CA2380509A1 - Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries - Google Patents
Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries Download PDFInfo
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- CA2380509A1 CA2380509A1 CA002380509A CA2380509A CA2380509A1 CA 2380509 A1 CA2380509 A1 CA 2380509A1 CA 002380509 A CA002380509 A CA 002380509A CA 2380509 A CA2380509 A CA 2380509A CA 2380509 A1 CA2380509 A1 CA 2380509A1
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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
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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
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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, i n which at least the anode is magnesium-based, and optionally also the cathode and the electrolyte contain magnesium. Assembly of the batteries involves th e preparation of the individual components and the interposition of a thin lay er of electrolyte between the magnesium-based anode and the cathode.
Description
MAGNESIUM-BASED PRIMARY (NON-RECHARGEABLE) AND SECONDARY
(RECHARGEABLE) BATTERIES
Scope of the invention The present invention regards primary (i.e., non-rechargeable) and secondary s (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.
Prior art As is known, the enormous and rapid development of digital electronics that has io taken place in recent years has enabled the creation of a large number of new portable devices, such as computers, cellphones, videocameras, etc. These devices are almost exclusively equipped with storage batteries built according to a single technology; namely nickel-cadmium (Ni-Cd) batteries.
The need to produce ever smaller and lighter portable devices, together with the is need for long operating autonomy of these devices, has pushed numerous private firms operating in the sector, as well as public research bodies, to carry out research aimed at developing new technologies capable of meeting the requirements referred to above.
In the late eighties and early nineties, two new types of batteries appeared on the 2o market: nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) batteries.
In just a few years, the performance of batteries produced using these technologies has improved considerably, to the extent that today the performance of these batteries is superior to that of nickel-cadmium batteries.
A further advantage of the batteries produced using these new technologies is the 2s absence of cadmium, which, since it is a heavy metal, has quite a serious detrimental impact on the environment.
As is known, 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 3o 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 s 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., Mn02). Thanks to the high electrochemical potential supplied by the lithium anode, these batteries provide high cell voltages, io and consequently also high energy densities.
However, these systems are not reversible, or at the most are usable for just a few cycles.
The idea of exploiting lithium to make secondary batteries has given rise to a first technology known as lithium-polymer (Li-polymer) technology. This method, which is exploits metallic lithium for making the anode, presents, however, serious difficulties in terms of reversibility. In fact, during the recharging phase, 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.
2o At best, the number of cycles obtained using systems of this type thus amounts to just a few dozens or hundreds.
On the other hand, 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.
zs 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.
3o In recent years, it has been possible to produce anodes based on carbon with properties of intercalation. 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 LiXCs type.
Other lithium-ion batteries are provided with an intercalated titanium disulphide-based (LixTiS2) anode. The latter has a behaviour similar to that of a carbon s electrode.
Usually the cathode is instead made using oxides of lithium and transition metals, among which the most widely used up to now is lithium cobaltate (LiCo02), which, for reasons of cost, availability, and toxicity, tends to be replaced by lithium nickelate (LiNi02) or lithium manganate (LiMn04).
io The number of cycles achievable using the rocking-chair technology reaches one thousand.
Usually, in these systems the electrolyte consists of an organic polymer with solvent properties, which is rendered ionic-conductive by being doped with special lithium salts (e.g., LiPFs, LiCl04, etc.).
is Notwithstanding the fact that the above-mentioned technological advances tend to solve the problems linked to the use of lithium on account of the high reactivity of this element, and in particular the main problem linked to the formation of dendrites on the anode, research for a complete solution to these problems is still very much in progress. The problem of the formation of dendrites has not yet been 2o completely solved, whilst likewise the problem of high reactivity of lithium, together with the known problems of safety referred to previously, and the problem of reversibility still remain open.
Magnesium could be an element usable for overcoming these problems, and in particular as a replacement for lithium.
2s As reported in the literature, 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 3o siemens/cm) for the production of primary and/or secondary batteries.
Nevertheless, in the patent US44575 Moulton suggests the possibility of making magnesium batteries, without, however, specifying the procedure, in particular OC-09-2Cj01 CA 02380509 2002-O1-28 EP000722~
(RECHARGEABLE) BATTERIES
Scope of the invention The present invention regards primary (i.e., non-rechargeable) and secondary s (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.
Prior art As is known, the enormous and rapid development of digital electronics that has io taken place in recent years has enabled the creation of a large number of new portable devices, such as computers, cellphones, videocameras, etc. These devices are almost exclusively equipped with storage batteries built according to a single technology; namely nickel-cadmium (Ni-Cd) batteries.
