CN1365524A - Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries - Google Patents

Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries Download PDF

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CN1365524A
CN1365524A CN00811017A CN00811017A CN1365524A CN 1365524 A CN1365524 A CN 1365524A CN 00811017 A CN00811017 A CN 00811017A CN 00811017 A CN00811017 A CN 00811017A CN 1365524 A CN1365524 A CN 1365524A
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battery
magnesium
anode
embedding
negative electrode
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V·迪诺托
M·法里
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UNI DEGLI STUDI DI PADOVA
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UNI DEGLI STUDI DI PADOVA
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Primary Cells (AREA)

Abstract

The batteries described herein are of the type comprising at least one anode, at least one cathode and at least one electrolyte, and current collectors, in which at least the anode is magnesium-based, and optionally also the cathode and the electrolyte contain magnesium. Assembly of the batteries involves the preparation of the individual components and the interposition of a thin layer of electrolyte between the magnesium-based anode and the cathode.

Description

Magnesium base primary cell (non-rechargeabel) and secondary (chargeable) battery
Invention field
The present invention relates to wherein at least that anode comprises magnesium, the method that optionally also has electrolyte and negative electrode also to comprise once (that is, non-rechargeabel) of magnesium and secondary (that is, chargeable) battery and make described battery.
Original technology
As known to, a large amount of and swift and violent development of the digitalized electron product that presents in recent years can create a large amount of novel moveable devices, for example computer, cellphone, video camera or the like.These devices almost are according to single-minded technology assembled batteries ad hoc; Nickel-cadmium (Ni-Cd) battery just.
Promoted many individuals' company and the work that public R﹠D institution is engaged in this respect for the needs of producing littler and lighter moveable device and for the work long hours needs of independence of these devices, be to reach the development Research on New of the demand to carry out its purpose.
In late nineteen eighties the early 1990s, two kinds of novel batteries appear on the market: nickel-metal hydrides (Ni-MH) and lithium ion (Li-lithium ion) battery.
In recent years, utilize the performance of the battery of these technology productions to have sizable raising, the performance of these batteries is better than nickel-cadmium cell at present.
Another advantage of battery of utilizing these new technologies to produce is not exist cadmium, because cadmium is a heavy metal, has quite serious adverse effect for environment.
As known to, lithium ion battery is still the most promising a kind of aspect energy, but their production cost is high relatively.But,, can notice with more economical nickel-cadmium cell and compare that they are competitive if consider the cost of the each circulation of these systems.Cost based on technical characteristic, environmental impact, each circulation in the world market rises appreciably for being desirably in of li-ion systems.
On the other hand, nickel metal hydride battery may have more appropriate growth, and estimates that nickel-cadmium cell may not can keep their present levels of production.
International situation shows most concentrations of production in the lithium ion battery part, and this is the development of lithium system.
Be widely used for disposable lithium-battery in calculator, clock, wrist-watch, the cardiac pacemaker etc. by lithium anode and transition metal oxide (for example, MnO 2) negative electrode made makes.Because lithium anode provides the high electrochemical electromotive force, these batteries provide high cell voltage, thereby also have high energy density.
But these batteries are irreversible, or can be used at the most circulating several times.
First kind of technology of lithium-polymer (Li-polymer) technology known to the idea of utilizing lithium to make secondary cell has occurred.But there is serious difficulty in this method of utilizing lithium metal to prepare anode aspect invertibity.In fact, in charging process, form the dendrite deposition on anode surface, this is because the result of lithium and the electrolytical reaction of organic polymer is the reason that causes such battery to damage fast.
At most, the cycle-index of utilizing such system and being obtained amounts to and has only tens times or hundreds of.
On the other hand, lithium also can become the reason of safety problem serious in battery self course of work for the reactivity of polymer dielectric.
The next stage in these device developments is the introducing of so-called lithium ion or rocking chair technology, and this technology can embed Li by insertion reaction by using in their structure +Composite material substitute lithium to solve the problem that on lithium anode, forms dendrite.
In recent years, can produce anode based on carbon with embedded performance.Have regular texture (vortex static state (turbostatic) or graphitisable) or have the particular carbon material of high crystalline texture (natural or synthetic graphite) and can be practically in their layer, embed Li in mode reversibly +Li appears in ion thus xC 6The synthetic of type.
Other lithium ion battery has the titanium disulphide thing base (Li of embedding xTiS 2) anode.The latter has the effect similar to carbon electrode.
Usually negative electrode alternatively utilizes the oxide of lithium and transition metal to make, wherein so far the most extensive employing be cobalt acid lithium (LiCoO 2), tend to by lithium nickelate (LiNiO for the reason of cost, availability, toxicity 2) or LiMn2O4 (LiMnO 4) replace.
Adopt the obtainable cycle-index of rocking chair technology to reach 1,000.
Usually, in the electrolyte system that the organic polymer with solvent nature constitutes, this organic polymer passes through with special lithium salts (for example, LiPF 6, LiClO 4Deng) mixing presents ionic conduction.
The problem that the employing of the element therewith that the high response of lithium causes although the fact of above-mentioned technological progress is tending towards solving is relevant, especially relevant with the formation of dendrite on anode subject matter, but the research that solves fully for these problems is still in constantly carrying out.Dendrite forms problem and also solves fully, resembles the height reaction problem of lithium simultaneously, existing problem and reversible problem of the fail safe formerly mentioned still exists.
Magnesium can be the element that is used to overcome these problems, especially as the substitute to lithium.
As the report in the document, many researchers, for example Farrington and Cherng have explored development magnesium base polymer electrolyte system for the possible development of magnesium cell, but have only some achievements seldom.In fact, the polymer dielectric that is obtained conductivity at room temperature for once and/or the secondary cell product too high (that is, conductivity is lower than 10 -6Siemens/cm).
Yet in patent US44575, Moulton proposes to make the possibility of magnesium cell, but does not specify operation, does not especially specify and how to make anode, negative electrode and polymer dielectric.Quoted the polymer dielectric that mixes with magnesium salts as proof, when test, the above-mentioned polymer dielectric that mixes with magnesium salts at room temperature produces and is higher than 10 7The resistance of ohmcm, however in order to make battery, resistance value must drop to and is lower than 10 5Ohmcm.
Main task of the present invention is successfully to develop once (non-chargeable) battery and/or secondary (chargeable) battery, and this primary cell and/or secondary cell have overcome the reaction of lithium-base battery and the problem of invertibity aspect.
In the framework of above-mentioned task, thing followed primary and foremost purpose is that development has high-level technical characteristic and the battery that has reduced production cost.
