CN112397768A - Novel secondary battery and preparation method thereof - Google Patents

Novel secondary battery and preparation method thereof Download PDF

Info

Publication number
CN112397768A
CN112397768A CN201910758927.4A CN201910758927A CN112397768A CN 112397768 A CN112397768 A CN 112397768A CN 201910758927 A CN201910758927 A CN 201910758927A CN 112397768 A CN112397768 A CN 112397768A
Authority
CN
China
Prior art keywords
sodium
active material
electrolyte
electrode active
positive electrode
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.)
Pending
Application number
CN201910758927.4A
Other languages
Chinese (zh)
Inventor
唐永炳
蔡菁华
姚文娇
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 CN201910758927.4A priority Critical patent/CN112397768A/en
Publication of CN112397768A publication Critical patent/CN112397768A/en
Pending 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
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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

Landscapes

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

Abstract

本发明提供的新型二次电池，包括依次设置的负极集流体层、负极活性材料层、电解液、正极活性材料层及正极集流体层，所述电解液中设有隔膜，所述电解液包括电解质，所述电解质为电解质钠盐，所述正极活性材料层包括正极活性材料，所述正极活性材料为能容许钠离子自由嵌入与脱出的Na2M2(C2O4)3·2H2O材料，M为Co,Ni,Mn中的至少一种，本发明提供的新型二次电池由于不含锂材料，不受锂资源的制约，电池可以得到长足发展，生产成本显著降低。与现有钠离子电池相比，其电池的电化学性能较为优异，电池的使用寿命较长，容量保持率高，容量相对较高，且正负极材料简单、易得、环保，致使全电池的生产工艺简单，成本低。

Figure 201910758927

The novel secondary battery provided by the present invention includes a negative electrode current collector layer, a negative electrode active material layer, an electrolyte solution, a positive electrode active material layer and a positive electrode current collector layer arranged in sequence, wherein a separator is arranged in the electrolyte solution, and the electrolyte solution includes An electrolyte, the electrolyte is an electrolyte sodium salt, the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material is Na 2 M 2 (C 2 O 4 ) 3 ·2H 2 that can allow free insertion and extraction of sodium ions O material, M is at least one of Co, Ni, and Mn. Since the novel secondary battery provided by the present invention does not contain lithium material, it is not restricted by lithium resources, the battery can be developed by leaps and bounds, and the production cost is significantly reduced. Compared with the existing sodium-ion battery, the electrochemical performance of the battery is relatively excellent, the battery life is longer, the capacity retention rate is high, the capacity is relatively high, and the positive and negative materials are simple, easy to obtain, and environmentally friendly, resulting in a full battery. The production process is simple and the cost is low.

