EP1205003A1 - Batteries primaires (non rechargeables) et secondaires (rechargeables) a base de magnesium - Google Patents

Batteries primaires (non rechargeables) et secondaires (rechargeables) a base de magnesium

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Publication number
EP1205003A1
EP1205003A1 EP00949410A EP00949410A EP1205003A1 EP 1205003 A1 EP1205003 A1 EP 1205003A1 EP 00949410 A EP00949410 A EP 00949410A EP 00949410 A EP00949410 A EP 00949410A EP 1205003 A1 EP1205003 A1 EP 1205003A1
Authority
EP
European Patent Office
Prior art keywords
magnesium
batteries according
chosen
anode
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP00949410A
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German (de)
English (en)
Inventor
Vito Di Noto
Maurizio Fauri
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Universita degli Studi di Padova
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Universita degli Studi di Padova
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Publication date
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Publication of EP1205003A1 publication Critical patent/EP1205003A1/fr
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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

Definitions

  • the present invention regards primary (i.e., non-rechargeable) and secondary (i.e., rechargeable) batteries in which at least the anode contains magnesium, and optionally also the electrolyte and cathode contain magnesium, as well as methods for making said batteries.
  • Ni-Cd nickel-cadmium
  • Ni-MH nickel-metal hydride
  • Li-ion lithium-ion
  • a further advantage of the batteries produced using these new technologies is the absence of cadmium, which, since it is a heavy metal, has quite a serious detrimental impact on the environment.
  • lithium-ion batteries are, in energy terms, still the most promising ones, but their production cost is relatively high. However, if the cost per cycle of these systems is considered, it may be noted that they become competitive as compared to the more economical nickel-cadmium batteries. On the basis of the technical characteristics, environmental impact, and cost per cycle, a considerable growth is expected for the lithium-ion system on the world market. On the other hand, nickel-metal hydride batteries are likely to have a more modest growth, whilst it is estimated that nickel-cadmium batteries are unlikely to maintain their current production levels. The international scenario witnesses a concentration of the majority of production in the sector of lithium-ion batteries, which are an evolution of lithium systems.
  • Primary lithium batteries which are widely used in calculators, clocks and watches, cardiac pacemakers, etc., are made with a lithium anode and a cathode made of transition metal oxide (e.g., MnO 2 ). Thanks to the high electrochemical potential supplied by the lithium anode, these batteries provide high cell voltages, and consequently also high energy densities.
  • transition metal oxide e.g., MnO 2
  • Li-polymer Li-polymer
  • This method which exploits metallic lithium for making the anode, presents, however, serious difficulties in terms of reversibility.
  • dendritic deposits are formed on the surface of the anode, which are the result of the reaction of the lithium with the organic polymeric electrolyte and are responsible for the fast deterioration of this type of battery.
  • the number of cycles obtained using systems of this type thus amounts to just a few dozens or hundreds.
  • the reactivity of the lithium in regard to the polymeric electrolyte may also become a cause of serious problems of safety in the operating phase of the battery itself.
  • the next step in the development of these devices was that of the introduction of the so-called lithium-ion or rocking-chair technology, which is based on solutions that tend to solve the problem of formation of dendrites on the lithium anode by replacing the lithium with composite materials capable of intercalating Li + in their structure via insertion reactions.
  • Certain carbons with a regular structure (turbostatic or graphitizable) or with a highly crystalline structure (natural or synthetic graphites) can in fact intercalate the Li + ion in their layers in a reversible manner, thus giving rise to complexes of the Li x C 6 type.
  • lithium-ion batteries are provided with an intercalated titanium disulphide- based (Li x TiS 2 ) anode.
  • the latter has a behaviour similar to that of a carbon electrode.
  • the cathode is instead made using oxides of lithium and transition metals, among which the most widely used up to now is lithium cobaltate (LiCoO 2 ), which, for reasons of cost, availability, and toxicity, tends to be replaced by lithium nickelate (LiNiO 2 ) or lithium manganate (LiMnO ).