The need to produce ever smaller and lighter portable devices, together with the is need for long operating autonomy of these devices, has pushed numerous private firms operating in the sector, as well as public research bodies, to carry out research aimed at developing new technologies capable of meeting the requirements referred to above.
In the late eighties and early nineties, two new types of batteries appeared on the 2o market: nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) batteries.
In just a few years, the performance of batteries produced using these technologies has improved considerably, to the extent that today the performance of these batteries is superior to that of nickel-cadmium batteries.
A further advantage of the batteries produced using these new technologies is the 2s absence of cadmium, which, since it is a heavy metal, has quite a serious detrimental impact on the environment.
As is known, 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 3o 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 s 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., Mn02). Thanks to the high electrochemical potential supplied by the lithium anode, these batteries provide high cell voltages, io and consequently also high energy densities.
However, these systems are not reversible, or at the most are usable for just a few cycles.
The idea of exploiting lithium to make secondary batteries has given rise to a first technology known as lithium-polymer (Li-polymer) technology. This method, which is exploits metallic lithium for making the anode, presents, however, serious difficulties in terms of reversibility. In fact, during the recharging phase, 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.
2o At best, the number of cycles obtained using systems of this type thus amounts to just a few dozens or hundreds.
On the other hand, 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.
zs 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.
3o In recent years, it has been possible to produce anodes based on carbon with properties of intercalation. 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 LiXCs type.
Other lithium-ion batteries are provided with an intercalated titanium disulphide-based (LixTiS2) anode. The latter has a behaviour similar to that of a carbon s electrode.
Usually the cathode is instead made using oxides of lithium and transition metals, among which the most widely used up to now is lithium cobaltate (LiCo02), which, for reasons of cost, availability, and toxicity, tends to be replaced by lithium nickelate (LiNi02) or lithium manganate (LiMn04).
io The number of cycles achievable using the rocking-chair technology reaches one thousand.
Usually, in these systems the electrolyte consists of an organic polymer with solvent properties, which is rendered ionic-conductive by being doped with special lithium salts (e.g., LiPFs, LiCl04, etc.).
is Notwithstanding the fact that the above-mentioned technological advances tend to solve the problems linked to the use of lithium on account of the high reactivity of this element, and in particular the main problem linked to the formation of dendrites on the anode, research for a complete solution to these problems is still very much in progress. The problem of the formation of dendrites has not yet been 2o completely solved, whilst likewise the problem of high reactivity of lithium, together with the known problems of safety referred to previously, and the problem of reversibility still remain open.
Magnesium could be an element usable for overcoming these problems, and in particular as a replacement for lithium.
2s As reported in the literature, 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 3o siemens/cm) for the production of primary and/or secondary batteries.
Nevertheless, in the patent US44575 Moulton suggests the possibility of making magnesium batteries, without, however, specifying the procedure, in particular OC-09-2Cj01 CA 02380509 2002-O1-28 EP000722~
without specifying how to make the anode, cathode and polymeric electrolyte.
Polymeric electrolytes doped with magnesium salts are cited, which, when tested, yielded resistivities higher than 10' ohm~cm at room temperature, whereas in order to be able to make the batteries it. is necessary for the resis_ tivity values to s drop below than 105 ohm~cm.
The main task of the present invention is to succeed in developing primary (non-rechargeable) batteries andlor secondary (rechargeable) batteries that overcome the problems of reactivity and reversibility typical of lithium-based batteries.
In the framework of the above-mentioned task, a consequent primary purpose is to io 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.
1 s A further important purpose is to arrive at the almost total elimination of environmental impact.
Summary of the invention These and other purposes, which will appear more clearly in what follows, are achieved by primary (non-rechargeable) and secondary (rechargeable) batteries 2o 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 preferentially also the electrolyte contain magnesium. Also the cathode of the batteries that form the object of the present invention may optionally incorporate magnesium.
Zs The anode included in the present invention is characterized in that it uses magnesium in the various states of oxidation Mg"+ t°5"~I, 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 3o good ionic conductivity and capable of solvation of the said ionic species.
When 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 AMENDED SHEET
0~-09-20'01 CA 02380509 2002-O1-28 EP000722 s 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 s 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 the electrolyte contain magnesium and even the cathode can optionally contain magnesium.
Further characteristics and advantages will emerge more clearly from the ensuing io detailed description of the invention, an embodiment of which is illustrated, merely for the purpose of providing a non-limiting example, in the attached plate of drawing.
Brief description of the figure Figure 1 is a schematic sectional view of a battery built according to the present is invention, where:
designates an anode which has the characteristics and is made as is described in detail in what follows;
- 11 designates a cathode which has the characteristics and is made as is described in detail in what follows; and - 12 designates an electrolyte which has the characteristics and is made as is described in detail in what follows.