Another main purpose is reducing and a lightweight battery of development.
Also purpose of the present invention is that development is suitable for use in the battery in the removable digital electronic device.
Another free-revving engine is to reach almost all eliminating of environmental impact.
Summary of the invention
By once (non-chargeable) and secondary (chargeable) battery that reaches target of the present invention, the more clearly these and other objects of performance in as described below have been realized, the battery of this type comprises at least one anode, at least one negative electrode, at least a electrolyte and collector, and described battery is characterised in that: at least anode and selectivity simultaneously electrolyte contain magnesium.And the negative electrode that reaches the battery of target of the present invention can optionally contain magnesium.
The anode that comprises among the present invention is characterised in that: it uses magnesium Mg that optionally combine with magnesium metal, various oxidation state N+ (0≤n≤2)May contain the electrolytical of magnesium is characterised in that: it is included in the magnesium of any ionic species in the solvent, above-mentioned solvent comprises polymer solvent, and this polymer solvent is can produce to have the electrolytical of good ionic conductivity and can make described ionic substance solvation.
When negative electrode comprises magnesium, this is 2 +The magnesium form of the state of oxidation can have the substrate of the inorganic or organic material of high conduction, perhaps can embed or be embedded in the inorganic or organic material of high conduction.
Another object of the present invention is to be used to produce the described primary cell of following type and the method for secondary cell, the battery of this type comprises at least one anode, at least one negative electrode, be arranged at least a electrolyte between the anode and cathode, be electrically connected collector, and the characteristics of described battery are at least anode, optionally electrolyte and negative electrode contain magnesium.
Also purpose of the present invention is the employing at the δ form chlorination magnesium salts that is used for preparation of electrolyte, and adopts Grignard (Grignard) magnesium as the material for electrolyte generation magnesium cation.
In conjunction with the accompanying drawings from the detailed description of the present invention followed with clearer further characteristics and the advantage of demonstrating, described embodiment is only for the purpose of non-limitative example.
Brief description of drawings Fig. 1 is the cross-sectional view of the battery of formation according to the present invention, wherein:
10 expressions possess described characteristic, the anode as making in the following detailed description;
11 expressions have described characteristic, the negative electrode as making in the following detailed description;
12 expressions have described characteristic, the electrolyte as making in the following detailed description.
Detailed description of the invention
Although with reference to the above-mentioned fact of attempting failing for desirable result, the inventor now surprised discovery magnesium be can be used in effectively manufacturing once with secondary cell in element.
Along with extensively a large amount of research, in fact the inventor finds, for purposes of the present invention, if promptly for obtain technical performance be not better than being comparable to yet present employing or known lithium battery once and secondary cell, with reference to above-mentioned accompanying drawing, the battery that forms the object of the invention can be following type once and secondary cell, the battery of this type comprises at least one anode, at least one negative electrode, at least a electrolyte, the collector that is arranged between anode and the negative electrode, and described battery is characterised in that at least this anode, optionally electrolyte also contains magnesium simultaneously.
In reaching the battery of target of the present invention, negative electrode also can optionally contain magnesium.
When electrolyte or negative electrode do not contain magnesium, they are conventional electrolyte or negative electrodes, so known to they self are, therefore are not described further at this.
What reach target of the present invention once can also comprise possible insulating barrier with secondary cell, does not illustrate in the drawings.Especially, can constitute by following according to battery of the present invention:
Anode 10 is characterised in that: it comprises magnesium Mg that optionally combine with magnesium metal, various oxidation state N+ (0≤n≤2)
In described anode, magnesium can former state ground involved, perhaps magnesium also can have high conductivity inorganic or organic material substrate or have can be by containing the substrate of inorganic or organic material that (englobing) reduced the high conductivity of the magnesium crystallite of size or magnesium monocrystal in the matrix that embeds or be embedded into them.
Especially, anode 10 can be made of magnesium metal same as before, and in this case, magnesium can adopt with the form of lamination or sintering.
On the contrary, under so a kind of situation, magnesium has the substrate of high conductive material, and these can be from by metal (for example aluminium, the suitable metal with other of copper), or oxide, the inorganic material of selecting in the group that the fabric that alloy and described same material constitute constitutes.Described high-conductivity backing material also can be organically, also can be polymer type; In the later case, they are from carbon fibre fabric for example, graphite or even graphite-base composite material or be suitable for selecting other suitable material of this purpose.
And embedding or embedded material is used under the situation of anode, its both can be organic also can be inorganic.The embedding or the embedded material that can be used for the object of the invention are transistion metal compound, alkali metal compound, alkaline earth metal compound, can also be the nonmetallic compounds of selecting from oxide, sulfide, phosphate, phosphide, for example tungsten oxide (W yO x), iron oxide (Fe yO x), titanium sulfide (Ti yS x), cobalt oxide (Co yO x), nickel oxide (Ni yO x), manganese oxide (Mn yO x) or other suitable compound, or has a carbon-based material that embeds characteristic and high crystalline texture or irregular structure, or suitable material, also or the material of polymer type, for example can contain magnesium crystallite or the carbon-based polymer of magnesium monocrystal or the suitable polymer that has reduced size by embedding or be embedded in they self the matrix.
Described in addition anode 10 can be optionally with the oxidant oxidation and by handling stabilisation with stabilizer, above-mentioned oxidant for example is oxygen or H for example 2O 2Or peroxide such as organic peroxide, the aforementioned stable agent for example is alkoxide class (as four alkoxytitaniums, tetraalkoxysilane, tri-alkoxy aluminium, four zirconium alkoxides or a dialkoxy magnesium, or suitable compound).
Negative electrode 11 is characterised in that it comprises and has 2 +The magnesium material of the state of oxidation.
Contain at negative electrode under the situation of magnesium, magnesium can have the inorganic of high conductivity or comprise the substrate of the organic material of polymeric material, perhaps this magnesium can embed or be embedded to inorganic or organic material in.Have substrate and embed or imbed the material that can adopt under the both of these case at magnesium identical at magnesium with the aforementioned material that is used for anode.
Can adopt such negative electrode, active material is distributed in the matrix of porous and conduction.This employing mode has the advantage of the chemical property that improves battery.
And negative electrode can be optionally with identical oxidant oxidation.The oxidation of negative electrode can be carried out in situ and after its preparation as anode, and is perhaps different with anode, and negative electrode can be used in before its preparation partly that the electrochemical active material of oxidation prepares.
When negative electrode 11 does not comprise magnesium, therefore conventional negative electrode and himself be known is not further describing at this.In this case, in any case negative electrode comprises electrochemical active material, this electrochemical active material has the reduction of proper proportion or the metal mixture basis of oxidised form.For this purpose, as known in the art, can adopt the material that contains transition metal, for example, but not ad hoc, have from 7 +To 2 +Manganese and other suitable metal of the state of oxidation.
