CN109196701A - A kind of Magnesium ion battery and preparation method thereof - Google Patents

A kind of Magnesium ion battery and preparation method thereof Download PDF

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Publication number
CN109196701A
CN109196701A CN201680085081.7A CN201680085081A CN109196701A CN 109196701 A CN109196701 A CN 109196701A CN 201680085081 A CN201680085081 A CN 201680085081A CN 109196701 A CN109196701 A CN 109196701A
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China
Prior art keywords
magnesium
metal
electrolyte
anode
battery
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唐永炳
圣茂华
张帆
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/399—Cells with molten salts
    • 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

Abstract

Invention provides a kind of Magnesium ion battery and preparation method thereof, including battery cathode, electrolyte, diaphragm and anode；Wherein, the anode includes plus plate current-collecting body and anode active material layer, and the anode active material layer includes positive electrode active materials, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；The battery cathode includes one or more of metal, metal alloy or metal composite conductive material.The present invention provides a kind of Magnesium ion batteries, replace lithium with magnesium, solve the problems, such as that lithium resource reserves are limited；The volume and weight for saving a component can reduce the weight and volume of battery, improve battery energy density；And the reactive agent of the electrochemical reaction occurred is magnesium ion, there are two charges for magnesium ion band, improve the capacity of battery.

Description

A kind of Magnesium ion battery and preparation method thereof Technical field
The present invention relates to field of batteries, in particular to a kind of Magnesium ion battery and preparation method thereof.
Background technique
In today that new energy technology and application become more and more important, lithium ion battery becomes the first choice of current electronic product power source since specific capacity is high, energy density is high, have extended cycle life, cost performance is high and obtains extensive concern and application.The core building block of lithium ion battery generally comprises anode, cathode and electrolyte.Commercial lithium ion battery is mainly using transition metal oxide or polyanionic metallic compound as positive electrode active materials at present, and using carbon materials such as graphite as negative electrode active material, electrolyte is the esters containing lithium salts.But the negative electrode active materials such as graphite occupy substantial portion of volume and weight in the battery, constrain the battery capacity and energy density of lithium ion battery.Lithium ion battery haves the shortcomings 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 Magnesium ion battery and preparation method thereof.
In a first aspect, the present invention provides a kind of Magnesium ion battery, including battery cathode, electrolyte, diaphragm and anode；
Wherein, the anode includes plus plate current-collecting body and anode active material layer, and the anode active material layer includes positive electrode active materials, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；
The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；
The battery cathode includes one of metal, metal alloy or metal composite conductive material or several Kind.
Preferably, the metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal.
Preferably, the positive electrode active materials include the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
Preferably, the magnesium salts includes one or more of organic type magnesium salts or inorganic type magnesium salts.
Preferably, the concentration range of the magnesium salts is 0.1-10mol/L.
Preferably, the solvent includes one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
Second aspect, the present invention also provides a kind of preparation methods of Magnesium ion battery, this method comprises:
Battery cathode is prepared, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment.
Electrolyte is prepared, a certain amount of magnesium salts electrolyte is added in coordinative solvent, dissolution is sufficiently stirred.
Diaphragm is prepared, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm.
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；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried.
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 Magnesium ion battery, replace lithium with magnesium, solve the problems, such as that lithium resource reserves are limited；While Magnesium ion battery provided by the invention Battery cathode plays electric action and simultaneously as the material with cationoid reaction in electrolyte, the cathode of middle battery has generally included the collector of electric action and the active material for reacting compared with the prior art, save the volume and weight of a component, it can reduce the weight and volume of battery, improve battery energy density；And the reactive agent of electrochemical reaction that Magnesium ion battery provided by the invention is occurred is magnesium ion, there are two charges for magnesium ion band, improve the capacity of battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of Magnesium ion battery provided in an embodiment of the present invention.
Specific embodiment
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.
The present invention provides a kind of Magnesium ion batteries, structure is as shown in Figure 1, including battery cathode 1, electrolyte 2, diaphragm 3 and anode 4, wherein, the anode includes plus plate current-collecting body 42 and anode active material layer 41, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；The battery cathode includes one or more of metal, metal alloy or metal composite conductive material.