Detailed description of the invention Notwithstanding the fact that the attempts referred to above failed to lead to promising results, the present inventors have now surprisingly found that 2s magnesium is an element that can be usefully employed in making primary and secondary batteries.
Following on extensive and ample research, the present inventors have in fact found that, for the purposes of the present invention, i.e., for obtaining primary and secondary batteries with technical performance comparable, if not superior, to that of lithium batteries at present in use or known, reference being made to the AMENDED SHEET
06'-09-2001 CA 02380509 2002-O1-28 EP000722 aforementioned Figure, 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 s the anode and preferentially also the electrolyte contain magnesium.
In the batteries that form the object of the present invention also the cathode may optionally incorporate magnesium.
When the cathode does not contain magnesium, it is a conventional cathode, and hence is in itself known, and consequently will not be described further herein.
~o The primary and secondary batteries that form the object of the present invention may moreover comprise possible dielectric spacers, not illustrated in the Figure.
In particular, 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"+~osns2)~ optionally combined with metallic magnesium.
~s In said anode, 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.
2o in particular, the anode 10 may consist of metallic magnesium as such, and in this case the magnesium may be used in laminated or sintered form.
In the case, instead, where the magnesium has 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, Zs 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.
3o Also in the case where intercalation or embedding materials are used for the anode, this may be either organic or inorganic. The intercalation or embedding AMENDED SHEET
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 (WYOx), ferric s oxides (FeyOX), titanium sulphides (TiySx), cobalt oxides (CoYOX), nickel oxides (NiyOX), manganese oxide (MnyOX), 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 io capable of englobing, by intercalation or embedding into their own matrices, magnesium crystallites of reduced dimensions or magnesium monocrystals.
Furthermore said anode 10 may be optionally oxidized with oxidizing agents such as oxygen gas or peroxide, such as H202, or organic peroxides and stabilized by treatment with stabilizing agents such as alkoxides, (e.g. tetra-alkoxy titanium, is 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+.
In the case where the cathode contains magnesium, the latter may have a Zo 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.
2s 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.
Also 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 3o preparation or, unlike the anode, the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to its preparation.
When the cathode 11 does not contain magnesium, it is a conventional cathode and is in itself known; consequently, it is not further described herein. In this case, anyway, the cathode contains electrochemically active materials having a base of metallic mixtures in appropriate proportions in a reduced or oxidized form.
For this s purpose, as is known from the prior art, materials containing transition metals may be used, such as, but not exclusively, manganese with state of oxidation ranging from 7+ 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 io 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)yX2_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 is C~-C~ chains, whilst X may be chosen from among halides, CI04, (CF3)~+XSO3_X , with Osx<_2, SCN', P043', or chlorides in 8 form, or other equivalents.
The compounds of the general formula Mg(R)yX2_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.
2o 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.
2s In the case of 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. These solvents may therefore be chosen from among ethers, alcohols, di-alcohols, esters, amines and amides, thioethers, thioalcohols, thioesters, alkyl carbonates 3o and alkyl thiocarbonates, or other equivalents.
In the case where 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, s 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.
Also usable for the purpose are polyphosphazene polymers functionalized with the 1o polymers and/or copolymers mentioned previously.
To provide examples, among 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 is 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.
2o Also usable for the purpose are copolymers derived from the polyalkylene oxides and polyalkylene glycols, polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate; polyalkylene glycols and polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate; polycarbonates and polyalkyl siloxanes, polyethylene diaminotetra-acetate; polyalkyl siloxanes and polyethylene 2s diaminotetra-acetate such as, as example, polyethylene oxide-polypropylene oxide, polymethylene oxide-polyethylene oxide, and polymethylene oxide polypropylene oxide; polyethylene oxide-polymethylene carbonate, polypropylene oxide-polyethylene carbonate, and polyethylene oxide- polypropylene carbonate;
polyethylene glycol- polymethyl polysiloxane, polyethylene oxide-polymethyl 3o siloxane, and polyethylene oxide- polyethylene diaminotetra-acetate, etc.
It is also possible to use for the purpose, for instance, 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 s latter.
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.
In the case where the electrolyte is acidified, however, the preferential acidifying to agents for the electrolyte are compounds with a base of phosphorus, polyphosphates, P205, or equivalents of the orthophosphoric-acid type. In the case where the electrolyte is alkalinized, 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.
is 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.
2o This process is, however, to be preferred in the case where non-stabilized electrodes are used.