Electrolyte 12 is characterised in that it is included in any ionic substance in the solvent, and above-mentioned solvent comprises polymer solvent, and this solvent can produce to have good ionic conductivity and can make described material solvation.
Electrolyte according to the present invention comprises that as magnesium salts or the general formula ionic substance of magnesium, that have low-down electric charge/volume ratio (charge/volume ratio) rate be Mg (R) yX 2-yThe complex of (0≤y≤2).
Radicals R can be from by for example having C 1-C 7Select in the group that the alkyl of chain constitutes, X can be from halide, ClO simultaneously 4, (CF 3) 1+xSO 3-x(0≤x≤2), SCN -, PO 4 3-, with what select in the chloride of δ form or other the suitable thing.
In addition, the electrolytical general formula that can be used for mixing is Mg (R) yX 2-yThe compound of (0≤y≤2) can be that preferably lattice energy is lower than magnesium salts or the magnesium complex of 500kcal/mol.
Being used for electrolytical solvent can be all kinds and since required main performance they should have good ionic conductivity and under any circumstance they should can make magnesium salts or the magnesium complex solvation of having selected simultaneously.For this purpose, thus they can be liquid flux or be in solid or the solvent of viscous state.
Under the situation of liquid flux, these are to select from the material with polar group, and these polar groups can coordination and the magnesium salts or the complex of dissociating ions, and these polar groups comprise oxygen, nitrogen, sulphur and carbon.Therefore these solvents can be from ether, alcohol, glycol, ester, amine and acid amides, thioether, mercaptan, thioesters, alkyl carbonate, thiocarbonic acid Arrcostab or other suitable thing.
Be used under the situation that electrolytical solvent is solid or viscosity, it can be a polymer type.
What can be used for this purpose is all polymer or its copolymers with different molecular weight, and this polymer or copolymer can be used in the magnesium salts or the complex solvation of this purpose.These polymer and/or copolymer can be from polyoxyalkylene, PAG, Merlon, poly-alkylsiloxane, poly-diaminourea tetraacethyl second diester (polyethylene-diaminotetra-acetate) or suitable polymer or have different molecular weight and also contain the copolymer of aerobic, nitrogen, silicon and the heteroatomic identical macromolecular structure of phosphorus type their chain.
What also can be used for this purpose is with aforementioned polymer of mentioning and/or the functionalized polyphosphazene polymer of copolymer.
For example is provided, in polyoxyalkylene, following may relating to: polymethylene oxide, poly(ethylene oxide), PPOX etc.; In PAG, following may being mentioned to: polymethylene glycols, polyethylene glycol, polypropylene glycol with and fluorinated derivatives or other etc.; In Merlon, following may being mentioned to: polymerized thylene carbonate methyl ester, polymerized thylene carbonate ethyl ester and poly (propylene carbonate) etc.; In poly-alkylsiloxane, following may being mentioned to: polymethyl siloxane, poly-ethylsiloxane and poly-propyl-siloxane etc.
What also can be used for this purpose is copolymer, and it derives from polyoxyalkylene and PAG, Merlon, poly-alkylsiloxane, gathers diaminourea tetraacethyl second diester; PAG and Merlon, poly-alkylsiloxane, poly-diaminourea tetraacethyl second diester; Merlon and poly-alkylsiloxane, poly-diaminourea tetraacethyl second diester; Poly-alkylsiloxane and poly-diaminourea tetraacethyl second diester be poly(ethylene oxide)-PPOX, polymethylene oxide-poly(ethylene oxide) and polymethylene oxide-PPOX for example; Poly(ethylene oxide)-polymerized thylene carbonate methyl ester, PPOX-polymerized thylene carbonate ethyl ester and poly(ethylene oxide)-poly (propylene carbonate); The copolymer of polyethylene glycol-methyl polysiloxane, poly(ethylene oxide)-polymethyl siloxane and poly(ethylene oxide)-poly-diaminourea tetraacethyl second diester or the like.
For this purpose, can also adopt polymer and/or the functionalized polyphosphazene copolymer of copolymer of for example using types such as poly(ethylene oxide) with different molecular weight.
Can be used for the polymer of preparation of electrolyte and/or copolymer can also with in conjunction with or the group functionalization of coordination magnesium so that improve them and the interaction of the salt of magnesium or complex.
In order to improve electrolytical ionic conductivity, therefore this can also will no longer further describe in detail according to optionally acidifying or the alkalization of existing operation.
But, electrolyte is being carried out under the situation of acidifying, being used for electrolytical preferred acidulant is to have phosphorus, polyphosphate, P 2O 5, or the compound on the basis of the suitable material of orthophosphoric acid type.Under the electrolytical condition of alkalization, the compound that can adopt is a kind of of nitrogen base, preferably amine or ammonia in the case, and the alkaline derivant of sulphur or phosphorus.
Acidifying has improved electrolytical conductivity, and this step will can not satisfy whenever carrying out of application in electrolytical performance.This step is preferred under the situation of stabilized electrodes.
Equally, alkalization has improved electrolytical conductivity, and the execution of alkalization helps the electrochemical action of electrode.But this step preferably adopts under the situation of astable electrode.
By dividing plate (not shown) inorganic or that organic material constitutes be can see through ion and have a high insulation characterisitic; If necessary, in order to remove the polar group that may be present in fiber surface, suitably functionalized to these.For this purpose, can adopt for example cellulose, glass fabric, organic barrier film or other suitable material.
Collector 13 can be a metal or nonmetal, in order to collect electronics and for the electrical connection of the pole of cell device, has electric conductivity and is not higher than the resistance of 10ohmm.For this purpose, for example can adopt metal, even with the form of oxide, alloy, the fabric that is manufactured from the same material, for example aluminium, copper, steel, brass, or the like; The perhaps organic material of making by carbon or carbon fibre fabric or analog material.
Preparation is provided with one of following step at least according to the method for once of the present invention and/or secondary cell:
Anode preparation is characterized in that it comprises the magnesium Mg of the various oxidation state that selectively are combined with metal M g N+(0≤n≤2), described anode have the basis of the basis of such a magnesium metal or the magnesium on the inorganic or organic material substrate of high conduction or on the basis of the magnesium of the inorganic or organic material of embedding that is used for magnesium or embedding;
Negative electrode preparation is characterized in that it comprises the substrate of the inorganic or organic material with high conductivity or at the magnesium material of the 2+ oxidation state of the inorganic or organic composite material of embedding that is used for magnesium or embedding.