Figure 201910758927

Description

Novel secondary battery and preparation method thereof
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a novel secondary battery.
Background
A secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and used for many times. Compared with a primary battery which can not be repeatedly used, the secondary battery has the advantages of low use cost and high resource utilization rate. The main secondary battery technologies at present are lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries and lithium ion batteries. Among them, lithium ion batteries are most widely used. However, lithium ion batteries face the current situation that the storage capacity of lithium resources is limited and the cost is higher and higher. Sodium ion batteries have gained increased attention in recent years as an energy storage technology that potentially replaces lithium ion batteries. The abundance of sodium in the earth crust is about 1000 times that of lithium, and the chemical property of sodium is the closest to that of lithium, so the sodium-ion battery is expected to become a new generation of high-performance and low-cost energy storage technology. The operating principle of a sodium ion battery is similar to that of a lithium ion battery, except that the storage and release of charge in the sodium ion battery is achieved by the migration of sodium ions. The core component parts of the sodium ion battery comprise a positive electrode, a negative electrode and electrolyte, and the sodium ion battery realizes the storage and release of electric energy through the oxidation-reduction reaction of ion transmission and electron transmission separation which occurs on the interfaces of the positive electrode, the negative electrode and the electrolyte. During charging, sodium ions are removed from the positive active material and are embedded into the negative active material; during discharge, sodium ions are extracted from the negative electrode active material and inserted into the positive electrode active material. Common sodium ion batteries use transition metal-containing salts such as phosphates, fluorosulfates, and silicates as positive active materials and carbon materials as negative active materials. However, the types of positive electrode materials developed based on sodium ion batteries are very limited, research is basically limited to half batteries of sodium sheets, the electrochemical performance of the sodium ion batteries based on the developed materials is not ideal, and the preparation process is complex.
Disclosure of Invention
Therefore, there is a need to provide a novel sodium ion secondary battery with excellent electrochemical performance, long cycle life, high capacity retention rate, relatively high capacity and simple process, which overcomes the drawbacks of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a novel secondary battery, is including the negative pole current collector layer, negative pole active material layer, electrolyte, anodal active material layer and the positive pole current collector layer that set gradually, be equipped with the diaphragm in the electrolyte, the electrolyte includes electrolyte sodium salt, anodal active material layer includes anodal active material, anodal active material is the Na that can allow free embedding of sodium ion and deviate from2M2(C2O4)3·2H2O material, M is at least one of Co, Ni and Mn.
In some preferred embodiments, the negative current collector layer is a metal conductive material, and the metal conductive material is one of aluminum, tin, zinc, lead, antimony, cadmium, gold, bismuth and germanium or an alloy or composite material formed by the above materials.
In some preferred embodiments, the negative active material layer includes a negative active material that is at least one of artificial graphite, natural graphite, spherulitic graphite, crystalline flake graphite, MCMB, soft carbon, hard carbon, graphite fluoride, mesocarbon microbeads, petroleum coke, carbon brazes, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys, carbon nanotubes, nanoalloy materials, nanooxide materials, triiron tetroxide, trimong tetroxide, alpha-ferric oxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide, and vanadium sulfide.
In some preferred embodiments, the negative active material layer further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
In some preferred embodiments, the content of the negative active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
In some preferred embodiments, the electrolyte sodium salt comprises one or more of sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methylsulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonimide, or sodium trifluoromethanesulfonate, and the concentration of the electrolyte sodium salt is in the range of 0.1-10 mol/L.
In some preferred embodiments, the electrolyte further comprises an electrolyte solvent comprising Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethylsulfone (MSM), and mixtures thereof, Dimethyl ether (DME), vinyl sulfite (ES), Propylene Sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, propylene glycol, 1-butyl-1-methylimidazole-bis (trifluoromethyl) sulfonyl imide salt, N-butyl-N-methylpyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl-N-propyl pyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
In some preferred embodiments, the electrolyte further comprises an additive comprising fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethylphosphonic acid, bromo-butyrolactone, fluoroacetoxyethane, fluoroethylene, methyl sulfite, ethyl sulfite, methyl sulfite, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown-6, 4-fluorophenylmethyl ether, fluoro, Phosphate, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and one or more of lithium carbonate.
In some preferred embodiments, the positive active material layer further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefins.
In some preferred embodiments, the content of the positive electrode active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
In some preferred embodiments, the positive current collector layer comprises one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or alloys or composites thereof.
In some preferred embodiments, the separator is an insulating porous polymer film or an inorganic porous film, the porous polymer film is one or more of a porous polypropylene film, a porous polyethylene film or a porous composite polymer film, and the inorganic porous film is one or more of a glass fiber paper or a porous ceramic separator.
In addition, the invention also provides a preparation method of the secondary battery, which comprises the following steps:
uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting after the negative electrode active material layer is dried to obtain the battery negative electrode;
cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is dried to obtain the battery positive electrode;
assembling the battery cathode, the electrolyte, the diaphragm and the battery anode to obtain the secondary battery;
the electrolyte comprises electrolyte, the electrolyte comprises electrolyte sodium salt, the positive active material layer comprises positive active material, and the positive active material is Na capable of allowing sodium ions to be freely inserted and extracted2M2(C2O4)3·2H2O material, M is at least one of Co, Ni and Mn.
The invention adopts the technical scheme that the method has the advantages that:
