CN109155415A - A kind of sodium-ion battery and preparation method thereof - Google Patents
A kind of sodium-ion battery and preparation method thereof Download PDFInfo
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- CN109155415A CN109155415A CN201680085087.4A CN201680085087A CN109155415A CN 109155415 A CN109155415 A CN 109155415A CN 201680085087 A CN201680085087 A CN 201680085087A CN 109155415 A CN109155415 A CN 109155415A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
Abstract
The present invention relates to field of batteries, in particular to a kind of sodium-ion battery and preparation method thereof.Sodium-ion battery provided by the invention, including battery cathode, electrolyte, diaphragm and anode, wherein battery cathode includes negative current collector, does not include negative electrode active material；Negative current collector includes metal, metal alloy or metal composite conductive material；Electrolyte includes solvent and electrolyte, and electrolyte is sodium salt；Anode includes plus plate current-collecting body and anode active material layer, and plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, and anode active material layer includes the positive electrode active materials of freely reversible deintercalation sodium ion.By replacing lithium with sodium, solve the problems, such as that lithium resource reserves are limited, while the cathode of sodium-ion battery provided by the invention does not include negative electrode active material, can greatly simplify the production technology of battery, cost is reduced, and further increases the energy density and power density of the type sodium-ion battery.
Description
The present invention relates to field of batteries, in particular to a kind of sodium-ion battery and preparation method thereof.
Secondary cell is also referred to as rechargeable battery, is a kind of repeatable charge and discharge, using multiple battery.Compared to not re-usable one-shot battery, secondary cell has the advantages that use cost is low, environmental pollution is small.Current main secondary cell technology has lead-acid battery, Ni-Cr battery, nickel-metal hydride battery, lithium ion battery.It is wherein especially the most extensive with lithium ion battery applications.Lithium ion battery has extended cycle life because of its specific capacity height, and cost performance height becomes the first choice of current electronic product power source.The core building block of lithium ion battery generally comprises anode, cathode and electrolyte.Commercial lithium ion battery is using transition metal oxide or polyanionic metallic compound as positive electrode active materials, and using graphite or carbon as negative electrode active material, esters are electrolyte.But using graphite as negative electrode active material, graphite occupies substantial portion of volume and weight in the battery, constrains the battery capacity and energy density of lithium ion battery.Lithium ion battery is faced with the disadvantage that lithium resource reserves are limited, at high cost simultaneously.
Summary of the invention
In order to overcome above-mentioned technical problem, the present invention provides a kind of sodium-ion battery and preparation method thereof, it is intended to solve the problems, such as existing lithium battery tankage and energy density is low and to be faced with lithium resource reserves limited, at high cost.
First aspect, the present invention provides a kind of sodium-ion batteries, including battery cathode, electrolyte, diaphragm and anode, wherein
Battery cathode includes negative current collector, does not include negative electrode active material；The negative current collector includes metal, metal alloy or metal composite conductive material；
The electrolyte includes solvent and electrolyte, and the electrolyte is sodium salt；
The anode includes plus plate current-collecting body and anode active material layer, and the plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation sodium ion.
Preferably, the positive electrode active materials include the one or more of the phosphoric acid salt polyanionic compound of sodium, the iron cyanide and its Prussian blue complex, active redox polymer, tunnel structure compound, spinel oxides, stratiform transition metal oxide.
Preferably, the negative current collector includes the compound or in which the alloy of any one of one of aluminium, magnesium, vanadium, lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
Preferably, the negative current collector is tin or zinc.
Preferably, the plus plate current-collecting body includes the compound or in which the alloy of any one of one of aluminium, magnesium, vanadium, lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
Preferably, the plus plate current-collecting body is aluminium.
Preferably, the electrolyte includes sodium chloride, sodium fluoride, sodium sulphate, sodium carbonate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, lauryl sodium sulfate, trisodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium hexafluoro phosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, sodium perchlorate, the one or more of trifluoromethanesulfonimide sodium, and the concentration range of sodium salt is 0.1-10mol/L.
Preferably, the solvent includes esters, sulfone class, the one or more of ethers, nitrile organic solvent or ionic liquid.
Preferably, the solvent include propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester,
Carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1,3- dioxolanes, 4- methyl-1,3- dioxolanes, dimethoxymethane, 1, one or more of 2- dimethoxy, 1,2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether.
Preferably, the electrolyte further includes additive, and the additive includes esters, sulfone class, the one or more of ethers, nitrile or olefines organic additive, and the additive amount of the additive in the electrolytic solution is 0.1-20wt%.