The embodiment of the present invention, during the charging process, magnesium ion deposit to battery cathode surface from positive electrode abjection, directly react to form magnesium-metal alloy with the metal or metal alloy of battery cathode or metal composite；In discharge process, it is embedded in positive electrode active materials after magnesium-metal alloy de-magging of cathode by electrolyte, to realize reversible charge and discharge.
Battery cathode in the Magnesium ion battery of the embodiment of the present invention plays electric action and simultaneously as the material reacted with magnesium ion, the cathode of middle battery has generally included the collector of electric action and the active material for reacting compared with the prior art, save the volume and weight of a component, the weight and volume of battery is reduced, battery energy density is improved；And the reactive agent of electrochemical reaction that Magnesium ion battery provided by the invention is occurred is magnesium ion, there are two charges for magnesium ion band, and the capacity of battery can be improved；Magnesium ion battery provided by the invention replaces lithium with magnesium simultaneously, solves the problems, such as that lithium resource reserves are limited.
In a preferred embodiment, the positive electrode active materials include but is not limited to the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
In a preferred embodiment, the positive electrode active materials include but is not limited to the metal oxide of magnesium, such as Mgx1MoO3, magnesium ferrite, mangaic acid magnesium, vanadic acid magnesium, vanadium magnesium ferrite, magnesium stannate, spinel-type MgCo0.4Mn1.6O4、MgM2O4；The metal sulfide of magnesium, such as Mgx2Mo3S4, Mgx3NS2；The polyanionic compound of magnesium, such as the silicate series MgASiO of orthohormbic structure4, sulfate series MgASO4, series of phosphate MgAPO4One or more of.The wherein any number of x1, x2, x3 between 0-1, M Mn, Ni, Co, Fe, Zn, Ti or Al, N Ti, Zr, Hf, Nb, Ta, Mo, W or V, A Fe, Mn, Ni, Al, V, Ti, Zn or Co.
In a preferred embodiment, the metal, metal alloy or metal composite conductive material include but is not limited to the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal, as long as deposition dissolution magnesium or form alloy with magnesium that the metal can be reversible, the present invention does not limit the type of metal.
Cathode of the invention, also using other metal or alloy materials or compound that alloying reaction can occur with magnesium, increases the alternative of negative electrode material other than magnesium metal or alloy material.
In a preferred embodiment, the plus plate current-collecting body include but is not limited to aluminium, lithium, magnesium, The compound or in which the alloy of any one of one of vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
In the embodiment of the present invention, the anode active material layer further includes conductive agent and binder.
In a preferred embodiment, the anode active material layer, by weight percentage, including 60~90wt% positive electrode active materials.
In a preferred embodiment, the anode active material layer, by weight percentage, including 0.1~30wt% conductive agent.
In a preferred embodiment, the anode active material layer, by weight percentage, including 0.1~10wt% binder.
It is understood that the binder and conductive agent in the anode active material layer are it is not also specifically limited, this field is existing common common.
In a preferred embodiment, the conductive agent is one or more of black conductive acetylene, conductive carbon ball, electrically conductive graphite, carbon nanotube, graphene.
In a preferred embodiment, the binder is one or more of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, butadiene-styrene rubber, polyolefins.
In the embodiment of the present invention, electrolyte is magnesium salts, including one or more of organic type magnesium salts or inorganic type magnesium salts.
In one embodiment of the present invention, the concentration range of the magnesium salts is 0.1-10mol/L.
In one embodiment of the present invention, the organic type magnesium salts includes but is not limited to RMgX, methylphenylamine magnesium bromide, pyrrole radicals magnesium bromide, ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg), N, N- bis- (trimethyl silicon substrate) amino magnesium chloride, Mg (SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2One or more of type complex, wherein R is alkyl, and X is halogen, A Al, B, As, P, Sb, Ta or Fe, and Z is Cl or Br, and R' is aryl, and n'+n "=n.
In one embodiment of the present invention, the inorganic type magnesium salts includes but is not limited to Mg (ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2One or more of.
It is understood that the solvent is not particularly limited, as long as making ion can be with free migration.
In a preferred embodiment, the solvent includes but is not limited to one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
In a preferred embodiment, the solvent is selected from 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, acetonitrile, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether, 1- Ethyl-3-methylimidazole-hexafluorophosphate, 1- ethyl-3-methylimidazole-tetrafluoroborate, 1- ethyl-3-methylimidazole-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazole-hexafluorophosphate, 1- propyl -3- methylimidazole-tetrafluoroborate, 1- propyl -3- methylimidazole-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazole-tetrafluoroborate, 1- butyl -1- methylimidazole-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyl sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyl sulfimide salt, N- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine- Bis trifluoromethyl sulfimide salt, N- first, one or more of butyl piperidine-bis trifluoromethyl sulfimide salt.