Preparation of electrolyte is characterized in that it is included in any ionic substance of the magnesium in the solvent, and above-mentioned solvent can produce to have good ionic conductivity electrolyte and can dissolve described ionic substance.
As previously mentioned, electrolyte can optionally strengthen with dividing plate.
Above-mentioned three kinds of elements contact with each other, and the layer of electrolyte 12 is arranged between anode 10 and the negative electrode 11.Also can obtain in the tight contact between anode 10, electrolyte 12, the negative electrode 11 by under the temperature between room temperature and about 150 ℃, on the combination of elements body, applying slight pressure.
In order to obtain the battery of enough performances, can adopt with known lithium battery to prepare identical technology.
Particularly, can:
Adopt single or multiple lift button cell technology;
Connect parallel multilayer film (parallel stack), perhaps be connected in series multilayer film (bipolar laminated), be used for non-foldable structure;
Adopt flat roll designing technique or rubber roll designing technique, or be used for the flat stack designing technique of foldable structure.
What below describe in detail is when discrete component comprises magnesium, is used for the preparation method of these individual components, therefore aspect characteristic and aspect production method for any technical staff of this area be not conventional with known to.A-is used for the A.1-preparation of anode 10 of conventional method of component fabrication
For purposes of the present invention, can adopt three types anode 10: magnesium base anode with above-mentioned characteristic of having mentioned, (i), perhaps (ii) on substrate, (iii) embed or imbed and be used for embedding or the material of embedding magnesium with high conduction organic or inorganic material by such.
Such magnesium can be to begin stackedly from Grignard magnesium, maybe can be the powder type with suitable particle diameter, or commercially available form with the different length ribbon.In addition, also can this magnesium of sintering.
Anode also can be made of the magnesium on the substrate of the organic or inorganic material of high conductivity, and above-mentioned material comprises foregoing polymeric material.This anode type can be by chemistry, vapours, electrolysis or the electrochemical deposition method preparation of magnesium material.
Other type of anode 10 is made by the material of embedding that is used for magnesium or embedding.Especially this anode mixture by suspension polyethylene, polyvinyl chloride, polyacrylamide, polyacrylonitrile or some other analog and insert material in solvent prepares, described solvent is benzene, toluene, N-N dimethylacetylamide, dimethyl formamide, oxolane etc. for example, and above-mentioned insert material is anticipated with magnesium and evenly mixed fully.Above-mentioned material distributes fully and uniformly in solvent self up to obtaining to handle this system.Then by the composite membrane of slow evaporating solvent acquisition based on embedding or embedded material (base).
Except some were described in the front, other method that the anode that is obtained is embedded can for example spray the magnesium plasma or be splashed in selected embedding or the embedded material according to physical method.
No matter adopt the anode of any type, this anode can both be subsequently with oxygen or peroxide H for example 2O 2Or organic peroxide oxidation.In addition, can carry out in addition and possible stabilization processes by antianode.As stabilizer, can adopt alkoxide class (for example four alkoxytitaniums, tetraalkoxysilane, tri-alkoxy aluminium, four zirconium alkoxides or dialkoxy magnesium, or suitable compound).
With above-mentioned further operation, can obtain to show the anode of better stability, invertibity and exchanging electric current.A.2-the preparation of negative electrode 11
The substrate that both can be provided for magnesium also can prepare negative electrode 11 with the compound with embedding or embedded material basis, wherein adopts and above-mentioned anode 10 similar methods that are used for, and owing to this reason, is not described further at this.Insert material is used for the identical of anode with those, for example can be, but be not uniquely, has carbon, graphite, titanium disulfide (TiS 2), cobalt dioxide (CoO 2), nickel dioxide (NiO 2), manganese dioxide (MnO 2) or other suitable material of selecting among above-mentioned mentioned any.
As anode, negative electrode also can be in position and accept other oxidation operation after its preparation, these operations and being described in front.But different with anode, negative electrode can be used in the electrochemical active material preparation of partial oxidation before the negative electrode preparation.A.3-the preparation of insert material
Insert material is to select among the material that can be used for this purpose male or female, according to general operation preparation described below.With insert material in grinding in ball grinder up to the structural disorder completely that obtains this material.Subsequently, this material is closely contacted with magnesium carbonate or magnesium oxide.After evenly mixing also nodularization, thus obtained mixture brought up under about 100 ℃ to 400 ℃ temperature keep between 1 to 3 hour, (for example argon gas) reaches the temperature between 800 ℃ to 1200 ℃ in inert gas afterwards, and keeps 1 to 5 day in temperature range under vacuum condition.A.4-the preparation of electrolyte 12
Electrolyte 12 according to the present invention can adopt solvent preparation, above-mentioned solvent to comprise, but is not uniquely, and polymer solvent, above-mentioned polymer solvent can make the ionic substance solvation of any magnesium, and can produce the electrolyte with good ionic conductivity.Electrolyte according to the present invention comprises that as the magnesium salts with low-down electric charge/volume ratio of ionic substance or general formula be Mg (R) yX 2-yThe complex of (0≤y≤2).Radicals R can be from by for example having C 1-C 7Select in the group that the alkyl of chain constitutes, X can be from halide, ClO simultaneously 4, (CF 3) 1+xSO 3-x(0≤x≤2), SCN -, PO 4 3-, select in the chloride with the δ form.In addition, the electrolytical general formula that can be used for mixing is Mg (R) yX 2-yThe compound of (0≤y≤2) can be that preferably lattice energy is lower than the magnesium salts of 500kcal/mol or the ionic complex of magnesium.
According to following prepared in reaction:
Solvent+salt/inorganic complexes → electrolyte
Can be according to the electrolytical mode of above-mentioned prepared in reaction according to following three basic working procedure.First operation relates to magnesium salts or complex directly dissolving in liquid flux or molten polymer (when the words that the latter allows).Second operation relates to polymer solvent and magnesium salts or complex and dissolves in cosolvent with the slow evaporation acquisition polymer film (solvent-cast) by solvent.The 3rd operation relates to the acquisition polymer dielectric, and this polymer dielectric can have high conductivity and be based on the polymer dielectric with height commissure.In these cases, for various reasons, the preparation polymer dielectric obtains the solution of monomer and the solution of magnesium salts or cooperation earlier like this, carries out polymerization reaction subsequently.