the novel secondary battery comprises a negative electrode current collector layer, a negative electrode active material layer, electrolyte, a positive electrode active material layer and a positive electrode current collector layer which are sequentially arranged, wherein a diaphragm is arranged in the electrolyte, the electrolyte comprises electrolyte, the electrolyte is electrolyte sodium salt, the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material is Na which can allow sodium ions to be freely embedded and removed2M2(C2O4)3·2H2O material, M is Co, Ni, Mn or moreOne of the sodium ions is removed from the positive active material and moves into the electrolyte in the charging process of the novel secondary battery, the sodium ions in the electrolyte migrate to the negative electrode, the valence of the transition metal is changed from +2 to +3, and the generated free electrons move to the negative electrode through an external circuit to balance the positive charges carried by the sodium ions; in the discharging process, sodium ions are separated from the negative electrode material and return to the electrolyte, the sodium ions in the electrolyte return to the positive electrode material, and free electrons return to the positive electrode material through an external circuit, so that the whole charging and discharging process is realized. Because the lithium-free material is not contained, the lithium-free lithium ion battery is not limited by lithium resources, the battery can be developed greatly, and the production cost is obviously reduced. Compared with the existing sodium ion battery, the battery has the advantages of excellent electrochemical performance, long cycle service life, high capacity retention rate, high capacity, simple and easily-obtained anode and cathode materials and environmental protection, so that the production process of the full battery is simple and the cost is low.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a novel secondary battery provided in an embodiment of the present invention.
Fig. 2 is a flowchart illustrating steps of a novel secondary battery according to an embodiment of the present invention.
Fig. 3 is a constant current charging and discharging curve diagram of the novel secondary battery provided by the embodiment of the invention.
Fig. 4 is a graph showing the long cycle capacity of the novel secondary battery according to the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic structural diagram of a novel secondary battery according to an embodiment of the present invention, and for convenience of description, only the portions related to the embodiment of the present invention are shown, which is described in detail below.
The present invention provides a novel secondary battery 100 including: the negative current collector layer 1, the negative active material layer 2, the electrolyte 3, the positive active material layer 5 and the positive current collector layer 6 that set gradually, be equipped with diaphragm 4 in the electrolyte 3 layer.
Specifically, the electrolytic solution 3 includes an electrolyte including an electrolyte sodium salt.
The invention can be understood that sodium salt with abundant reserves and low price is taken as the electrolyte of the sodium ion secondary battery, thereby not only reducing the cost of the battery, but also not causing dendrites to pierce the diaphragm in the reaction process and having better safety performance.
The positive active material layer comprises a positive active material which is Na capable of allowing sodium ions to be freely inserted and extracted2M2(C2O4)3·2H2O material, M is at least one of Co, Ni and Mn.
The composition of the substances included in each layer is described in detail below.
In some preferred embodiments, the negative current collector layer 1 is a metal conductive material, and the metal conductive material is one of aluminum, tin, zinc, lead, antimony, cadmium, gold, bismuth and germanium, or an alloy or a composite material formed by the above materials.
Further, the negative current collector layer is aluminum.
In some preferred embodiments, the negative active material layer 2 includes a negative active material that is at least one of artificial graphite, natural graphite, spherulitic graphite, crystalline flake graphite, MCMB, soft carbon, hard carbon, graphite fluoride, mesocarbon microbeads, petroleum coke, carbon fibrils, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys, carbon nanotubes, nano-alloy materials, nano-oxide materials, triiron tetroxide, trimong tetroxide, α -ferric oxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide, and vanadium sulfide.
Further, in some preferred embodiments, the negative active material layer 2 further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefins.
In some preferred embodiments, the content of the negative active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
In some preferred embodiments, the electrolyte sodium salt comprises one or more of sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methylsulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonimide, or sodium trifluoromethanesulfonate, and the concentration of the electrolyte sodium salt is in the range of 0.1-10 mol/L.
More further, the concentration of the sodium salt of the electrolyte is in the range of 0.5 to 1mol/L, for example 0.5mol/L, 0.7mol/L, or 1 mol/L.
In some preferred embodiments, the electrolyte 3 further comprises an electrolyte solvent including Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethylsulfone (MSM), and dimethylsulfone (MSM), Dimethyl ether (DME), vinyl sulfite (ES), Propylene Sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, propylene glycol, 1-butyl-1-methylimidazole-bis (trifluoromethyl) sulfonyl imide salt, N-butyl-N-methylpyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl-N-propyl pyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
In some preferred embodiments, the electrolyte 3 further comprises an additive comprising fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromo butyrolactone, fluoroacetoxyethane, fluoro alkyl ether, and mixtures thereof, Phosphate, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and one or more of lithium carbonate.
It can be understood that the additive added in the electrolyte can form a stable solid electrolyte membrane on the surface of the negative current collector, thereby improving the service life of the battery.
In some preferred embodiments, the positive active material layer 5 further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
In some preferred embodiments, the content of the positive electrode active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
In some preferred embodiments, the positive current collector layer 6 includes one or more of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or alloys or composites thereof.
Further, the positive current collector layer is aluminum.
In some preferred embodiments, the separator 4 is an insulating porous polymer film or an inorganic porous film, the porous polymer film is one or more of a porous polypropylene film, a porous polyethylene film or a porous composite polymer film, and the inorganic porous film is one or more of a glass fiber paper or a porous ceramic separator.
It can be understood that in the charging process of the novel secondary battery provided by the invention, sodium ions in the positive active material are removed and moved into the electrolyte, the sodium ions in the electrolyte are moved to the negative electrode, the valence of the transition metal is changed from +2 to +3, and the generated free electrons are moved to the negative electrode through an external circuit to balance positive charges carried by the sodium ions; during the discharging process, sodium ions are separated from the negative electrode material and return to the electrolyte, the sodium ions in the electrolyte return to the positive electrode material, and free electrons return to the positive electrode material through an external circuit, so that the whole charging and discharging process is realized. Because the battery does not contain lithium materials and is not limited by lithium resources, the battery can be developed greatly, and the production cost is obviously reduced.