  • LiCoO 2 lithium cobaltate
  • LiNiO 2 lithium nickelate
  • LiMnO lithium manganate
  • the electrolyte consists of an organic polymer with solvent properties, which is rendered ionic-conductive by being doped with special lithium salts (e.g., LiPF 6 , LiCIO l etc.).
  • lithium salts e.g., LiPF 6 , LiCIO l etc.
  • a number of researchers, such as Farrington and Cherng have sought to develop magnesium-based polymeric electrolyte systems for the possible development of magnesium batteries, with, however, somewhat meagre results.
  • the polymeric electrolytes obtained had, in fact, conductivities which, at room temperature, were too high (i.e., with conductivity lower than 10 "6 siemens/cm) for the production of primary and/or secondary batteries.
  • the main task of the present invention is to succeed in developing primary (non- rechargeable) batteries and/or secondary (rechargeable) batteries that overcome the problems of reactivity and reversibility typical of lithium-based batteries.
  • a consequent primary purpose is to develop batteries with high-level technical characteristics allied to a reduction in production costs.
  • Another important purpose is to develop miniaturized and lightweight batteries. Yet a further purpose is to develop batteries suitable for use in portable digital electronic equipment. A further important purpose is to arrive at the almost total elimination of environmental impact. Summary of the invention
  • primary (non-rechargeable) and secondary (rechargeable) batteries that form the object of the present invention, of the type comprising at least one anode, at least one cathode, at least one electrolyte, and current collectors, said batteries being characterized in that at least the anode and optionally also the electrolyte contain magnesium. Also the cathode of the batteries that form the object of the present invention may optionally incorporate magnesium.
  • the anode included in the present invention is characterized in that it uses magnesium in the various states of oxidation Mg n+ ⁇ 0 ⁇ n ⁇ 2) , optionally combined with metallic magnesium, and the electrolyte, possibly containing magnesium, is characterized in that it comprises any ionic species of magnesium in solvents, including polymeric solvents, that are capable of producing electrolytes having good ionic conductivity and capable of solvation of the said ionic species.
  • the cathode contains magnesium
  • this is a species of magnesium in the state of oxidation 2 + and may have a substrate of highly conductive inorganic or WO 01/09972 PCTVEPOO/07221
  • organic materials or else may be intercalated or embedded in highly conductive inorganic or organic materials.
  • Forming a further object of the present invention are methods for the production of said primary and secondary batteries of the type comprising at least one anode, at least one cathode, at least one electrolyte set between anode and cathode, and electrical-connection collectors, said batteries being characterized in that at least the anode and optionally also the electrolyte and the cathode contain magnesium.
  • Yet another object of the invention is the use of salts of magnesium chloride in the ⁇ form for the preparation of the electrolyte, and the use of Grignard magnesium as species generating magnesium cations for the electrolyte.
  • Figure 1 is a schematic sectional view of a battery built according to the present invention, where:
  • the batteries that form the object of the present invention may be primary and secondary batteries of the type comprising at least one anode, at least one cathode, at least one electrolyte set between anode and cathode, and current collectors, said batteries being characterized in that at least the anode and optionally also the electrolyte contain magnesium.
  • the cathode may optionally incorporate magnesium.
  • the electrolyte or the cathode do not contain magnesium, they are a conventional electrolyte or cathode, and hence are in themselves known, and consequently will not be described further herein.
  • the primary and secondary batteries that form the object of the present invention may moreover comprise possible dielectric spacers, not illustrated in the Figure.
  • the batteries according to the present invention may be made up of: An anode 10 characterized in that it comprises magnesium in the various states of oxidation Mg n+(0 ⁇ n ⁇ 2) , optionally combined with metallic magnesium.
  • the magnesium may be included as such or may also have a substrate of highly conductive inorganic or organic materials, or else of highly conductive inorganic or organic materials that are capable of englobing, by intercalation or embedding into their own matrices, magnesium crystallites of reduced dimensions or magnesium monocrystals.
