种钠离子电池负极材料及其制备方法和钠离子电池负极
CN114221031A (zh) * 2021-11-26 2022-03-22 四川英能基科技有限公司 用于钠离子电池的电解液配方、应用及制备工艺
CN114373982A (zh) * 2021-12-30 2022-04-19 复旦大学 一种基于液态醚类有机电解液的少负极二次钠电池及其制备方法
US11417884B2 (en) 2017-12-20 2022-08-16 Cornell University Titanium disulfide-sulfur composites
CN115064771A (zh) * 2022-06-23 2022-09-16 华中科技大学 一种钠离子电池电解液、电池和应用
CN115498177A (zh) * 2019-01-11 2022-12-20 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片及钠离子电池
CN116154106A (zh) * 2023-02-13 2023-05-23 华星先进科学技术应用研究(天津)有限公司 一种用于钠离子二次电池的多层复合锡箔负极及其制备方法
CN113745647B (zh) * 2021-07-30 2023-08-08 东莞力朗电池科技有限公司 一种可充电钠离子二次电池及制作方法
US20230369594A1 (en) * 2020-09-25 2023-11-16 The Board Of Trustees Of The Leland Stanford Junior University Primary and secondary sodium and lithium batteries
CN117923437A (zh) * 2024-01-29 2024-04-26 江苏大学 一种还原氧化石墨烯/硒化铋复合材料的制备方法及其在水系锌离子电池中的应用
WO2024108365A1 (zh) * 2022-11-22 2024-05-30 中国科学院深圳先进技术研究院 兼具双离子和摇椅式机理的二次电池及其制备方法和应用
CN118281298A (zh) * 2024-05-08 2024-07-02 天津润雅科技股份有限公司 提升钠离子电池容量的电化学补钠方法
WO2024160211A1 (zh) * 2023-01-31 2024-08-08 比亚迪股份有限公司 钠电池及用电设备
CN118900822A (zh) * 2024-05-10 2024-11-05 昆明理工大学 一种碳纳米管-亲钠金属无负极钠金属电池电极材料制备方法及其应用
CN118993020A (zh) * 2023-05-19 2024-11-22 中国石油化工股份有限公司 一种钠离子电池负极材料及其制备方法和包含其负极材料的负极极片、钠离子二次电池
CN121063520A (zh) * 2025-11-03 2025-12-05 山东海化集团有限公司 一种钠离子电池负极材料的制备方法及应用

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109390624B (zh) * 2018-11-09 2020-12-11 清华-伯克利深圳学院筹备办公室 一种钠基全碳电池及其制备方法
CN112397768A (zh) * 2019-08-16 2021-02-23 深圳先进技术研究院 一种新型二次电池及其制备方法
CN111969185B (zh) * 2020-07-07 2022-04-01 湖南大学 包覆TiO2的石墨双离子电池复合正极材料及其制备方法
CN113437356B (zh) * 2021-06-26 2022-03-22 宁德时代新能源科技股份有限公司 平板式钠金属电池、电化学装置
CN114256459A (zh) * 2021-12-14 2022-03-29 上海电力大学 一种氟代混合焦磷酸铁锰钠二元正极材料、制备方法及其在钠离子电池中的应用
CN114597389B (zh) * 2022-01-25 2024-06-25 中南大学 NaCrO2@氟磷酸过渡金属钠/C复合材料及其制备和在钠离子电池中的应用
CN115132986B (zh) * 2022-06-24 2026-03-31 中国科学院苏州纳米技术与纳米仿生研究所 一种钠离子电池及其制备方法
CN115020645B (zh) * 2022-07-26 2023-12-08 山东仁丰特种材料股份有限公司 一种复合电极材料及其制备方法和固态电池
CN115763821B (zh) * 2022-12-28 2024-11-05 珠海科创能源技术有限公司 一种自补钠负极材料及在钠离子电池中的应用
CN120398128B (zh) * 2025-06-27 2025-09-12 东华理工大学南昌校区 一种钠离子电池层状氧化物正极材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103094583A (zh) * 2011-11-03 2013-05-08 苏州宝时得电动工具有限公司 电池及电池集流体的处理方法
CN103493279A (zh) * 2011-03-28 2014-01-01 日产自动车株式会社 钠离子二次电池用添加剂以及钠离子二次电池
WO2015037489A1 (ja) * 2013-09-11 2015-03-19 国立大学法人 東京大学 ナトリウムイオン二次電池用正極材料