The solvent that can be used for this purpose is all above-mentioned those that mentioned, for example is provided, especially have and cooperate and the magnesium salts of dissociating ions or complex, comprise oxygen, nitrogen, any fluent material of the polar group of sulphur and carbon, ether for example, alcohol, glycol, ester, amine and acid amides, thioether, mercaptan, thioesters, alkyl carbonate, the thiocarbonic acid Arrcostab, the polymer and/or the copolymer that perhaps have different molecular weight, polyoxyalkylene, PAG, Merlon, poly-alkylsiloxane, poly-diaminourea tetraacethyl second diester or derivatives thereof, in these polymer and/or copolymer, one or more atoms in chain are by from oxygen, nitrogen, silicon, the one or more hetero-atoms of selecting in the phosphorus replace, and with above-mentioned polymer or the functionalized polyphosphazene polymer of copolymer.
At magnesium salts that can be used for the object of the invention or complex, particularly advantageous is δ-MgCl 2, because it has low-down lattice energy for example near Okcal/mol., because of it can be dissolved in can the organic solvent of coordination magnesium in, particularly advantageous also have Grignard magnesium, is used for electrolytical cationic material as generation.
Also can utilize according to the electrolyte that one of said method obtained operation and method known to this purpose are carried out acidifying or alkalization.Under the electrolytical situation of acidifying, for purposes of the present invention, can preferably under stirring condition, add the phosphorio compound of appropriate amount, for example P 2O 5Or other suitable thing, up to dissolving fully.Under the situation of electrolyte, use similar operation with the alkaline derivant alkalization of nitrilo compound or sulphur and phosphorus.A.5-the preparation of insulating barrier
Insulating barrier can see through insulating material by any ion with good insulation performance intensity and dielectric constant characteristic and make.Have in its surface at material under the situation of polar group, carry out chemical passivation to prevent the interaction with the ionic complex of magnesium ion or magnesium by suitable functionalized mode.For example under the situation of glass fibre, being present in lip-deep hydroxyl is by losing activity with the reaction of triethoxy alkyl silane, staying high nonpolar baffle surface thus.B-is used for the general example that element is produced
Below to the present invention its general aspect and further illustrate by several examples of implementing, these examples only are used to illustrate the present invention, and not by any way the qualification to its scope.B.1-the example for preparing anode 10 by sintering
From the magnesium metal of fine gtinding preparation anode 10 and applying sintering under the pressure of 1400MPa.By this way, after having applied about 10 minutes pressure, obtained to have the metal film of desired thickness.B.2-the pre-preparation that embeds the graphite of magnesium of heat
Utilize ball milling to make the magnesium oxide of about 3% weight ratio, the mixture of graphite be rendered as disordered state.This mechanical mixture step was carried out about 30 minutes so that two kinds of components homogenizing closely.In addition, the mechanism of ball milling has increased the randomness of graphite crystallization.Next, thus obtained material is incorporated into quartz ampoule and accepts six nitrogen-vacuum cycle to eliminate any trace air.
Subsequently, the mode of this quartz ampoule by diffusion pump reached 10 -6Vacuum under the pressure of millibar, and reach 700 ℃ of temperature, and under this temperature, kept about 14 hours.B.3-the preparation of composite cathode 11
With reference to example B.2, the graphite after the embedding is suspended in the xylene solution, and this solution contains the polyethylene that is dissolved in 10wt% wherein.From thus obtained mixture, make solvent slowly evaporate (solvent-pouring procedure) with obtain black, mucous membrane slightly, these adhesive films are broken into very little thin slice and by converting the negative electrode 11 of sintering after the pressure that adopts 1400MPa to.B.4-the example example that is used for electrolytical polymer manufacture B.4.1
Can adopt commercially available polyethylene glycol with molecular weight of from 200 to 1000.Example B.4.2
In order to prepare polymer, can adopt commercially available polymer, for example Merlon or quite thing.Example is (synthesizing of polyethylene glycol-dimethyl polysiloxane copolymer) B.4.3-
The dimethyldichlorosilane aliquots of about 3 gram amount of reagent are put into the PEG400 reaction of toluene and 50mol%.Reaction is 10 hours in nitrogen.Acquisition has the transparent polymer of high viscosity.With about 120 ℃ temperature under vacuum condition (10 -3Bar) remove after the residue of toluene and dimethyldichlorosilane, obtain thick liquid polymers, in appearance the spitting image of honey.The analysis showed that synthetic thus material is the copolymer with poly(ethylene oxide) and dimethyl silicone polymer block.Example is (synthesizing of the dianhydride monomer of ethylidene-diaminourea tetraacethyl (ethylene-diaminotetra-acetateacid)) B.4.4-
Ethylidene-diaminourea tetraacethyl of about 3g is placed in the toluene and acetic anhydride, and wherein above-mentioned reaction is to carry out existing under a small amount of pyridine condition.After about two hours backflow, at first filter out the white depositions of the acid anhydrides of ethylidene-diaminourea tetraacethyl, in the inert nitrogen atmosphere of strictness, clean then with toluene.Then with about one day of thus obtained white solid vacuumize.The analysis showed that product is the acid anhydrides of pure ethylidene-diaminourea tetraacethyl.Example is (copolymer synthetic with ethylidene-diaminourea tetraacethyl-polyethylene glycol block) B.4.5-
Make aliquot reaction in 1: 1 of the polyethylene glycol of the acid anhydrides of ethylidene-diaminourea tetraacethyl and molecular weight 400-800.B.5-the preparation example of δ magnesium chloride
One gram magnesium metal is incorporated in the flask of 250ml in the inert argon atmosphere of strictness.Preparing this flask in backflow skirt and the vacuum cock argon gas drying baker with having.Utilize the n-chlorobutane that skirt will about 100ml to add in the magnesium.The boiling point of thus obtained mixture at chlorobutane under flowing, argon gas reacted about 8 hours.After two hours reaction, obtain to have the gray solid of powdery appearance.After vacuumize six hours, obtain white powder.