  • the anode 10 may consist of metallic magnesium as such, and in this case the magnesium may be used in laminated or sintered form.
  • the magnesium may have a substrate of highly conductive materials, these may be inorganic materials chosen from the group made up of metals, for example aluminium, copper, and other equivalent metals, or oxides, alloys, and fabrics made of the same.
  • the said highly conductive substrate materials may also be organic, and also of a polymeric type; in the latter case, they are chosen from among materials such as carbon-fibre fabrics, graphite, or even graphite-based composite materials, or other equivalent materials suitable for the purposes.
  • intercalation or embedding materials are used for the anode, this may be either organic or inorganic.
  • the intercalation or embedding materials that may be used for the purposes of the present invention are transition- metal compounds, alkaline-metal compounds, and alkaline earth-metal compounds, as well as non-metal compounds, chosen from among oxides, sulphides, phosphates or phosphides, such as tungsten oxides (W y O x ), ferric oxides (Fe y O x ), titanium sulphides (Ti y S x ), cobalt oxides (Co y O x ), nickel oxides (Ni y O x ), manganese oxide (Mn y O x ), or else other equivalent compounds, or carbon-based materials with intercalation properties and with a highly crystalline structure or an irregular structure, or equivalent materials, or else a material of a polymeric type, such as carbon-based polymers or equivalent polymers that are capable of englob
  • anode 10 may be optionally oxidized with oxidizing agents such as oxygen gas or peroxide, such as H 2 O 2 , or organic peroxides and stabilized by treatment with stabilizing agents such as alkoxides, (e.g. tetra-alkoxy titanium, tetra-alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide, or equivalent compounds).
  • oxidizing agents such as oxygen gas or peroxide, such as H 2 O 2 , or organic peroxides
  • stabilizing agents such as alkoxides, (e.g. tetra-alkoxy titanium, tetra-alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide, or equivalent compounds).
  • a cathode 11 characterized in that it contains magnesium species with state of oxidation 2 + .
  • the cathode may have a substrate of highly conductive inorganic or organic materials, including polymeric materials, or else the magnesium may be intercalated or embedded in inorganic or organic materials.
  • the materials that may be used both in the case where the magnesium has a substrate and in the case where the magnesium is intercalated or embedded are the same as the materials mentioned previously for the anode.
  • This type of cathode may be used, dispersing the active material in a porous and conductive matrix. This use affords the advantage of improving the electrochemical properties of the batteries.
  • the cathode may be optionally oxidized with the same oxidizing agents.
  • the oxidation of the cathode may be, like the anode, in situ and following on its preparation or, unlike the anode, the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to its preparation.
  • the cathode 11 does not contain magnesium, it is a conventional cathode and is in itself known; consequently, it is not further described herein.
  • the cathode contains electrochemically active materials having a base of metallic mixtures in appropriate proportions in a reduced or oxidized form.
  • materials containing transition metals may be used, such as, but not exclusively, manganese with state of oxidation ranging from to 2 + , and other equivalent metals.
  • An electrolyte 12 characterized in that it comprises any ionic species of magnesium in solvents, including polymeric solvents, capable of producing electrolytes with good ionic conductivity and capable of solvating said species.
  • the electrolyte according to the present invention comprises, as ionic species of magnesium, magnesium salts or complexes of the general formula Mg(R) y X 2-y , with 0 ⁇ y ⁇ 2, having a very low charge/volume ratio.
  • the radical R may be chosen from the group consisting, for example, of alkyls with C1-C 7 chains, whilst X may be chosen from among halides, CIO 4 , (CF 3 ) 1+x SO 3-x , with 0 ⁇ x ⁇ 2, SCN ' , PO 3" , or chlorides in ⁇ form, or other equivalents.