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009231234A (ja) * 2008-03-25 2009-10-08 Fuji Heavy Ind Ltd 負極用炭素材料、蓄電デバイス、及び蓄電デバイス搭載品
WO2010036448A2 (en) * 2008-07-24 2010-04-01 California Institute Of Technology Carbon cathodes for fluoride ion storage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103493279A (zh) * 2011-03-28 2014-01-01 日产自动车株式会社 钠离子二次电池用添加剂以及钠离子二次电池
CN103094583A (zh) * 2011-11-03 2013-05-08 苏州宝时得电动工具有限公司 电池及电池集流体的处理方法
WO2015037489A1 (ja) * 2013-09-11 2015-03-19 国立大学法人 東京大学 ナトリウムイオン二次電池用正極材料

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108470908A (zh) * 2017-02-23 2018-08-31 深圳先进技术研究院 一种二次电池及其制备方法
CN108470908B (zh) * 2017-02-23 2021-02-09 深圳先进技术研究院 一种二次电池及其制备方法
CN111542960A (zh) * 2017-10-11 2020-08-14 法国国家科学研究中心 包括特定的添加剂的组合的电解质组合物、其作为非水性液态电解质在Na-离子电池中的用途以及包括这种电解质组合物的Na-离子电池
CN111542960B (zh) * 2017-10-11 2023-11-17 法国国家科学研究中心 电解质组合物、其在钠离子电池中的用途以及包括其的钠离子电池
US11417884B2 (en) 2017-12-20 2022-08-16 Cornell University Titanium disulfide-sulfur composites
CN108172903A (zh) * 2017-12-26 2018-06-15 深圳先进技术研究院 电解液、钠离子二次电池及其制备方法
CN108242560B (zh) * 2017-12-26 2021-04-20 深圳先进技术研究院 锌基双离子电池及其制备方法
CN108172903B (zh) * 2017-12-26 2020-11-03 深圳先进技术研究院 电解液、钠离子二次电池及其制备方法
CN108242560A (zh) * 2017-12-26 2018-07-03 深圳先进技术研究院 锌基双离子电池及其制备方法
CN111321477A (zh) * 2018-12-17 2020-06-23 深圳先进技术研究院 SnX2纳米纤维材料、制备方法、负极活性材料、负极、二次电池或电容器及其制备方法
CN115498177A (zh) * 2019-01-11 2022-12-20 宁德时代新能源科技股份有限公司 正极活性材料及其制备方法、正极极片及钠离子电池
CN113474931A (zh) * 2019-02-28 2021-10-01 三菱化学株式会社 钠离子二次电池用非水系电解液和钠离子二次电池
US12456760B2 (en) 2019-02-28 2025-10-28 Mitsubishi Chemical Corporation Non-aqueous electrolyte solution for sodium ion secondary battery, and sodium ion secondary battery
EP3933997A4 (en) * 2019-02-28 2022-04-27 Mitsubishi Chemical Corporation ANHYDROUS ELECTROLYTE SOLUTION FOR SODIUM ION SECONDARY BATTERY AND SODIUM ION SECONDARY BATTERY
CN111453759A (zh) * 2020-03-25 2020-07-28 陕西科技大学 一种钠离子电池用铜箔原位生长三维硫化铜负极材料、制备方法及应用
US20230369594A1 (en) * 2020-09-25 2023-11-16 The Board Of Trustees Of The Leland Stanford Junior University Primary and secondary sodium and lithium batteries
CN113437276A (zh) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 正极活性材料、电化学装置与电子设备
CN113540446A (zh) * 2021-07-05 2021-10-22 武汉钜能科技有限责任公司 一种锂离子电池负极材料及其制备方法
CN113540446B (zh) * 2021-07-05 2022-10-25 常德昆宇新能源科技有限公司 一种锂离子电池负极材料及其制备方法
CN113745647B (zh) * 2021-07-30 2023-08-08 东莞力朗电池科技有限公司 一种可充电钠离子二次电池及制作方法
CN114050246B (zh) * 2021-11-16 2023-02-07 郑州大学 微米级多孔硫酸亚铁钠/碳复合正极材料及其制备的钠离子电池或钠电池
CN114050246A (zh) * 2021-11-16 2022-02-15 郑州大学 微米级多孔硫酸亚铁钠/碳复合正极材料及其制备的钠离子电池或钠电池
CN114221031A (zh) * 2021-11-26 2022-03-22 四川英能基科技有限公司 用于钠离子电池的电解液配方、应用及制备工艺
CN114142027A (zh) * 2021-12-09 2022-03-04 广东工业大学 一种钠离子电池负极材料及其制备方法和钠离子电池负极
CN114373982B (zh) * 2021-12-30 2024-02-27 复旦大学 一种基于液态醚类有机电解液的少负极二次钠电池及其制备方法
CN114373982A (zh) * 2021-12-30 2022-04-19 复旦大学 一种基于液态醚类有机电解液的少负极二次钠电池及其制备方法
CN115064771A (zh) * 2022-06-23 2022-09-16 华中科技大学 一种钠离子电池电解液、电池和应用
WO2024108365A1 (zh) * 2022-11-22 2024-05-30 中国科学院深圳先进技术研究院 兼具双离子和摇椅式机理的二次电池及其制备方法和应用
WO2024160211A1 (zh) * 2023-01-31 2024-08-08 比亚迪股份有限公司 钠电池及用电设备
CN116154106A (zh) * 2023-02-13 2023-05-23 华星先进科学技术应用研究(天津)有限公司 一种用于钠离子二次电池的多层复合锡箔负极及其制备方法
CN118993020A (zh) * 2023-05-19 2024-11-22 中国石油化工股份有限公司 一种钠离子电池负极材料及其制备方法和包含其负极材料的负极极片、钠离子二次电池
CN117923437A (zh) * 2024-01-29 2024-04-26 江苏大学 一种还原氧化石墨烯/硒化铋复合材料的制备方法及其在水系锌离子电池中的应用
CN117923437B (zh) * 2024-01-29 2025-12-12 江苏大学 一种还原氧化石墨烯/硒化铋复合材料的制备方法及其在水系锌离子电池中的应用
CN118281298A (zh) * 2024-05-08 2024-07-02 天津润雅科技股份有限公司 提升钠离子电池容量的电化学补钠方法
CN118900822A (zh) * 2024-05-10 2024-11-05 昆明理工大学 一种碳纳米管-亲钠金属无负极钠金属电池电极材料制备方法及其应用
CN121063520A (zh) * 2025-11-03 2025-12-05 山东海化集团有限公司 一种钠离子电池负极材料的制备方法及应用