Referring to fig. 2, a flowchart of steps for manufacturing a novel secondary battery according to an embodiment of the present invention includes the following steps:
step S110: uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting after the negative electrode active material layer is dried to obtain the battery negative electrode;
specifically, the negative electrode active material is weighed according to a certain proportion (a conductive agent and a binder can be added according to the situation), and a proper solvent is added to be fully mixed into uniform slurry to prepare a negative electrode active material layer; cleaning a negative current collector, uniformly coating the negative active material layer on the surface of the negative current collector, and cutting after the negative active material layer is completely dried to obtain the battery negative electrode with the required size;
step S120: cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is dried to obtain the battery positive electrode;
specifically, the positive active material Na is weighed according to a certain proportion2M2(C2O4)3·2H2O material, M is at least one of Co, Ni and Mn (conductive agent and binder can be added according to the situation), and proper solvent is added to be fully mixed into uniform slurry to prepare a positive active material layer; cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is completely dried to obtain a battery positive electrode with a required size;
step S130: assembling the battery cathode, the electrolyte, the diaphragm and the battery anode to obtain the secondary battery;
the electrolyte comprises electrolyte, the electrolyte comprises electrolyte sodium salt, the positive active material layer comprises positive active material, and the positive active material is Na capable of allowing sodium ions to be freely inserted and extracted2M2(C2O4)3·2H2O material, M is at least one of Co, Ni and Mn.
The material composition of each layer is described in detail above, and is not described herein again.
In the charging process of the novel secondary battery, sodium ions in the positive active material are removed and moved into electrolyte, the sodium ions in the electrolyte are moved to the negative electrode, the valence of the transition metal is changed from +2 to +3, and the generated free electrons are moved to the negative electrode through an external circuit to balance positive charges carried by the sodium ions; in the discharging process, sodium ions are separated from the negative electrode material and return to the electrolyte, the sodium ions in the electrolyte return to the positive electrode material, and free electrons return to the positive electrode material through an external circuit, so that the whole charging and discharging process is realized.
The preparation method of the novel secondary battery provided by the embodiment of the invention has the advantages of simple production process and low cost, and compared with the existing sodium ion battery, the novel secondary battery has the advantages of excellent electrochemical performance, long cycle service life, high capacity retention rate, relatively high capacity, simple and easily available anode and cathode materials and environmental protection.
The above technical solution is described in detail with reference to specific embodiments below.
Example 1: based on Na2Co2(C2O4)3·2H2Sodium ion half-cell of O positive electrode
Preparing a battery cathode: metal sodium is rolled on an aluminum foil (namely, a negative electrode current collector) to form a foil, and the obtained sodium-aluminum composite foil is cut into a circular sheet with the diameter of 12mm to be used as a battery negative electrode for standby.
Preparing a diaphragm: the glass fiber film was cut into a circular sheet having a diameter of 16mm and used as a separator.
Preparing an electrolyte: 0.6122g of sodium perchlorate is weighed and added into 10ml of propylene carbonate solvent, the sodium perchlorate is stirred and completely dissolved, then fluoroethylene carbonate with the mass fraction of 3 percent is added as an additive, and the mixture is fully stirred uniformly and then used as electrolyte for standby.
Preparing a battery positive electrode: 0.8g of Na2Co2(C2O4)3·2H2Adding O crystal powder, 0.1g of conductive agent carbon black and 0.1g of binder polyvinylidene fluoride into 2ml of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; the slurry was then uniformly coated on the aluminum foil surface (i.e., the positive current collector) and vacuum dried. And cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as the battery anode for standby.
Assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared negative current collector, the diaphragm and the battery positive electrode in sequence, dropwise adding electrolyte to completely soak the diaphragm, and packaging the stacked part into a button battery shell to finish battery assembly.
Fig. 3 is a graph of a stable charge-discharge curve of the battery obtained in this example at 0.2C, and it can be seen from the graph that the discharge capacity of the battery can reach 80 mAh/g.
Fig. 4 is a graph of the long cycle capacity of the battery obtained in this example, from which it can be seen that the capacity remained at about 80mAh/g after 400 cycles, the coulombic efficiency remained close to 98%, the capacity fade was relatively slow, and the cycle life was long.
Examples 2 to 25: based on Na2M2(C2O4)3·2H2Sodium ion full battery with O (Co, Ni, Mn) anode
Preparing a battery cathode: adding a negative electrode active material, a negative electrode conductive agent and a negative electrode binder into 2ml of nitrogen methyl pyrrolidone solution according to a certain ratio (shown in table 1), and fully grinding to obtain uniform slurry; and then uniformly coating the slurry on the surface of the negative current collector and performing vacuum drying. And cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery cathode for standby.
Preparing a diaphragm: the glass fiber film was cut into a circular sheet having a diameter of 16mm and used as a separator.
Preparing an electrolyte: weighing a certain amount of electrolyte salt, adding the electrolyte salt into a certain amount of organic solvent, stirring until the electrolyte salt is completely dissolved, then adding a certain amount of additive, and fully and uniformly stirring to obtain the electrolyte for later use.
Preparing a battery positive electrode: mixing Na2M2(C2O4)3·2H2Adding O (M ═ Co, Ni and Mn) crystal powder, a positive electrode conductive agent and a positive electrode binder into 2ml of nitrogen methyl pyrrolidone solution according to a certain proportion (mass ratio) (see table 1), and fully grinding to obtain uniform slurry; and then uniformly coating the slurry on the surface of the positive current collector and performing vacuum drying. And cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as the battery anode for standby.
Assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared negative current collector, the diaphragm and the battery positive electrode in sequence, dropwise adding electrolyte to completely soak the diaphragm, and packaging the stacked part into a button battery shell to finish battery assembly.
Table 1: performance parameter Table of sodium ion Secondary batteries of examples 2 to 25 of the present invention
Figure BDA0002169640750000121
Figure BDA0002169640750000131
Figure BDA0002169640750000141
The secondary battery according to the present invention may be designed in the form of a flat battery, a cylindrical battery, or the like, depending on the core components, without being limited to a button battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Of course, the novel secondary battery of the present invention may have various changes and modifications, and is not limited to the specific structure of the above-described embodiment. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.