  • the compounds of the general formula Mg(R) y X 2-y , with 0 ⁇ y ⁇ 2, usable for doping the electrolyte may moreover be preferentially magnesium salts or magnesium complexes with lattice energy lower than 500 kcal/mol.
  • the solvents used for the electrolyte may be of various types, since the essential characteristic required is that they should possess good ionic conductivity and in any case that they should at the same time be able to solvate the magnesium salts or magnesium complexes that have been chosen. For the purpose, they may therefore be liquid solvents or solvents in the solid or viscous state.
  • liquid solvents these are chosen from among materials having polar groups which are able to co-ordinate and dissociate the ionic magnesium salts or complexes and which contain oxygen, nitrogen, sulphur and carbon.
  • solvents may therefore be chosen from among ethers, alcohols, di-alcohols, esters, amines and amides, thioethers, thioalcohols, thioesters, alkyl carbonates and alkyl thiocarbonates, or other equivalents.
  • the solvent for the electrolyte is solid or viscous
  • it may be of a polymeric type.
  • Usable for the purpose are all the polymers or copolymers of the same having different molecular weights, which are capable of solvating magnesium salts or complexes suitable for the purpose.
  • Such polymers and/or copolymers may be chosen from among polyalkylene oxides, polyalkylene glycols, polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate, or equivalent polymers or copolymers of the same macromolecular frameworks having different molecular weights, also containing, in their chains, hetero-atoms of the oxygen, nitrogen, silicon, and phosphorus types.
  • polyphosphazene polymers fu notional ized with the polymers and/or copolymers mentioned previously.
  • polyalkylene oxides the following may be mentioned: polymethylene oxide, polyethylene oxide, polypropylene oxide and others; among polyalkylene glycols, the following may be mentioned: polymethylene glycols, polyethylene glycols, polypropylene glycols and fluorinated derivatives of the same and others; among polycarbonates, the following may be mentioned: polymethylene carbonates, polyethylene carbonates, and polypropylene carbonates and others; among the polyalkyl siloxanes, the following may be mentioned: polymethyl siloxane, polyethyl siloxane, and polypropyl siloxane and others.
  • polyphosphazene polymers functionalized with polymers and/or copolymers of the polyethylene-oxide type or the like having different molecular weights.
  • the polymers and/or copolymers that may be used for the preparation of the electrolyte may moreover be functionalized with groups that bond or co-ordinate magnesium so as to improve their interaction with the salts or complexes of the latter.
  • the electrolyte For the purpose of improving the ionic conductivity of the electrolyte, this may also be optionally acidified or alkalinized according to known procedures, which, consequently, will not be described in greater detail herein.
  • the preferential acidifying agents for the electrolyte are compounds with a base of phosphorus, polyphosphates, P 2 O 5 , or equivalents of the orthophosphoric-acid type.
  • the compounds that may be used are nitrogen- based ones and, in this case, are preferentially amines or ammonia, as well as basic derivatives of sulphur and phosphorus.
  • Acidification improves the conductivity of the electrolyte, and this process is to be carried out whenever the performance of the electrolyte is not adequate for the application. This process is to be preferred in the case of stabilized electrodes. Also alkalinization improves the conductivity of the electrolyte and is carried out with the purpose of favouring the electrochemical functioning of the electrodes. This process is, however, to be preferred in the case where non-stabilized electrodes are used.
  • Spacers consisting of inorganic or organic materials which are permeable to ions and have high dielectric characteristics; these are appropriately functionalized, if necessary, in order to eliminate the polar groups that may be present on the surfaces of the fibres.
  • cellulose, glass-fibre fabrics, organic membranes, or other equivalent materials for example, cellulose, glass-fibre fabrics, organic membranes, or other equivalent materials.
  • Current collectors 13 either metallic or non-metallic, with conductive characteristics and with a resistivity of not more than 10 ohm»m for collecting the electrons and for electrical connection of the poles of the battery element.
  • metals even in the form of oxides, alloys, and fabrics made of the same, such as aluminium, copper, steel, brass, etc., or organic materials made of carbon or carbon-fibre fabrics, or similar materials.