Also Published As

Publication number Publication date
CN107148697A (zh) 2017-09-08

Similar Documents

Publication Publication Date Title
WO2017113234A1 (zh) 一种新型钠离子电池及其制备方法
KR102091376B1 (ko) 이차전지 및 그 제조방법
CN108172903B (zh) 电解液、钠离子二次电池及其制备方法
WO2017190365A1 (zh) 一种钠离子电池及其制备方法
CN108511803A (zh) 一种二次电池及其制备方法
CN108321387A (zh) 碲基材料用作负极活性材料在钠基双离子电池中的应用、钠碲双离子电池及其制备方法
WO2018152755A1 (zh) 一种二次电池及其制备方法
WO2017190355A1 (zh) 一种电解液、含有所述电解液的二次电池及其制备方法
CN108630979B (zh) 一种基于钙离子的二次电池及其制备方法
CN109659528B (zh) 钾离子电池负极活性材料、钾离子电池负极材料、钾离子电池负极、钾离子电池及其应用
CN111354924A (zh) 钠离子电池正极活性材料、钠离子电池正极材料、钠离子电池正极和钠离子电池及制备方法
WO2021104059A1 (zh) 一种新型电池及其制备方法
CN108155409B (zh) 钡基双离子电池及其制备方法
CN108470908A (zh) 一种二次电池及其制备方法
CN108615933A (zh) 一种基于新型正极材料的铝离子电池及其制备方法
WO2018170925A1 (zh) 一种基于钙离子的二次电池及其制备方法
CN112397768A (zh) 一种新型二次电池及其制备方法
WO2017206062A1 (zh) 一种二次电池及其制备方法
CN108172896B (zh) 钙离子二次电池及其制备方法
KR102848096B1 (ko) 리튬-황 이차전지용 캡슐 및 이를 포함하는 리튬-황 이차전지
CN103138002A (zh) 新型锂-硫电池及其制备方法
CN109962231A (zh) 金属箔材用作镧离子二次电池负极和镧离子二次电池及其制备方法
JP6966149B2 (ja) 水系電解液およびこれを含むエネルギー貯蔵装置
WO2018152754A1 (zh) 一种二次电池及其制备方法
CN107275097A (zh) 金属导电材料用作钾离子混合超级电容器负极和钾离子混合超级电容器及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15911863

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 05/09/2018)

122 Ep: pct application non-entry in european phase

Ref document number: 15911863

Country of ref document: EP

Kind code of ref document: A1