Claims (13)

1.一种新型二次电池，其特征在于，包括依次设置的负极集流体层、负极活性材料层、电解液、正极活性材料层及正极集流体层，所述电解液中设有隔膜，所述电解液包括电解质，所述电解质包括电解质钠盐，所述正极活性材料层包括正极活性材料，所述正极活性材料为能容许钠离子自由嵌入与脱出的Na2M2(C2O4)3·2H2O材料，M为Co,Ni,Mn中的至少一种。1. a novel secondary battery, it is characterized in that, comprise the negative electrode current collector layer, negative electrode active material layer, electrolyte, positive electrode active material layer and positive electrode current collector layer that are arranged successively, be provided with diaphragm in the described electrolyte, so The electrolyte solution includes an electrolyte, the electrolyte includes an electrolyte sodium salt, the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material is Na 2 M 2 (C 2 O 4 ) that can allow free insertion and extraction of sodium ions 3 · 2H 2 O material, M is at least one of Co, Ni, and Mn. 2.如权利要求1所述的新型二次电池，其特征在于，所述负极集流体层为金属导电材料，所述金属导电材料为铝、锡、锌、铅、锑、镉、金、铋、锗中的一种或上述材料形成的合金或复合材料。2 . The novel secondary battery according to claim 1 , wherein the negative electrode current collector layer is a metal conductive material, and the metal conductive material is aluminum, tin, zinc, lead, antimony, cadmium, gold, and bismuth. 3 . , one of germanium or an alloy or composite material formed from the above materials. 3.如权利要求1所述的新型二次电池，其特征在于，所述负极活性材料层包括负极活性材料，所述负极活性材料为人工石墨、天然石墨、球星石墨、鳞片石墨、MCMB、软碳、硬碳、氟化石墨、中间相碳微球、石油焦、碳钎维、热解树脂碳、锡基合金、硅基合金、锗基合金、铝基合金、锑基合金、镁基合金、碳纳米管、纳米合金材料、纳米氧化物材料、四氧化三铁、四氧化三猛、α-三氧化二铁、钼氧化物、钨氧化物、钒氧化物、钴氧化物、锰氧化物、钛化物、氮化钛、氮化钒、氮氧化钨、硫化镍及硫化钒中的至少一种。3. novel secondary battery as claimed in claim 1, is characterized in that, described negative electrode active material layer comprises negative electrode active material, and described negative electrode active material is artificial graphite, natural graphite, spherical graphite, flake graphite, MCMB, soft graphite, etc. Carbon, hard carbon, fluorinated graphite, mesocarbon microspheres, petroleum coke, carbon brazing, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys , carbon nanotubes, nano-alloy materials, nano-oxide materials, ferric oxide, manganese tetroxide, α-iron oxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide , at least one of titanium compounds, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide and vanadium sulfide. 4.如权利要求3所述的新型二次电池，其特征在于，所述负极活性材料层还包括导电剂以及粘结剂，所述导电剂为导电炭黑、导电碳球、导电石墨、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯中的一种或多种，所述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、聚烯烃类中的一种或多种。4. The novel secondary battery of claim 3, wherein the negative electrode active material layer further comprises a conductive agent and a binder, and the conductive agent is conductive carbon black, conductive carbon balls, conductive graphite, carbon One or more of nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide, and the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, One or more of polyolefins. 5.如权利要求4所述的新型二次电池，其特征在于，所述负极活性材料的含量为60-90wt％，导电剂的含量为5-30wt％，粘结剂的含量为5-10wt％。5. The novel secondary battery according to claim 4, wherein the content of the negative electrode active material is 60-90 wt %, the content of the conductive agent is 5-30 wt %, and the content of the binder is 5-10 wt % %. 6.根据权利要求1所述的新型二次电池，其特征在于，所述电解质钠盐包括高氯酸钠、六氟磷酸钠、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、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、三氟甲烷磺酰亚胺钠或三氟甲烷磺酸钠中的一种或几种，所述电解质钠盐的浓度范围为0.1–10mol/L。6. The novel secondary battery according to claim 1, wherein the electrolyte sodium salt comprises sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate , sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, Sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium silicate, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenic One or more of sodium, sodium tetrafluoroborate, sodium trifluoromethanesulfonimide or sodium trifluoromethanesulfonate, and the concentration range of the electrolyte sodium salt is 0.1-10 mol/L. 7.根据权利要求1所述的新型二次电池，其特征在于，所述电解液还包括电解液溶剂，所述电解液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、1-乙基-3-甲基咪唑-六氟磷酸盐、1-乙基-3-甲基咪唑-四氟硼酸盐、1-乙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丙基-3-甲基咪唑-六氟磷酸盐、1-丙基-3-甲基咪唑-四氟硼酸盐、1-丙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基咪唑-六氟磷酸盐、1-丁基-1-甲基咪唑-四氟硼酸盐、1-丁基-1-甲基咪唑-双三氟甲基磺酰亚胺盐、N-丁基-N-甲基吡咯烷-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲基-N-丙基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲,丙基哌啶-双三氟甲基磺酰亚胺盐、N-甲,丁基哌啶-双三氟甲基磺酰亚胺盐中的一种或几种。7. The novel secondary battery according to claim 1, wherein the electrolyte further comprises an electrolyte solvent, and the electrolyte solvent comprises propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate Ester, methyl ethyl carbonate, methyl formate, methyl acetate, N,N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, γ-butyrolactone , tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, triethyl Glycol dimethyl ether, dimethyl sulfone, dimethyl ether, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether, 1-ethyl-3-methylimidazole - Hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bis-trifluoromethanesulfonimide, 1-propyl- 3-Methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bis-trifluoromethanesulfonimide salt, 1-Butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bis-trifluoromethanesulfonate Imide salt, N-butyl-N-methylpyrrolidine-bis-trifluoromethylsulfonimide salt, 1-butyl-1-methylpyrrolidine-bis-trifluoromethylsulfonimide salt , N-methyl-N-propylpyrrolidine-bis-trifluoromethylsulfonimide salt, N-methyl, propylpiperidine-bis-trifluoromethylsulfonimide salt, N-methyl, butyl One or more of piperidine-bis-trifluoromethanesulfonimide salts. 