  • the method for making the primary and/or secondary batteries according to the present invention envisages at least one of the following steps: - preparation of an anode characterized in that it comprises magnesium in the various states of oxidation Mg n+ ⁇ 0 ⁇ n ⁇ 2 optionally combined with metallic Mg, said anode having a base of metallic magnesium as such, or else of magnesium on a substrate of highly conductive inorganic or organic materials, or in inorganic or organic materials for intercalation or embedding of the magnesium; - preparation of a cathode characterized in that it comprises species of magnesium in the state of oxidation 2 + having a substrate of highly conductive inorganic or organic materials or in inorganic or organic composite materials for intercalation or embedding of the magnesium;
  • an electrolyte characterized in that it comprises any ionic species of magnesium in solvents that are capable of producing electrolytes having good ionic conductivity and of solvating said species.
  • the electrolyte may moreover optionally be reinforced with spacers as described previously.
  • the above three components are put in contact with one another, the layer of electrolyte 12 being set in between the anode 10 and the cathode 11.
  • the intimate contact between anode 10, electrolyte 12, and cathode 11 may also be obtained by exerting a slight pressure on the ensemble of components at temperatures of between room temperature and approximately 150°C.
  • anode 10 may be used: a magnesium-based anode having the characteristics already mentioned previously, (i) as such or (ii) on a substrate of highly conductive organic or inorganic materials, or (iii) intercalated or embedded in material for intercalation or embedding of magnesium.
  • the magnesium as such may be laminated starting from Grignard-grade magnesium, or may be in the form of powder of appropriate grain size, or else in the form of a ribbon of varying length, which is commercially available.
  • the magnesium may also be sintered.
  • the anode may also consist of magnesium on a substrate of highly conductive organic or inorganic materials, including polymeric materials, as described previously. This type of anode may be prepared by chemical, thermal vapour, electrolytic, or electrochemical deposition methods of magnesium species.
  • the other type of anode 10 is made with intercalation or embedding material for magnesium.
  • this anode is prepared by suspending, in a solvent such as benzene, toluene, N-N dimethyl acetamide, dimethyl formamide, or tetrahydrofuran or the like, a mixture of polyethylene or polyvinyl chloride, or polyacrylamide, or polyacrylonitrile, or some other, with intercalation material previously extended up to complete homogenization with magnesium.
  • the system is treated until complete and homogeneous distribution of the above described materials in the solvent itself is obtained.
  • the composite film with a base of intercalation or embedding material is then obtained by slow evaporation of the solvent.
  • intercalation in addition to the ones described previously, for obtaining the anode, may be based on physical methodologies, such as plasma spraying or sputtering of the magnesium into the intercalation or embedding material chosen. Whatever the type of anode, this may possibly be subsequently oxidized with oxygen gas or peroxide, such as H 2 O 2 , or organic peroxides.
  • the anode may, moreover, be subjected to a further and possible stabilization treatment.
  • stabilizing agents may be used alkoxides, such as tetra-alkoxy titanium, tetra- alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide, or other equivalent compounds.
  • the cathode 11 may be prepared either providing a substrate for the magnesium or with a composite having a base of intercalation or embedding material, adopting methodologies that are similar to the ones already described for the anode 10, and which, for this reason, will not be described further herein.
  • the intercalation materials are the same as those usable for the anode and may be, for example, but not exclusively, with a base of carbon, graphite, titanium disulphide (TiS 2 ), cobalt dioxide (CoO 2 ), nickel dioxide (NiO 2 ), manganese dioxide (MnO 2 ), or other equivalents chosen from among the ones already mentioned previously.
  • TiS 2 titanium disulphide
  • CoO 2 cobalt dioxide
  • NiO 2 nickel dioxide
  • MnO 2 manganese dioxide
  • the cathode may undergo further processes of oxidation in situ and following on its preparation, these processes having already been described previously.