In a preferred embodiment, the solvent is ethers, compares other kinds of solvent, ether The stronger ethers of class especially polarity will not form oxide layer on the metal or metal alloy of battery cathode or metal composite surface, be conducive to when charge and discharge magnesium ion in the deposition or abjection of battery cathode.
Specifically, the ether solvent include but is not limited to include tetrahydrofuran (THF), 2- methyltetrahydrofuran (2Me-THF), 1, one or more of 3- dioxolanes (DN), Isosorbide-5-Nitrae-dioxane, diethyl ether (DEE), glycol dimethyl ether (DME) and tetraethyleneglycol dimethyl ether.
In a preferred embodiment, additive, such as LiCl can be added in the electrolyte, and the effect of additive is the comprehensive performances such as high temperature performance, security performance, the cycle performance for improving the ionic conductivity of electrolyte or improving battery.
It is understood that the diaphragm is it is not also specifically limited, existing common common using this field.
In an embodiment of the present invention, the diaphragm includes but is not limited to the porous polymer film or inorganic porous film to insulate.
In a preferred embodiment, the diaphragm includes but is not limited to porous polypropylene film, porous polyethylene film, porous compound polymer film, non-woven fabrics, all-glass paper or porous ceramics diaphragm.
In a preferred embodiment, the diaphragm is all-glass paper or non-woven fabrics.
It is understood that the form of Magnesium ion battery provided by the present invention is not particularly limited, it is commonly used in the art, such as the forms such as button cell, flat plate cell, cylindrical battery.
Second aspect, the embodiment of the invention also provides the methods for preparing above-mentioned Magnesium ion battery, comprising:
Step 101, preparation battery cathode, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment.
Specifically, metal, metal alloy or metal composite conductive material are selected from one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which the compound or in which the alloy of any one of any one metal.
Step 102 prepares electrolyte, and a certain amount of magnesium salts electrolyte is added in coordinative solvent, dissolution is sufficiently stirred.
The magnesium salts electrolyte specifically includes one or more of organic type magnesium salts or inorganic type magnesium salts.
Specifically, the organic type magnesium salts includes RMgX, methylphenylamine magnesium bromide, pyrrole radicals magnesium bromide, ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg), N, N- bis- (trimethyl silicon substrate) amino magnesium chloride, Mg (SnPh3)2、Mg(BR2R'2)2、Mg(AZ3-nRn'R'n”)2One or more of type complex.Wherein, R is alkyl, and X is halogen, A Al, B, As, P, Sb, Ta or Fe, and Z is Cl or Br, and R' is aryl, and n'+n "=n.
Specifically, the inorganic type magnesium salts includes Mg (ClO4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2One or more of.
Specifically, the magnesium salts is obtained by directly purchase or by the way that two kinds of solution allocations reacts acquisition together.
The solvent includes but is not limited to esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, one or more of amides ionic liquid, selected from 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 , acetonitrile, dimethyl ether, ethylene sulfite, sulfurous acid propylene rouge, two formicester of sulfurous acid, sulfurous acid diethyl rouge, crown ether, 1- ethyl-3-methylimidazole-hexafluorophosphate, 1- ethyl-3-methylimidazole-tetrafluoroborate, 1- ethyl-3-methylimidazole-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazole-hexafluorophosphate, 1- propyl -3- methylimidazole-tetrafluoroborate, 1- propyl -3- methylimidazole-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazole-tetrafluoroborate, 1- butyl -1- methylimidazole-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyl sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyl sulfimide salt, N- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis trifluoromethyl sulfimide salt, N- first, one or more of butyl piperidine-bis trifluoromethyl sulfimide salt.
The magnesium salts electrolyte is added in the solvent, dissolution is sufficiently stirred, the concentration range of magnesium salts described in the electrolyte of configuration is 0.1-10mol/L.
Step 103 prepares diaphragm, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm.
Specifically, the porous polymer film or inorganic porous film include but is not limited to porous polypropylene film, porous polyethylene film, porous compound polymer film, non-woven fabrics, all-glass paper or porous ceramics diaphragm.
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；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried.
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% in anode active material layer, and the content of conductive agent is 0.1-30wt%, and the content of binder is 0.1-10wt%.
The positive electrode active materials include but is not limited to one or more of metal oxide, metal sulfide, polyanionic compound of magnesium.
The conductive agent includes but is not limited to one or more of black conductive acetylene, conductive carbon ball, electrically conductive graphite, carbon nanotube, graphene.
The binder includes but is not limited to one or more of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, butadiene-styrene rubber, polyolefins
Step 105 is assembled using the battery cathode, electrolyte, diaphragm and anode.