Preferably, the additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-N-morpholinopropanesulfonic acid lactone, 1, 4- butyl sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide, methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown- 6, 4- fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, be carbonized dimethylamine, cyclobutyl One or more of sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, aluminum oxide, magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate.
Second aspect, the present invention also provides a kind of preparation methods of sodium-ion battery, this method comprises:
Prepare battery cathode, metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as negative current collector, using the negative current collector as battery cathode；
Electrolyte is prepared, a certain amount of sodium salt electrolyte is weighed and is added in coordinative solvent, dissolution is sufficiently stirred；
Diaphragm is prepared, porous polymer film, inorganic porous film or all-glass paper are cut into required size, cleaned up；
Anode is prepared, positive electrode active materials, conductive agent and binder living is weighed by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Metal, metal alloy or metal composite conductive material surface are cleaned and are used as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, is cut after the anode active material layer is completely dried, obtains the anode of required size；
It is assembled using the battery cathode, electrolyte, diaphragm and anode.
Compared with prior art, the beneficial effects of the present invention are: the present invention provides a kind of sodium-ion battery, replace lithium with sodium, solve the problems, such as that lithium resource reserves are limited；The cathode of sodium-ion battery provided by the invention does not include negative electrode active material simultaneously, due to cancelling negative electrode active material, significantly reduces the weight and volume of battery；It regard the negative current collector that metal or metal alloy is constituted as reaction material simultaneously, effectively improves the battery capacity of battery；By the reduction of the weight and volume of battery and the raising of battery capacity, the energy density of battery is improved significantly, and battery has good charge-discharge performance.
Fig. 1 is the structural schematic diagram of sodium-ion battery provided in an embodiment of the present invention.
Invention is further described in detail with reference to the accompanying drawings and detailed description.The following is a preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the principles of the embodiments of the present invention; several improvements and modifications can also be made, these modifications and embellishments are also considered to be within the scope of the present invention.
Figure one is the structural schematic diagram of sodium-ion battery provided in an embodiment of the present invention.Referring to figure one, the embodiment of the invention provides sodium-ion battery, including battery cathode 1, electrolyte 2, diaphragm 3 and anode 4, anode 4 include anode active material layer 41 and plus plate current-collecting body 42.Wherein, battery cathode 1 includes negative current collector, does not include negative electrode active material, negative current collector includes metal, metal alloy or metal composite conductive material.Electrolyte includes solvent and electrolyte, and electrolyte is sodium salt.Anode includes plus plate current-collecting body and anode active material layer, plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, anode active material layer includes the positive electrode active materials of freely reversible deintercalation sodium ion, positive electrode active materials can be the oxide of sodium or the composite material of the compound of sodium or sodium, specifically without limitation, as long as sodium ion is allowed freely to deviate from and insertion, for example the oxide of sodium can be the transition metal oxide of sodium and its binary or ternary transition metal oxide of doping, the compound of sodium can be the phosphate compounds of sodium, the fluorophosphate compound or sodium superionic conductors of sodium.
Battery working principle provided in an embodiment of the present invention are as follows: sodium-ion battery provided in an embodiment of the present invention is free of negative electrode active material, during the charging process, sodium ion deposits to negative current collector surface from positive electrode abjection, directly reacts to form sodium-metal alloy with the metal or metal alloy of cathode；In discharge process, it is embedded in positive electrode active materials after sodium-metal alloy removing sodium of cathode by electrolyte, to realize charge and discharge process.It does not need to need as conventional lithium ion battery in this process to reduce volume and cost using graphite as cathode；Alloying reaction, which occurs, for metal and sodium ion simultaneously bigger battery capacity, by the reduction of the weight and volume of battery and the raising of battery capacity, improves the energy density of battery significantly, and can save production cost.Lithium is replaced with sodium simultaneously, solves the problems, such as that lithium resource reserves are limited.
Preferably, in the embodiment of the present invention, positive electrode active materials include the phosphoric acid salt polyanionic compound of sodium, the iron cyanide and its Prussian blue complex, active redox polymer, tunnel structure compound, spinel oxides, the one or more of stratiform transition metal oxide.Such as: Na2V3(PO4)3、Na2Zn3[Fe(CN)6]2`xH2O、Na2Fe(SO4)2、NaMn2O4、Na0.61[Mn0.27Fe0.34Ti0.39]O2、NaCoO2。
Preferably, in the embodiment of the present invention, negative current collector and plus plate current-collecting body include: aluminium, magnesium, vanadium,
The compound or in which the alloy of any one of one of lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
Further, in the embodiment of the present invention, negative current collector is preferably tin or zinc, and plus plate current-collecting body is preferably aluminium.