  • the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to the preparation of the cathode.
  • the intercalation material is chosen from among the materials that may be used for this purpose in the anode or in the cathode, and is prepared according to the general procedure described in what follows.
  • the intercalation material is ground in a ball mill until complete structural disorder of the material is achieved. Subsequently, the material is brought into intimate contact with magnesium carbonates or magnesium oxides.
  • the mixture thus obtained, after homogenization and pelletization is brought up to a temperature of approximately 100°C to 400°C for a period of between 1 and 3 hours, and subsequently to a temperature of between 800°C and 1200°C under a inert atmosphere (for example, an argon atmosphere), and then kept at the temperature range indicated in vacuum conditions for 1 to 5 days.
  • a inert atmosphere for example, an argon atmosphere
  • the electrolyte 12 according to the present invention may be prepared using solvents, including, but not exclusively, polymeric solvents, capable of solvating any ionic species of magnesium and of producing electrolytes having good ionic conductivity.
  • the electrolyte according to the present invention comprises, as ionic species, magnesium salts or magnesium complexes of the general formula Mg(R) y X 2-y , with 0 ⁇ y ⁇ 2, having a very low charge/volume ratio.
  • the radical R may be chosen from the group consisting, for example, of alkyls with C 1 -C 7 chains, whilst X may be chosen from among halides, CIO , (CF 3 ) 1+x SO 3-x , with 0 ⁇ x ⁇ 2, SCN " , PO4 3" , or chlorides in ⁇ form.
  • the compounds of the general formula Mg(R) y X 2 . y , with 0 ⁇ y ⁇ 2, usable for doping the electrolyte, may moreover be preferentially magnesium salts or ionic complexes of magnesium with lattice energy lower than 500 kcal/mol.
  • the preparation is according to the following reaction: solvent + salt / inorganic complex -> electrolyte
  • the mode of preparation of the electrolyte 12 according to the above reaction can follow three general procedures.
  • the first regards the direct dissolution of the magnesium salt or complex in the liquid solvent or in the melted polymer (when the latter so permits).
  • the second procedure regards the dissolution of the polymer solvent and the magnesium salt or complex in a common solvent to obtain the polymeric film through slow evaporation of the solvent (solvent-casting).
  • the third procedure regards obtaining polymeric electrolytes which can have a high conductivity and which are based on polymeric electrolytes having a high degree of crosslinking.
  • the polymeric electrolyte for obvious reasons, must be prepared obtaining solutions of the monomer and of the magnesium salt or complex preliminarily, and carrying out the polymerization reaction subsequently.
  • the solvents usable for the purpose are all those already mentioned previously, and in particular, to provide an example, any liquid material having polar groups containing oxygen, nitrogen, sulphur, and carbon, which co-ordinate and WO 01/09972 PCTYEPOO/07221
  • ionic magnesium salts or complexes such as ethers, alcohols, di- alcohols, esters, amines and amides, thioethers, thioalcohols, thioesters, alkyl carbonates and alkyl thiocarbonates, or else polymers and/or copolymers with different molecular weights, polyalkylene oxides, polyalkylene glycols, polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate, derivatives thereof in which one or more atoms in the chain are substituted with one or more hetero-atoms chosen from among oxygen, nitrogen, silicon, and phosphorus and polyphosphazene polymers functionalized with the polymers or copolymers mentioned previously.
  • magnesium salts or complexes that may be used for the purposes of the present invention, particularly advantageous is ⁇ -MgCI 2 , which, since it has a very low lattice energy, i.e., close to 0 kcal/mol., may be solubilized in organic solvents that are capable of co-ordinating the magnesium, and Grignard magnesium as species generating cations for the electrolyte.
  • the electrolyte obtained according to one of the processes described above may also be acidified or alkalinized with the use of procedures and means known for the purpose.
  • the electrolyte is acidified, it may be preferential for the purposes of the present invention to add appropriate amounts of phosphorus- based compounds, such as P 2 Os, or other equivalents, under stirring and up to complete dissolution.