The analysis showed that this is the magnesium chloride of δ form.B.6-the example of magnesium base polymer electrolyte preparation (polymer dielectric polyethylene glycol/(MgCl B.6.1- 2) x) preparation
Magnesium salts is dissolved in the ethyl acetate in advance.In identical solvent, prepare polyglycol solution individually.Thus obtained two kinds of solution mix.Heating is after about 1 hour, by it is carried out vacuum (10 under refluxing -3Mbar) handling and be heated to about 100 ℃ removes and to desolvate.Subsequently under high vacuum condition (10 -6Mbar) any residual solvent that will be left was removed about 2 days.Example is (synthesizing of electrolysis (electrolitic) polymer poly ethylene glycol (polyethileneglycol)-polymethyl siloxane (poymethil siloxane)) B.6.2-
A certain amount of polymer poly ethylene glycol-polymethyl siloxane is dissolved in the complete anhydrous ethanol.Individually, the solution of preparation δ magnesium chloride in identical solution.Then two kinds of solution that obtained are mixed.Subsequently solvent is removed with 80 ℃ to 100 ° temperature in a vacuum.Example is B.6.3-by the synthetic of poly-ethylidene-diaminourea four-acetate-polyethers (polyetheal) electrolysis polymerization thing that copolymer obtained of mixing with magnesium salts)
Poly-ethylidene-diaminourea four-acetate-the copolyether that is synthesized directly mixes with magnesium salts under the fusion temperature of copolymer.Example is (polymer based with polyethylene glycol or poly(ethylene oxide) and δ magnesium chloride is electrolytical directly synthetic, does not promptly have solvent) B.6.4-
The polyether polymer of various molecular weight (200 to 200,000) is directly used δ-MgCl 2Handle.Make thus obtained heterogeneous system homogenize so that salt dissolving fully in polymer by heating and lasting the stirring.B.6.5-(polymer based with polyethylene glycol or poly(ethylene oxide) and δ magnesium chloride is electrolytical directly synthetic, does not promptly use solvent, uses P for example 2O 5Acidifying)
B.6.4 the polymer dielectric that is obtained according to above-mentioned example is with the P of 8wt% 2O 5Handle.Obtain polymer dielectric and make P by stirring 2O 5All the dissolving required time is about 4 hours.P 2O 5Interpolation improved the viscosity of polymer.B.7-the example of the preparation of the polymer dielectric 12 that strengthens with glass fibre
The liquid polymers electrolyte or the solid polymer electrolyte of molten condition are used for the impregnated glass fiber fabric.By this way, obtain the polymer dielectric thin layer, it strengthens with glass fibre.The example of the preproduction that C-produced (prototype)
The task of finishing setting and the preproduction of purpose are carried out actual test.
Particularly, in first kind of situation (single element button cell) with polymer dielectric of strengthening with porous filter paper, after two kinds of compounds heated in advance, the anode disc (anode 10) that will be made by sintering metal magnesium and have the 8mm diameter was mutually stacked with the film of the polymer dielectric PEG400 that strengthens with the paper disc with same diameter.Place composite cathode films (negative electrode 11) on the top of polymer dielectric film, this composite cathode films has according to basis previous example preparation, dried the insert material that is constituted subsequently by metal oxide in the liquid suspension and graphite.Thus obtained element is contained in the system that is made of two collectors 13.The a bit of time after assembling, this preproduction has shown about 0.8 voltage.In about 5-6 hour, the voltage increases of battery preproduction is up to about 1.8V.Recharging several times with the constant current between 5 to the 150 μ A, the threshold voltage of preproduction is between 2 to 3V.After discharge, voltage is got back to 1.8V.
In second kind of situation (the single element button cell of the polymer dielectric of strengthening with glass fibre), according to preparing anode 10 and negative electrode 11 with first kind of identical operation of preproduction.Under half situation, as the reinforcement material of polymer dielectric 12, employing thickness is glass fibre O.02mm.Those of the performance of this preproduction and first preproduction are identical, but invertibity significantly improves.
(has the P of using in the third situation 2O 5The single element button cell of acidifying and the polymer dielectric strengthened with glass fibre) in, prepares anode 10 and negative electrode 11 with the operation identical with first preproduction.Pass through P 2O 5The acidifying of the polymer dielectric 12 that carries out can obtain the voltage of about 2.2V and excellent invertibity, high specific energy density and considerable charging capacity.
In the example that provides from above, clearly demonstrate the advantage that battery product obtained that magnesium is used to realize the object of the invention.In addition, compare with lithium, very light element magnesium presents better processability energy, good reactivity and the characteristics of oxide recovery voltage.The possibility that magnesium can exchange two electronics can reach 100% efficient, and compares with lithium with identical volume, and magnesium can reach and improve 80% aspect charging, improves 45% aspect energy.
In fact, the system of developing according to technology described herein can obtain excellent technical performance, and has an advantage that reduces production costs, and, reach total reduction of environmental impact in view of composition material all is that medical treatment and Clinical Application free of contamination and by magnesium show that it is safe element.
Under the situation of the scope that does not break away from the invention thought, can carry out different variations and modification to the present invention who imagines thus, for a person skilled in the art, it is possible that once (non-chargeable) that reach the object of the invention and secondary cell (chargeable) are made amendment, and what all modifications and improvement were derived from this area knows putting into practice and the natural evolvement of state of the art of the general knowledge and the industry altogether.

Claims (84)

1. once (non-chargeable) and secondary (chargeable) battery, this type battery comprises at least one anode, at least one negative electrode, is arranged at least a electrolyte and collector between anode and the negative electrode, and described battery characteristics is that anode contains magnesium at least.
2. according to the battery of claim 1, it is characterized in that negative electrode also contains magnesium.
3. according to the battery of claim 1, it is characterized in that electrolyte also contains magnesium.
4. according to the battery of claim 1, wherein anode comprises magnesium Mg that optionally combine with magnesium metal, various oxidation state N+ (0≤n≤2)
5. according to the battery of claim 4, wherein anode comprises the magnesium with the magnesium metal form.
6. according to the battery of claim 5, wherein magnesium metal is a lamination.
7. according to the battery of claim 5, wherein magnesium metal is a sintering.
8. according to the battery of claim 4, wherein anode is included in the magnesium on the high organic or inorganic material substrate of conducting electricity.
9. battery according to Claim 8, wherein the inorganic substrate material of high conduction is to select from the group that is made of metal, oxide, alloy or its fabric.
10. battery according to Claim 8, wherein inorganic or organic backing material of high conduction is selected from carbon fiber, carbon fibre fabric, graphite, graphite-base composite material.
11. according to the battery of claim 4, wherein anode comprises the magnesium in the organic or inorganic material that embeds or be embedded in high conductivity, above-mentioned organic or inorganic material embeds or imbeds magnesium crystal grain or the magnesium monocrystalline that has reduced size in their matrix.
12. according to the battery of claim 11, wherein said embedding or embedding inorganic material are to select from the phosphate of transition metal or phosphide, oxide, sulfide, alkali metal, alkaline-earth metal and nonmetallic compound.
13. according to the battery of claim 11, wherein embedding or embedding organic material have the carbon back plinth of highly crystalline or irregular structure.
14. according to the battery of claim 11, wherein embedding or embedding organic material are carbon-based polymers.
15. according to the battery of claim 4 to 14, the wherein anode oxidant oxidation of from oxygen, hydrogen peroxide or organic peroxide, selecting.