In embodiments of the present invention, the solvent in electrolyte is not particularly limited, as long as solvent can make electrolyte be dissociated into cation and anion, and cation and anion can be with free migrations.For example, solvent of the embodiment of the present invention includes esters, sulfone class, ethers or nitrile organic solvent.Specifically, including propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester, carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1, 3- dioxolanes, 4- methyl-1, 3- dioxolanes, dimethoxymethane, 1, 2- dimethoxy, 1, 2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, one or more of crown ether.
In embodiments of the present invention, sodium salt as electrolyte is also not particularly limited, as long as cation and anion can be dissociated into, it such as may include sodium chloride, sodium fluoride, sodium sulphate, sodium carbonate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, lauryl sodium sulfate, trisodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium hexafluoro phosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, sodium perchlorate, the one or more of trifluoromethanesulfonimide sodium.In the embodiment of the present invention, the concentration range of sodium salt is 0.1-10mol/L.
Negative current collector makes negative current collector knot in charge and discharge because of the destruction caused by volume change in order to prevent
Structure and function-stable, improve the service life and performance of negative current collector, to improve the cycling rate of sodium-ion battery, electrolyte increases additive in the embodiment of the present invention, additive includes esters, sulfone class, ethers, nitrile or olefines organic additive, and the additive amount of additive in the electrolytic solution is 0.1-20wt%.Additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-N-morpholinopropanesulfonic acid lactone, 1, 4- butyl sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide, methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown- 6, 4- fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, be carbonized dimethylamine, cyclobutyl sulfone, 1, 3- One or more of dioxolanes, acetonitrile, long-chain olefin, aluminum oxide, magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate.Increased additive can form stable solid electrolyte film on negative current collector surface in the electrolytic solution, so that negative current collector is not destroyed when reacting as active material, can maintain its function and shape, improve the service life of battery.
Further, the ingredient of diaphragm used in sodium-ion battery provided in an embodiment of the present invention is the porous polymer film or inorganic porous film of insulation, can select porous polypropylene film, porous polyethylene film, porous compound polymer film, all-glass paper or porous ceramics diaphragm.
Preferably, anode active material layer provided in an embodiment of the present invention further includes conductive agent and binder, and wherein the deal of positive electrode active materials is 60-90wt%, and the content of conductive agent is 30-5wt%, and the content of binder is 10-5wt%.Meanwhile conductive agent and binder are not particularly limited, using commonly used in the art.Conductive agent is one of conductive black, Super P conduction carbon ball, electrically conductive graphite KS6, carbon nanotube, conductive carbon fibre, graphene, redox graphene or a variety of.Binder is Kynoar, polytetrafluoroethylene (PTFE), gathers
One of vinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins are a variety of.
Second aspect, the embodiment of the invention also provides the methods for preparing above-mentioned sodium-ion battery, comprising:
Step 101, preparation battery cathode, metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as negative current collector, using the negative current collector as battery cathode.
Preferably, metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of aluminium, magnesium, vanadium, lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal, can be metal foil or metal alloy paillon.
Step 102 prepares electrolyte, weighs a certain amount of sodium salt electrolyte and is added in coordinative solvent, dissolution is sufficiently stirred.
It prepares electrolyte to specifically include: weighing a certain amount of electrolyte and additive is added in coordinative solvent, dissolution is sufficiently stirred, prepare electrolyte.Electrolyte is sodium salt, in embodiments of the present invention, sodium salt as electrolyte is also not particularly limited, as long as cation and anion can be dissociated into, it such as may include sodium chloride, sodium fluoride, sodium sulphate, sodium carbonate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, lauryl sodium sulfate, trisodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium hexafluoro phosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, sodium perchlorate, the one or more of trifluoromethanesulfonimide sodium.The concentration range of sodium salt is 0.1-10mol/L.
Solvent of the embodiment of the present invention includes esters, sulfone class, ethers or nitrile organic solvent, including propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate,
Methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester, carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1, 3- dioxolanes, 4- methyl-1, 3- dioxolanes, dimethoxymethane, 1, 2- dimethoxy, 1, 2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, one or more of crown ether.