  • phosphorus- based compounds such as P 2 Os, or other equivalents
  • a similar procedure is followed in the case where the electrolyte is alkalinized with nitrogen-based compounds or with basic derivatives of sulphur and phosphorus.
  • A.5 - Preparation of the dielectric spacers The dielectric spacers may be made of any ion-permeable insulating materials having good characteristics of insulating strength and dielectric constant.
  • the anode 10 is prepared starting from metallic magnesium which is finely ground and sintered applying a pressure of 1400 MPa. In this way, after applying the pressure for approximately 10 minutes, a metallic film is obtained having the desired thickness.
  • the intercalated graphite referred to in Example B.2, is suspended in a xylene solution containing, dissolved therein, 10 wt% of polyethylene. From the mixture thus obtained the solvent is made to evaporate slowly (solvent-casting method) to obtain a black, slightly gummy film, which is broken up into tiny flakes and subsequently converted into a sintered cathode 11 by application of a pressure of
  • polyethylene glycols with molecular weights from 200 up to 1000 may be used.
  • polymers for the preparation of the polymer, it is possible to use commercially available polymers, such as polycarbonates, or equivalent ones.
  • Example B.4.4 (Synthesis of the di-anhydride monomer of ethylene-diaminotetra- acetate acid) Approximately 3 grams of ethylene-diaminotetra-acetate acid are made to react in toluene with acetic anhydride in the presence of small amounts of pyridine. After approximately two hours of refluxing, the white precipitate of the anhydride of the ethylene-diaminotetra-acetate acid is first filtered and then washed with toluene in a rigorously inert nitrogen atmosphere. The white solid thus obtained is subsequently vacuum-dried for approximately one day. The analyses have shown that the product is the anhydride of pure ethylene-diaminotetra-acetate acid.
  • the anhydride of the ethylene-diaminotetra-acetate acid is made to a react with a 1 :1 aliquot of polyethylene glycol having a molecular weight of from 400 to 800.
  • Example B.6.1 Preparation of the polymeric electrolyte polyethylene glycol/(MgCI 2 ) x )
  • the magnesium salt is previously dissolved in ethyl acetate.
  • a polyethylene-glycol solution is prepared separately. The two solutions thus obtained are mixed together. After heating for approximately one hour under reflux, the solvent is removed by subjecting it to a vacuum (10 "3 mbar) and to heating to a temperature of approximately 100°C. Any traces of solvents that are left are subsequently eliminated under high-vacuum conditions (10 "6 mbar) for approximately two days.
  • Example B.6.2 (Synthesis of electrolitic polymer polyethilene glycol- poymethilsiloxane) An amount of polymer polyethilene glycol-poymethilsiloxane is dissolved in ethyl alcohol perfectly anhydrous. Separately in the same solvent is prepared a solution of ⁇ magnesium chloride. Then the two solutions obtained are mixed together . the solvent is subsequently removed under vacuum (10 "3 mbar)at temperatures from 80° to 100°C.
  • Example B.6.3 Synthesis of the electrolytic polymer obtained by doping the polyethylene-diaminotetra-acetate-polyethereal copolymer with magnesium salts
  • the synthesized polyethylene-diaminotetra-acetate-polyethereal copolymer is doped directly with magnesium salts at the melting temperature of the copolymer.
  • Example B.6.4 Direct synthesis, i.e., without solvents, of polymeric electrolytes with a base of polyethylene glycols or polyethylene oxides and ⁇ magnesium chloride)
  • Example B.6.5. - Direct synthesis, i.e., without solvents, of polymeric electrolytes having a base of polyethylene glycols or polyethylene oxides and ⁇ magnesium chloride, acidified with P 2 Os
  • the polymeric electrolyte obtained according to the foregoing Example B.6.4 is treated with 8 wt% of P 2 O 5 .