8.根据权利要求7所述的新型二次电池，其特征在于，所述电解液还包括添加剂，所述添加剂包括氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂、二甲基亚砜、苯甲醚、乙酰胺、二氮杂苯、间二氮杂苯、冠醚12-冠-4、冠醚18-冠-6、4-氟苯甲醚、氟代链状醚、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、溴代碳酸乙烯酯、三氟乙基膦酸、溴代丁内酯、氟代乙酸基乙烷、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、二氧化碳、二氧化硫、碳酸锂中的一种或几种。8 . The novel secondary battery according to claim 7 , wherein the electrolyte further comprises an additive, and the additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene ethylene carbonate, 1,3 -Propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazepine, metadiazepine, crown 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorinated chain ether, difluoromethyl ethylene carbonate, trifluoromethyl ethylene carbonate, chloroethylene carbonate, bromoethylene carbonate, trifluoromethyl ethylene carbonate Fluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phosphite, phosphazene, ethanolamine, carbodiamine, cyclobutylsulfone, 1,3-dioxolane , acetonitrile, long chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate, one or more. 9.根据权利要求1所述的新型二次电池，其特征在于，所述正极活性材料层还包括导电剂以及粘结剂，所述导电剂为导电炭黑、导电碳球、导电石墨、碳纳米管、导电碳纤维、石墨烯、还原氧化石墨烯中的一种或多种，所述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、聚烯烃类中的一种或多种。9 . The novel secondary battery according to claim 1 , wherein the positive electrode active material layer further comprises a conductive agent and a binder, and the conductive agent is conductive carbon black, conductive carbon balls, conductive graphite, carbon One or more of nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide, and the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, One or more of polyolefins. 10.根据权利要求9所述的新型二次电池，其特征在于，所述正极活性材料的含量为60-90wt％，导电剂的含量为5-30wt％，粘结剂的含量为5-10wt％。10 . The novel secondary battery according to claim 9 , wherein the content of the positive electrode active material is 60-90 wt %, the content of the conductive agent is 5-30 wt %, and the content of the binder is 5-10 wt % %. 11.根据权利要求1所述的新型二次电池，其特征在于，所述正极集流体层包括铝、铜、铁、锡、锌、镍、钛、锰、铅、锑、镉、金、铋，锗中的一种或上述材料形成的合金或复合材料。11. The novel secondary battery according to claim 1, wherein the positive electrode current collector layer comprises aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth , one of germanium or an alloy or composite material formed from the above materials. 12.根据权利要求1所述的新型二次电池，其特征在于，所述隔膜为绝缘的多孔聚合物薄膜或无机多孔薄膜，所述多孔聚合物薄膜为多孔聚丙烯薄膜、多孔聚乙烯薄膜或多孔复合聚合物薄膜中的一种或几种，所述无机多孔薄膜为玻璃纤维纸或多孔陶瓷隔膜中的一种或几种。12. The novel secondary battery according to claim 1, wherein the separator is an insulating porous polymer film or an inorganic porous film, and the porous polymer film is a porous polypropylene film, a porous polyethylene film or One or more of porous composite polymer films, and the inorganic porous film is one or more of glass fiber paper or porous ceramic membrane. 13.一种根据权利要求1所述的二次电池的制备方法，其特征在于，包括下述步骤：13. A method for preparing a secondary battery according to claim 1, characterized in that, comprising the steps of: 将所述负极活性材料层均匀涂覆于所述负极集流体层表面，待所述负极活性材料层干燥后进行裁切，得所述电池负极；uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting the negative electrode active material layer after drying to obtain the battery negative electrode; 将正极集流体层清洗干净，将所述正极活性材料层均匀涂覆于所述正极集流体层表面，待所述正极活性材料层干燥后进行裁切，得所述电池正极；cleaning the positive electrode current collector layer, uniformly coating the positive electrode active material layer on the surface of the positive electrode current collector layer, and cutting the positive electrode active material layer after drying to obtain the battery positive electrode; 利用所述电池负极、所述电解液、所述隔膜以及所述电池正极进行组装，得到所述二次电池；The secondary battery is obtained by assembling the battery negative electrode, the electrolyte, the separator and the battery positive electrode; 所述电解液包括电解质，所述电解质包括电解质钠盐，所述正极活性材料层包括正极活性材料，所述正极活性材料为能容许钠离子自由嵌入与脱出的Na2M2(C2O4)3·2H2O材料，M为Co,Ni,Mn中的至少一种。The electrolyte solution includes an electrolyte, the electrolyte includes an electrolyte sodium salt, the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material is Na 2 M 2 (C 2 O 4 ) that can allow free insertion and extraction of sodium ions. ) 3 ·2H 2 O material, where M is at least one of Co, Ni, and Mn.
CN201910758927.4A 2019-08-16 2019-08-16 Novel secondary battery and preparation method thereof Pending CN112397768A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910758927.4A CN112397768A (en) 2019-08-16 2019-08-16 Novel secondary battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910758927.4A CN112397768A (en) 2019-08-16 2019-08-16 Novel secondary battery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112397768A true CN112397768A (en) 2021-02-23