In the embodiment of the present invention, additive can also be added in electrolyte, and additive includes esters, sulfone class, ethers, nitrile or olefines organic additive, and the additive amount of additive in the electrolytic solution is 0.1-20wt%.Additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-N-morpholinopropanesulfonic acid lactone, 1, 4- butyl sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide, methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown- 6, 4- fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, be carbonized dimethylamine, cyclobutyl sulfone, 1, 3- One or more of dioxolanes, acetonitrile, long-chain olefin, aluminum oxide, magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate.Increased additive can form stable solid electrolyte film on negative current collector surface in the electrolytic solution, so that negative current collector is not destroyed when reacting as active material, can maintain its function and shape, improve the service life of battery.
Step 103 prepares diaphragm, and porous polymer film, inorganic porous film or all-glass paper are cut into required size, cleaned up.
Preferably, the diaphragm for preparing specifically includes: by porous polymer film, inorganic porous film or glass
Fibrous paper cuts into required size, cleans up.
Step 104 prepares anode, weighs positive electrode active materials, conductive agent and binder living by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Metal, metal alloy or metal composite conductive material surface are cleaned and are used as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, is cut after the anode active material layer is completely dried, obtains the anode of required size.
Plus plate current-collecting body plus plate current-collecting body is metal, metal alloy or metal composite conductive material, can be selected from one of aluminium, magnesium, vanadium, lithium, copper, iron, tin, zinc, nickel, titanium, manganese or in which the compound or in which the alloy of any one of any one metal.The deal of positive electrode active materials is 60-90wt%, and the content of conductive agent is 30-5wt%, and the content of binder is 10-5wt%.Positive electrode active materials can be selected from phosphoric acid salt polyanionic compound, the iron cyanide and its Prussian blue complex, active redox polymer, tunnel structure compound, spinel oxides, the one or more of stratiform transition metal oxide.Meanwhile conductive agent and binder are not particularly limited, using commonly used in the art.Conductive agent is one of conductive black, Super P conduction carbon ball, electrically conductive graphite KS6, carbon nanotube, conductive carbon fibre, graphene, redox graphene or a variety of.Binder is one of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins or a variety of.
Step 105 is assembled using the battery cathode, electrolyte, diaphragm and anode.
Preferably, it is assembled using the battery cathode, electrolyte, diaphragm and anode, it specifically includes: under inert gas or anhydrous and oxygen-free environment, by the cathode prepared, diaphragm, anode successively Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, then it is encapsulated into battery case, completes battery assembly.
It should be noted that although above-mentioned steps 101-104 is to describe the operation of preparation method of the present invention with particular order, this does not require that or implies must execute these operations in this particular order.Step
The preparation of 101-104 simultaneously or arbitrarily can be executed successively.
The sodium-ion battery preparation method and aforementioned sodium-ion battery are that based on the same inventive concept, have the institute of aforementioned sodium-ion battery effective using the sodium-ion battery that the sodium-ion battery preparation method obtains, details are not described herein.
Simultaneously; the above embodiment is only the preferred embodiment of the present invention; the scope of protection of the present invention is not limited thereto, and the variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to scope of the present invention.
Above-mentioned sodium-ion battery preparation method is further illustrated below by specific embodiment, it should be understood, however, that, these embodiments, which are only used for being described in more detail, to be used, and but should not be understood as present invention is limited in any form.
Embodiment 1
Preparation battery cathode: the zinc foil with a thickness of 0.02mm is taken, the disk of diameter 12mm is cut into, zinc foil surface is cleaned with ethyl alcohol, dries spare as negative current collector.
It prepares diaphragm: Celgard2400 porous polymer film being cut into the disk of diameter 16mm, is cleaned with acetone, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 3g sodium hexafluoro phosphate and be added in 5ml methyl ethyl carbonate, stirring to sodium hexafluoro phosphate is completely dissolved, and it is 2% vinylene carbonate as additive that mass fraction, which is then added, spare as electrolyte after stirring.
Prepare anode: by 0.8g NaVO2, 0.1g carbon black, 0.1g Kynoar be added in 2ml N-methyl pyrrolidone solution, be fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface (that is, plus plate current-collecting body) and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after killing.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
Embodiment 2-22
The secondary cell preparation process step of embodiment 2-22 is same as Example 1, and difference is to prepare the difference of material difference or material content, referring specifically to Tables 1 and 2.
1 embodiment 1-22 negative electrode material of table, electrolyte, diaphragm material compare
2 embodiment 1-22 positive electrode of table compares
Sodium-ion battery form of the present invention is not limited to button cell, and the forms such as flat plate cell, cylindrical battery can also be designed to according to core component.