  • the time required for obtaining a polymeric electrolyte by means of stirring and complete dissolution of the P 2 O 5 is approximately 4 hours.
  • the addition of P 2 Os increases the viscosity of the polymer.
  • B.7 - Example of preparation of the polymeric electrolyte 12 reinforced with glass fibres
  • liquid polymeric electrolyte or solid polymeric electrolyte in the molten state is used for impregnating a glass-fibre fabric. In this way, a thin layer of polymeric electrolyte is obtained which is reinforced with glass fibres.
  • anodic disk made of sintered metallic magnesium and having a diameter of 8 mm was interfaced with a film of polymeric electrolyte PEG 400 reinforced with a paper disk having the same diameter, after prior heating of the two compounds.
  • a composite cathodic film (cathode 11 ) having a base of intercalation material consisting of metal oxides with graphite in liquid suspension subsequently dried, prepared according to the previous examples. The element thus obtained was housed on a system consisting of two current collectors 13.
  • this prototype revealed a voltage of approximately 0.8 V. Within approximately 5-6 hours, the voltage of the battery prototype increased until it reached approximately 1.8 V. After a few rechargings were carried out at a constant current of between 5 and 150 ⁇ A, the prototype presented a threshold voltage between 2 and 3 V. After discharge, the voltage returned to 1.8 V.
  • the anode 10 and cathode 11 were prepared according to the same procedures as for the first prototype.
  • glass fibre having a thickness of 0.02 mm was used as reinforcement for the polymeric electrolyte 12.
  • the characteristics of this prototype were the same as for those of the first prototype, but the reversibility was considerably superior.
  • the anode 10 and cathode 11 were prepared following the same procedures as for the first prototype. Acidification of the polymeric electrolyte 12 by means of P 2 O 5 enabled a voltage of approximately 2.2 V to be obtained, together with excellent reversibility, a high specific energy density, and a considerable charge capacity.
  • magnesium which is a very light element, presents characteristics of better workability, together with a good reactivity and oxide-reducing voltage.
  • the possibility for magnesium to exchange two electrons may enable an efficiency of 100%, and, given the same volumes, magnesium may reach 80% more in terms of charge and 45% more in terms of energy as compared to lithium.
  • the systems developed according to the technology described herein enable, in fact, excellent technical performance to be achieved, allied to the advantage of a reduction in production costs and to the practically total absence of environmental impact, given that the component materials are all non-polluting and that magnesium is a safe element as demonstrated by its medical and clinical uses.
  • the invention thus conceived may undergo numerous modifications and variations, and, without departing from the scope of the inventive idea of the present invention, it is possible for a person skilled in the branch to make, to the primary (non-rechargeable) and secondary (rechargeable) batteries that form the object of the present invention, all the modifications and improvements resulting from normal technical know-how and experience in the sector, as well as from the natural evolution of the state of the art.

Abstract

L'invention concerne des batteries qui comprennent au moins une anode, au moins une cathode et au moins un électrolyte, ainsi que des collecteurs de courant. La ou les anodes considérées sont à base de magnésium. Eventuellement la ou les cathodes et le ou les électrolytes sont aussi à base de magnésium. Pour assembler les batteries, il est nécessaire de préparer les éléments constitutifs individuels et d'intercaler une mince couche d'électrolyte entre la ou les anodes et la ou les cathodes à base de magnésium.
EP00949410A 1999-07-29 2000-07-27 Batteries primaires (non rechargeables) et secondaires (rechargeables) a base de magnesium Ceased EP1205003A1 (fr)

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IT1999PD000179 IT1307220B1 (it) 1999-07-29 1999-07-29 Batterie primarie (non ricaricabili) e secondarie (ricaricabili) abase di elettroliti polimerici basati su ioni magnesio
ITPD990179 1999-07-29
PCT/EP2000/007221 WO2001009972A1 (fr) 1999-07-29 2000-07-27 Batteries primaires (non rechargeables) et secondaires (rechargeables) a base de magnesium

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