Specifically include: under inert gas or anhydrous and oxygen-free environment, by the cathode prepared, diaphragm, anode, successively Close stack, dropwise addition electrolyte make diaphragm complete wetting, are then encapsulated into battery case, complete 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.The preparation of step 101-104 simultaneously or arbitrarily can be executed successively.
The Magnesium ion battery preparation method and aforementioned Magnesium ion battery are that based on the same inventive concept, have the institute of aforementioned Magnesium ion battery effective using the Magnesium ion battery that the Magnesium ion battery preparation method obtains, details are not described herein.
Above-mentioned Magnesium 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: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: measuring 2.5ml MgBu2Solution and 2.5ml AlCl2The mixing of Et solution, then will be molten Agent is distilled off, by reaction product Mg (AlCl2BuEt)2It is added into appropriate high-purity tetrahydrofuran solution spare as electrolyte.
It prepares anode: 0.4g magnesium ferrite, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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
Preparation battery cathode: taking the nickel foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: measuring 4.5ml N, (trimethyl silicon substrate) the amino magnesium chloride solution of N- bis- and 1.5ml AlCl3Solution mixing, then solvent is distilled off, by reaction product [Mg2(μ-Cl)3·6THF][HMDSAlCl3] be added into appropriate high-purity tetrahydrofuran solution it is spare as electrolyte.
It prepares anode: 0.4g manganous silicate magnesium material, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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, then by above-mentioned stack portion Enfeoffment is packed into button cell shell, completes battery assembly.
Embodiment 3
Preparation battery cathode: taking the nickel foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous polyethylene film is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 2.15g ethylenediamine tetraacetic acid disodium magnesium salt (EDTA-Mg) and be added in 5ml formamide (FA), be stirred well to after ethylenediamine tetraacetic acid disodium magnesium salt is completely dissolved spare as electrolyte.
Prepare anode: by 0.4gMgxMo3S4, 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 and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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 4
Preparation battery cathode: taking the tinfoil paper with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: non-woven fabrics is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 0.5M pyrrole radicals magnesium bromide and be added in tetrahydrofuran (THF), be stirred well to after pyrrole radicals magnesium bromide is completely dissolved spare as electrolyte.
Prepare anode: by 0.4gMgCo0.4Mn1.6O4, 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 and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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 5
Preparation battery cathode: taking the zinc foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous ceramics diaphragm is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 1.11g magnesium perchlorate and be added in 2.5ml acetonitrile and 2.5ml ethylene carbonate, be stirred well to after magnesium perchlorate is completely dissolved spare as electrolyte.
It prepares anode: 0.4g titanium phosphate magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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 6
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: porous composite polymer membranes is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 0.475g magnesium chloride and be added in 2.5ml tetrahydrofuran (THF) and 2.5ml ethylene carbonate, be stirred well to after magnesium chloride is completely dissolved spare as electrolyte.
It prepares anode: 0.4g vanadium magnesium ferrite, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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 7
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, is used as negative current collector spare after cutting into the disk surfaces processing of diameter 12mm.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 2.22g magnesium perchlorate and be added to 5ml n,N-Dimethylformamide (DMF), be stirred well to after magnesium perchlorate is completely dissolved spare as electrolyte.
It prepares anode: 0.4g vanadic acid magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil table Face is simultaneously dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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 8
Preparation battery cathode: taking the aluminium foil with a thickness of 0.02mm, cut into the disk of diameter 12mm, spare as negative current collector after surface treatment.
It prepares diaphragm: all-glass paper is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
It prepares electrolyte: weighing 3.22gMg (CF3SO3)2It is added to 10mlN- Methyl-N-propyl pyrrolidines-bis trifluoromethyl sulfimide salt, is stirred well to Mg (CF3SO3)2It is spare as electrolyte after being completely dissolved.
It prepares anode: 0.4g cobalt phosphate magnesium, 0.1g carbon black, 0.1g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
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.
Magnesium 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.
Particular embodiments described above has been further described the purpose of the present invention, technical scheme and beneficial effects, it should be understood that the above is only a specific embodiment of the present invention, not For limiting 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 be should all be included in the protection scope of the present invention.