Novel sodium-ion battery main active proposed by the present invention is the material deviate from for sodium ion be embedded in.Meanwhile negative electrode material is not necessarily in novel sodium-ion battery system of the invention, thus battery self weight and cost are significantly reduced, promote battery energy density.
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effects are had been further described; it should be understood that; the above is only a specific embodiment of the present invention; it is not intended to limit the scope of protection of the present invention; all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done, should all be included in the protection scope of the present invention.
Claims (12)
- A kind of sodium-ion battery, including battery cathode, electrolyte, diaphragm and anode, which is characterized in that wherein,Battery cathode includes negative current collector, does not include negative electrode active material；The negative current collector includes metal, metal alloy or metal composite conductive material；The electrolyte includes solvent and electrolyte, and the electrolyte is sodium salt；The anode includes plus plate current-collecting body and anode active material layer, and the plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation sodium ion.
- Sodium-ion battery as described in claim 1, it is characterized in that, the positive electrode active materials include the one or more of the phosphoric acid salt polyanionic compound of sodium, the iron cyanide, the Prussian blue complex of the iron cyanide, active redox polymer, tunnel structure compound, spinel oxides, stratiform transition metal oxide.
- Sodium-ion battery as described in claim 1, which is characterized in that the negative current collector includes the compound or in which the alloy of any one of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
- Sodium-ion battery as claimed in claim 3, which is characterized in that the negative current collector is tin or zinc.
- Sodium-ion battery as described in claim 1, which is characterized in that the plus plate current-collecting body includes the compound or in which the alloy of any one of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
- Sodium-ion battery as claimed in claim 5, which is characterized in that the plus plate current-collecting body is aluminium.
- Sodium-ion battery as described in claim 1, which is characterized in that the electrolyte includes sodium chloride, sodium fluoride, sodium sulphate, sodium carbonate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, 12 Sodium alkyl benzene sulfonate, lauryl sodium sulfate, trisodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium hexafluoro phosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, the one or more of sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, sodium perchlorate, trifluoromethanesulfonimide sodium, and the concentration range of the sodium salt is 0.1-10mol/L.
- Sodium-ion battery as described in claim 1, which is characterized in that the solvent includes esters, sulfone class, the one or more of ethers, nitrile organic solvent or ionic liquid.
- Sodium-ion battery as claimed in claim 8, it is characterized in that, the solvent includes propene carbonate, ethylene carbonate, butylene, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dibutyl carbonate, carbonic acid first butyl ester, carbonic acid first isopropyl ester, methyl esters, methyl formate, methyl acetate, N, N- dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofuran, 1, 3- dioxolanes, 4- methyl-1, 3- dioxolanes, dimethoxymethane, 1, 2- dimethoxy, 1, 2- diformazan Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge , one or more of crown ether.
- Sodium-ion battery as claimed in one of claims 1 to 9, it is characterized in that, the electrolyte further includes additive, and the additive includes esters, sulfone class, the one or more of ethers, nitrile or olefines organic additive, and the additive amount of the additive in the electrolytic solution is 0.1-20wt%.
- Sodium-ion battery as claimed in claim 10, it is characterized in that, the additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3-N-morpholinopropanesulfonic acid lactone, Isosorbide-5-Nitrae-butyl sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide, benzene first Ether, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown- 6, 4- fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, be carbonized dimethylamine, cyclobutyl sulfone, 1, 3- dioxolanes, acetonitrile, long-chain olefin, aluminum oxide, magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, one or more of lithium carbonate.
- A kind of preparation method preparing the sodium-ion battery as described in one of claim 1-11 characterized by comprisingPrepare battery cathode, metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as negative current collector, using the negative current collector as battery cathode；Electrolyte is prepared, a certain amount of sodium salt electrolyte is weighed and is added in coordinative solvent, dissolution is sufficiently stirred；Diaphragm is prepared, porous polymer film, inorganic porous film or all-glass paper are cut into required size, cleaned up；Anode is prepared, positive electrode active materials, conductive agent and binder living is weighed by a certain percentage, is fully ground into uniform sizing material in addition appropriate solvent and anode active material layer is made；Metal, metal alloy or metal composite conductive material surface are cleaned and are used as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, is cut after the anode active material layer is completely dried, obtains the anode of required size；It is assembled using the battery cathode, electrolyte, diaphragm and anode.
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| PCT/CN2016/081347 WO2017190365A1 (en) | 2016-05-06 | 2016-05-06 | Sodium ion battery and preparation method therefor |
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