Family

ID=74602035

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910758927.4A Pending CN112397768A (en) 2019-08-16 2019-08-16 Novel secondary battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112397768A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112151751A (en) * 2020-10-15 2020-12-29 宁德新能源科技有限公司 Electrochemical and electronic devices
CN113113730A (en) * 2021-04-01 2021-07-13 溧阳中科海钠科技有限责任公司 Sodium ion battery ceramic diaphragm and preparation method thereof, and sodium ion battery and preparation method thereof
CN114156473A (en) * 2021-12-06 2022-03-08 深圳市启明新能源科技有限公司 A kind of sodium ion battery and its production method
WO2022077310A1 (en) * 2020-10-15 2022-04-21 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114725482A (en) * 2022-03-16 2022-07-08 江苏环峰电工材料有限公司 Rechargeable battery and application thereof
CN117497852A (en) * 2023-11-15 2024-02-02 安徽理士新能源发展有限公司 Electrolyte with negative electrode film forming additive and sodium ion battery
WO2024160211A1 (en) * 2023-01-31 2024-08-08 比亚迪股份有限公司 Sodium battery and electric device

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN203445193U (en) * 2013-08-20 2014-02-19 宋维鑫 Secondary battery with mixed ions
JP2014130752A (en) * 2012-12-28 2014-07-10 Nitto Denko Corp Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using the same and manufacturing method thereof
CN105374980A (en) * 2014-08-15 2016-03-02 中国科学院物理研究所 An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell
CN106784727A (en) * 2017-01-17 2017-05-31 东莞市迈科新能源有限公司 A kind of positive electrode material of polyanionic sodium ion battery and preparation method thereof
CN107148697A (en) * 2015-12-30 2017-09-08 深圳先进技术研究院 A kind of new sodium-ion battery and preparation method thereof
CN107565158A (en) * 2017-08-29 2018-01-09 深圳中科瑞能实业有限公司 Sodium-ion battery electrolyte, preparation method and the sodium-ion battery for including the sodium-ion battery electrolyte
US20180175463A1 (en) * 2013-11-28 2018-06-21 Centre National De La Recherche Scientifique Transparent autophotorechargeable electrochemical device
EP3370294A1 (en) * 2016-05-06 2018-09-05 Shenzhen Institutes of Advanced Technology Secondary battery and preparation method therefor
CN109155415A (en) * 2016-05-06 2019-01-04 深圳中科瑞能实业有限公司 A kind of sodium-ion battery and preparation method thereof
CN110021755A (en) * 2019-04-17 2019-07-16 湖南立方新能源科技有限责任公司 A kind of sodium-ion battery