Claims (7)

  1. A kind of Magnesium ion battery, including battery cathode, electrolyte, diaphragm and anode, which is characterized in that
    Wherein, the anode includes plus plate current-collecting body and anode active material layer, and the anode active material layer includes positive electrode active materials, and the anode active material layer includes the positive electrode active materials of freely reversible deintercalation magnesium ion；
    The electrolyte includes electrolyte and solvent, and the electrolyte is magnesium salts；
    The battery cathode includes one or more of metal, metal alloy or metal composite conductive material.
  2. Magnesium ion battery as described in claim 1, it is characterized in that, the metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of magnesium metal, nickel, tin, zinc, lithium, aluminium, copper, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, calcium, beryllium, gold, silver, barium or in which any one metal.
  3. Magnesium ion battery as described in claim 1, which is characterized in that the positive electrode active materials include the one or more of the metal oxide of magnesium, metal sulfide or polyanionic compound.
  4. Secondary cell as described in claim 1, which is characterized in that the magnesium salts includes one or more of organic type magnesium salts or inorganic type magnesium salts.
  5. Magnesium ion battery as described in claim 1, which is characterized in that the concentration range of the magnesium salts is 0.1-10mol/L.
  6. Magnesium ion battery as described in claim 1, which is characterized in that the solvent includes one or more of esters, sulfone class, ethers, nitrile organic solvent or imidazoles, piperidines, pyroles, quaternary amines, amides ionic liquid.
  7. A kind of preparation method preparing the Magnesium ion battery as described in one of claim 1-6, feature exist In, comprising:
    Battery cathode is prepared, the metal of required size, metal alloy or metal composite conductive material is spare as battery cathode after surface treatment；
    Electrolyte is prepared, a certain amount of magnesium salts electrolyte is weighed and is added in coordinative solvent, dissolution is sufficiently stirred；
    Diaphragm is prepared, using the porous polymer film of required size or inorganic porous film or organic/inorganic composite diaphragm as battery diaphragm；
    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；Using metal, metal alloy or metal composite conductive material as plus plate current-collecting body；Then the anode active material layer is evenly applied to plus plate current-collecting body surface, the anode of size needed for obtaining after the anode active material layer is completely dried；
    It is assembled using the battery cathode, electrolyte, diaphragm and anode.
CN201680085081.7A 2016-05-31 2016-05-31 A kind of Magnesium ion battery and preparation method thereof Pending CN109196701A (en)

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Application publication date: 20190111