16. according to the battery of claim 4 to 15, wherein anode is stablized by using the alkoxide of selecting from four alkoxytitaniums, tetraalkoxysilane, tri-alkoxy aluminium, four zirconium alkoxides or dialkoxy magnesium to handle.
17. according to the battery of claim 2, wherein negative electrode comprises the magnesium material of 2+ oxidation state.
18. according to the battery of claim 17, wherein negative electrode is included in the magnesium on the high organic or inorganic material substrate of conducting electricity.
19. according to the battery of claim 18, wherein the inorganic substrate material of high conduction is from by selecting metal, oxide, alloy or its fabric.
20. according to the battery of claim 18, wherein inorganic or organic backing material of high conduction is selected from carbon fiber, carbon fibre fabric, graphite, graphite-base composite material.
21. according to the battery of claim 17, wherein negative electrode is included in the magnesium in the organic or inorganic material that embeds or imbed magnesium.
22., wherein embed or the embedding inorganic material is to select phosphate, phosphide, oxide or sulfide, alkali metal, alkaline-earth metal and the nonmetallic compound from transition metal according to the battery of claim 21.
23. according to the battery of claim 21, wherein inorganic the or organic material of embedding or embedding has the carbon back plinth of highly crystalline or irregular structure.
24. according to the battery of claim 21, wherein embedding or embedding organic material are carbon-based polymers.
25. according to the battery of claim 17 to 24, wherein negative electrode is to use the oxidant oxidation of selecting from oxygen, hydrogen peroxide or organic peroxide in position.
26. according to the battery of claim 17 to 24, the wherein negative electrode electrochemical active material preparation of the oxidant partial oxidation of from oxygen, hydrogen peroxide or organic peroxide, selecting.
27. according to the battery of claim 3, wherein electrolyte is included in any ionic substance of the magnesium in the solvent, above-mentioned solvent can produce the electrolyte with good ionic conductivity and can dissolve described ionic substance.
28. according to the battery of claim 27, wherein electrolyte comprises magnesium salts with the lattice energy that is lower than 500kcal/mol or the complex as the ionic substance of magnesium.
29. according to the battery of claim 27, wherein electrolyte comprises that magnesium salts or general formula as the ionic substance of magnesium are Mg (R) yX 2-yThe complex of (0≤y≤2), R are from by having C 1-C 7Select in the group that the alkyl of chain constitutes, X is from halide, ClO 4, (CF 3) 1+xSO 3-x(0≤x≤2), SCN -, PO 4 3-, the δ form chloride in select.
30. according to the battery of claim 27, wherein solvent is any fluent material that the coordination and the having of magnesium salts or complex of dissociating contain the polar group of O, N, S, C.
31. according to the battery of claim 30, wherein solvent is selected from the group that is made of ether, alcohol, glycol, ester.
32. according to the battery of claim 30, wherein solvent is to select from the group of amine and acid amides formation.
33. according to the battery of claim 30, wherein solvent is to select from the group that thioether, mercaptan, thioesters constitute.
34. according to the battery of claim 30, wherein solvent is to select from the group that alkyl carbonate, thiocarbonic acid Arrcostab constitute.
35. battery according to claim 27, wherein polymer solvent is from by selecting the polymer with different molecular weight of polyoxyalkylene, PAG, Merlon, poly-alkylsiloxane, poly-diaminourea tetraacethyl second diester or their derivative and/or the group that copolymer constitutes, and wherein the atom of one or more in chain is replaced by one or more hetero-atoms of selecting from oxygen, nitrogen, silicon, phosphorus.
36. according to the battery of claim 27, wherein polymer solvent is to select from the group that polymer or the functionalized polyphosphazene polymer of copolymer with claim 35 constitute.
37. according to the battery of claim 35, the polyoxyalkylene that wherein has a different molecular weight from polymethylene oxide, poly(ethylene oxide), PPOX with and copolymer select.
38. according to the battery of claim 35, the PAG that wherein has different molecular weight is polymethylene glycols, polyethylene glycol, polypropylene glycol, its copolymer and their fluorinated derivatives.
39. according to the battery of claim 35, the Merlon that wherein has different molecular weight is selected from polymerized thylene carbonate methyl ester, polymerized thylene carbonate ethyl ester and poly (propylene carbonate) and copolymer thereof.
40. according to the battery of claim 35, the poly-alkylsiloxane that wherein has different molecular weight is selected from polymethyl siloxane, poly-ethylsiloxane and poly-propyl-siloxane and copolymer thereof.
41. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between polyoxyalkylene and PAG.
42. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between polyoxyalkylene and Merlon.
43. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between polyoxyalkylene and poly-alkylsiloxane.
44. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between polyoxyalkylene and poly-diaminourea tetraacethyl second diester.
45. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between PAG and Merlon.
46. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between PAG and poly-alkylsiloxane.
47. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between PAG and poly-diaminourea tetraacethyl second diester.
48. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between Merlon and poly-alkylsiloxane.
49. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between Merlon and poly-diaminourea tetraacethyl second diester.
50. according to the battery of claim 35, the copolymer that wherein has different molecular weight is between poly-alkylsiloxane and poly-diaminourea tetraacethyl second diester.
51., wherein have the polymer of different molecular weight and/or the group functionalization that copolymer is used combination or coordination magnesium salts or complex according to the battery of any claim 35-50.
52. according to the battery of any claim 35-51, wherein electrolyte is acidifying.
53. according to the battery of claim 52, wherein electrolyte is with having phosphorus, polyphosphate, P 2O 5Or the compound acidifying on ortho-phosphoric basis.
54. according to the battery of any claim 35-51, wherein electrolyte alkalizes.
55. according to the battery of claim 54, wherein electrolyte is with the compound of nitrogen base for example amine and ammonia alkaliization, or with the alkaline derivant alkalization of sulphur or phosphorus.
56. according to the battery of claim 1, wherein collector is to have the metal of the resistance that is no more than 10ohmm or nonmetal.
57. according to the battery of claim 56, wherein metal collector is to select from the group that the fabric of being made by metal, oxide, alloy or same material constitutes.
58. according to the battery of claim 56, wherein nonmetal collector is made by carbon or carbon fibre fabric.
59., also comprise dividing plate inorganic by ion permeability or that organic material constitutes with high insulation characterisitic according to the battery of claim 1 or 2 or 3.
60. according to the battery of claim 59, its median septum is selected from cellulose, glass fabric and organic barrier film.
61. according to the battery of claim 59 and 60, its median septum is present in its lip-deep any polar group through handling so that remove.
62. δ-magnesium chloride is as the purposes that is used for the ionic substance of electrolytical magnesium.