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014130752A (en) * 2012-12-28 2014-07-10 Nitto Denko Corp Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using the same and manufacturing method thereof
CN203445193U (en) * 2013-08-20 2014-02-19 宋维鑫 Secondary battery with mixed ions
US20180175463A1 (en) * 2013-11-28 2018-06-21 Centre National De La Recherche Scientifique Transparent autophotorechargeable electrochemical device
CN105374980A (en) * 2014-08-15 2016-03-02 中国科学院物理研究所 An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell
CN107148697A (en) * 2015-12-30 2017-09-08 深圳先进技术研究院 A kind of new sodium-ion battery and preparation method thereof
EP3370294A1 (en) * 2016-05-06 2018-09-05 Shenzhen Institutes of Advanced Technology Secondary battery and preparation method therefor
CN109155415A (en) * 2016-05-06 2019-01-04 深圳中科瑞能实业有限公司 A kind of sodium-ion battery and preparation method thereof
CN106784727A (en) * 2017-01-17 2017-05-31 东莞市迈科新能源有限公司 A kind of positive electrode material of polyanionic sodium ion battery and preparation method thereof
CN107565158A (en) * 2017-08-29 2018-01-09 深圳中科瑞能实业有限公司 Sodium-ion battery electrolyte, preparation method and the sodium-ion battery for including the sodium-ion battery electrolyte
CN110021755A (en) * 2019-04-17 2019-07-16 湖南立方新能源科技有限责任公司 A kind of sodium-ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
H. AHOUARI: "Synthesis, structure and electrochemical properties of metal malonate Na2M(H2C3O4)2·nH2O (n=0,2) compounds and comparison with oxalate Na2M2(C2O4)3·2H2O compounds", 《SOLID STATE SCIENCES》 *
WENJIAO YAO: "Reinvestigation of Na2Fe2(C2O4)3·2H2O: An Iron-Based Positive", 《CHEM. MATER》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112151751A (en) * 2020-10-15 2020-12-29 宁德新能源科技有限公司 Electrochemical and electronic devices
WO2022077310A1 (en) * 2020-10-15 2022-04-21 宁德新能源科技有限公司 Electrochemical device and electronic device
CN113113730A (en) * 2021-04-01 2021-07-13 溧阳中科海钠科技有限责任公司 Sodium ion battery ceramic diaphragm and preparation method thereof, and sodium ion battery and preparation method thereof
CN114156473A (en) * 2021-12-06 2022-03-08 深圳市启明新能源科技有限公司 A kind of sodium ion battery and its production method
CN114725482A (en) * 2022-03-16 2022-07-08 江苏环峰电工材料有限公司 Rechargeable battery and application thereof
WO2024160211A1 (en) * 2023-01-31 2024-08-08 比亚迪股份有限公司 Sodium battery and electric device
CN117497852A (en) * 2023-11-15 2024-02-02 安徽理士新能源发展有限公司 Electrolyte with negative electrode film forming additive and sodium ion battery

Similar Documents

Publication Publication Date Title
CN108172903B (en) Electrolyte solution, sodium ion secondary battery and preparation method thereof
CN108511803B (en) A kind of secondary battery and preparation method thereof
CN109075394B (en) Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
CN108028430B (en) Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
JP5277216B2 (en) Lithium secondary battery
JP5290247B2 (en) Electrolytic solution for lithium battery, lithium battery, and operating method of lithium battery
CN112397768A (en) Novel secondary battery and preparation method thereof
CN111354924B (en) Positive electrode active material for sodium ion battery, positive electrode material for sodium ion battery, positive electrode for sodium ion battery and sodium ion battery and preparation method
WO2017190365A1 (en) Sodium ion battery and preparation method therefor
CN109075393B (en) Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
CN108183257A (en) Organogel electrolyte, application, sodium base double ion organic solid-state battery and preparation method thereof
KR101724004B1 (en) Rechargeable lithium battery
JP5277225B2 (en) ELECTROLYTE SOLUTION FOR LITHIUM BATTERY, LITHIUM BATTERY CONTAINING THE SAME, AND METHOD FOR OPERATING LITHIUM BATTERY
KR20170121047A (en) Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising thereof
CN108470908B (en) Secondary battery and preparation method thereof
CN108630979B (en) A kind of secondary battery based on calcium ion and preparation method thereof
WO2018152755A1 (en) Secondary battery and preparation method therefor
KR20180057437A (en) Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
WO2018170925A1 (en) Calcium ion secondary cell, and manufacturing method thereof
KR20150057730A (en) Negative electrode active material layer composition for rechargeable lithium battery, manufacturing method of the same, and negative electrode and rechargeable lithium battery including the same
CN112670452A (en) Preparation method of negative electrode of sodium ion secondary battery and sodium ion secondary battery
KR101093697B1 (en) Positive electrode for lithium secondary battery and lithium secondary battery comprising same
JP2015088437A (en) Pre-doping method of nonaqueous secondary battery and battery obtained by pre-doping method
CN109962231B (en) Metal foil used as negative electrode of lanthanum ion secondary battery and lanthanum ion secondary battery and preparation method thereof
JP2015011991A (en) Electrolytic solution additive, electrolytic solution for lithium secondary battery, and lithium secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210223

RJ01 Rejection of invention patent application after publication