63. Grignard magnesium is used for the purposes of the material of electrolytical magnesium cation as generation.
64. a method that is used for according to the battery manufacturing of claim 1, it is characterized in that it may further comprise the steps :-anode preparation, this anode are characterised in that it comprises the magnesium Mg of the various oxidation state that selectively are combined with metal M g N+(0≤n≤2), described anode has the basis of magnesium metal of as original or the basis of the magnesium on the inorganic or organic material substrate of high conduction, perhaps on the magnesium basis of embedding that is used for magnesium or the inorganic or organic material imbedded, and optionally-the negative electrode preparation, this negative electrode is characterised in that it comprises the substrate of the inorganic or organic material with high conductivity or is used for embedding or the material of the magnesium of the 2+ oxidation state of the inorganic or organic material of embedding magnesium, and/or-preparation of electrolyte, this electrolyte is characterised in that it is included in any ionic substance of the magnesium in the solvent, and above-mentioned solvent can produce to have good ionic conductivity electrolyte and can dissolve described ionic substance.
65. prepare the method for battery according to claim 64, wherein anode is made by lamination magnesium.
66. prepare the method for battery according to claim 64, wherein anode is made by sintering magnesium.
67. prepare the method for battery according to claim 64, wherein have anode on the magnesium basis on the substrate and utilize chemistry or hot vapour deposition, electrolytic deposition or the electrochemical deposition of magnesium to prepare on by the inorganic material of in the fabric of making by metal, oxide, alloy or same material, selecting.
68. prepare the method for battery according to claim 64, wherein have anode on the magnesium basis on the substrate and utilize chemistry or hot vapour deposition, electrolytic deposition or the electrochemical deposition of magnesium to prepare on by the organic or inorganic material of in by carbon fiber, carbon fibre fabric, graphite or graphite-base composite material, selecting.
69. prepare the method for battery according to claim 64, wherein, have embed or embedded material in the anode on magnesium basis prepare by following steps: (i) will embed or the mixture homogenizing of embedded material and make granular, grinding is up to structural disorder completely, magnesium carbonate or magnesium oxide brought up to keep between 1 to 3 hour under about 100 ℃ to 400 ℃ temperature, (ii) in inert gas, reach the temperature between 800 ℃ to 1200 ℃ then, (iii) under vacuum condition, kept 1 to 5 day at last with this temperature.
70. prepare the method for battery according to claim 64, wherein, anode with the magnesium basis in embedding or embedded material prepares by solvent-cast: solvent is benzene, toluene, N-N dimethylacetylamide, dimethyl formamide or oxolane for example, the selected embedding that this solvent has comprised polymer selected from polyethylene, polyvinyl chloride, polyacrylamide, polyacrylonitrile or similar polymer and used the magnesium homogenizing fully in advance in the mode of homogenizing or the mixture of embedded material.
71., wherein magnesium is prepared to have by plasma spraying or the mode in selected embedding or the embedded material of being splashed to and is being used for embedding or the anode on the magnesium basis of the embedding of embedding magnesium or embedded material according to the preparation method of the battery of claim 64.
72. according to the preparation method of the battery of any claim 65-71, wherein anode uses the oxidant of selecting from oxygen, hydrogen peroxide, organic peroxide to come oxidation.
73. according to the battery preparation method of any claim 65-72, wherein anode is handled and stabilisation by use the alkoxide of selecting from four alkoxytitaniums, tetraalkoxysilane, tri-alkoxy aluminium, four zirconium alkoxides or dialkoxy magnesium.
74. preparation method according to the battery of claim 64, wherein, having negative electrode on the magnesium basis on the substrate utilizes chemistry or hot vapour deposition, electrolytic deposition or the electrochemical deposition of magnesium to prepare on by the inorganic material of selecting in the fabric of being made by metal, oxide, alloy or same material.
75. preparation method according to the battery of claim 64, wherein, have negative electrode on the magnesium basis on the substrate by the organic or inorganic material of in by carbon fiber, carbon fibre fabric, graphite or graphite-base composite material, selecting on chemistry or hot vapour deposition, electrolytic deposition or electrochemical deposition by magnesium prepare.
76. prepare the method for battery according to claim 64, wherein, have embed or embedded material in the negative electrode on magnesium basis prepare by following steps: (i) will embed or the mixture homogenizing of embedded material and make granular, grinding is up to structural disorder completely, magnesium carbonate or magnesium oxide brought up to keep between 1 to 3 hour under about 100 ℃ to 400 ℃ temperature, (ii) in inert gas, reach the temperature between 800 ℃ to 1200 ℃ then, (iii) under vacuum condition, kept 1 to 5 day at last with this temperature.
77. prepare the method for battery according to claim 64, wherein, negative electrode with the magnesium basis in embedding or embedded material prepares by solvent-cast: solvent is benzene, toluene, N-N dimethylacetylamide, dimethyl formamide or oxolane for example, this solvent comprises in the mode of homogenizing, from polyethylene, polyvinyl chloride, polyacrylamide, polyacrylonitrile or similar polymer selected polymer and in advance fully and the magnesium homogenizing selected embedding or the mixture of embedded material.
78., wherein magnesium is prepared to have by plasma spraying or the mode in selected embedding or the embedded material of being splashed to and is being used for embedding or the negative electrode on the magnesium basis of the embedding of embedding magnesium or embedded material according to the preparation method of the battery of claim 64.
79. according to the battery preparation method of any claim 74-78, wherein the magnesium of negative electrode is to use the oxidant of selecting from oxygen, hydrogen peroxide, organic peroxide to come oxidation in position.
80. according to the battery preparation method of any claim 74-78, wherein negative electrode be by use the oxidant partial oxidation from oxygen, hydrogen peroxide or organic peroxide, selected in advance the electrochemical active material preparation.
81. according to the battery preparation method of claim 64, wherein electrolyte by with magnesium salts or complex in liquid flux or molten polymer directly dissolving make.
82. according to the battery preparation method of claim 64, wherein electrolyte is to prepare by the solvent-casting with cosolvent magnesium salts or complex polymer.
83. according to the battery preparation method of claim 64, wherein electrolyte is by by magnesium salts or complex being dissolved in one or more monomers and polymerization reaction by subsequently prepares.
84. the method for magnesium cell is set according to above-mentioned any claim, wherein, with at least one anode, at least one negative electrode, at least a electrolyte, collector and optionally insulating barrier arrange in the mode that contacts with each other, will be arranged on room temperature in the electrolytical temperature between anode and the negative electrode between about 150 ℃.
CN00811017A 1999-07-29 2000-07-27 Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries Pending CN1365524A (en)

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