- Spacers (not shown in the Figure) 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 2s groups that may be present on the surfaces of the fibres. For the purpose it is possible to use, 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 3o electrons and for electrical connection of the poles of the battery element. For the purpose, it is possible, for example, to use 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:
s - preparation of an anode characterized in that it comprises magnesium in the various states of oxidation Mg"+ co<-"sz~, 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;
to - 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;
- preparation of an electrolyte characterized in that it comprises any ionic species is 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 2o 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.
To obtain batteries with adequate performance, the same technologies may be zs adopted as those used for the preparation of the already known lithium batteries.
In particular, it is possible to:
- use single-layer or multi-layer button battery technology;
- connect the multi-layer films in parallel (parallel stacking), or else connect the multi-layer films in series (bipolar stacking), for non-folded structures;
30 - use flat-roll design technology or jelly-roll design technology, or flat-stack design technology for folded structures.
Described in detail in what follows are the methodologies for the preparation of the individual components when these contain magnesium, and hence are not conventional and so known, both in terms of characteristics and in terms of production methodologies, to any person skilled in the branch.
A - General methodolocties for the preparation of the components s A.1 - Preparation of the anode 10 For the purposes of the present invention, three types of 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 to 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. In addition, the magnesium may also be sintered.
is 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 2o magnesium. Particularly 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 2s 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.
Other methods of intercalation, in addition to the ones described previously, for 30 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 H202, or organic peroxides. The anode may, moreover, be subjected to a further and possible stabilization treatment. As stabilizing agents may be used alkoxides, such as tetra-alkoxy titanium, tetra-s alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide, or other equivalent compounds.
With the above further processes it is possible to obtain an anode that presents better characteristics of stability, reversibility, and exchange currents.
A.2 - Preparation of the cathode 11 to 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, is but not exclusively, with a base of carbon, graphite, titanium disulphide (TiS2), cobalt dioxide (Co02), nickel dioxide (Ni02), manganese dioxide (Mn02), or other equivalents chosen from among the ones already mentioned previously.
Like the anode, also the cathode may undergo further processes of oxidation in situ and following on its preparation, these processes having already been 2o described previously. Unlike the anode, however, the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to the preparation of the cathode.
A.3 - Preparation of the intercalation material The intercalation material is chosen from among the materials that may be used 2s 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 3o 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.4 - Preparation of the electrolyte 12 The electrolyte 12 according to the present invention may be prepared using s 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)YX2_Y, with 0<_y_<2, having a very low charge/volume ratio. The radical R
may to be chosen from the group consisting, for example, of alkyls with C~-C7 chains, whilst X may be chosen from among halides, CI04, (CF3)~+XSO3_X, with 0<_x_<2, SCN-, PO43~, or chlorides in b form. The compounds of the general formula Mg(R)YX2_y, with Osy<_2, usable for doping the electrolyte, may moreover be preferentially magnesium salts or ionic complexes of magnesium with lattice Is 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 2o 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 2s high conductivity and which are based on polymeric electrolytes having a high degree of crosslinking. In these circumstances, 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.
3o 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 dissociate the 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, s 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.
to Among the magnesium salts or complexes that may be used for the purposes of the present invention, particularly advantageous is 8-MgCl2, 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.
is 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. In the case where 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 P205, or other equivalents, under stirring and up to 2o complete dissolution. 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 2s having good characteristics of insulating strength and dielectric constant.
In the case where the material has polar groups on its surface, chemical inertization is performed by means of appropriate functionalization to prevent interaction with the magnesium ions or with ionic complexes of magnesium. In the case of glass fibres, for example, the hydroxyl groups present on the surface are de-activated by 3o reaction with triethoxyalkyl silane, thus rendering the surface of the spacer highly apolar.
B - General examples for the production of the components The invention is hereinafter further clarified in its general aspects and through a few examples of practical implementation, which have the sole purpose of illustrating the invention without limiting the scope thereof in any way.
8.1 - Example of preparation of the anode 10 by sintering s 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.
B.2 - Preparation of graphite thermally pre-intercalated with magnesium to A mixture of magnesium oxide and graphite, in a weight ratio ca of 3% is rendered disordered using a ball mill. This mechanical mixing proceeds for approximately thirty minutes and has the purpose of intimately homogenizing the two components. The mechanical action of the min moreover increases the crystallographic disorder of the graphite. The material thus obtained is next is introduced into a quartz tube and subjected to six nitrogen-vacuum cycles to eliminate any traces of air.
Subsequently, the tube is subjected to a vacuum by means of a diffusion pump at a pressure of 10'6 mbar and brought up to a temperature of 700°C, at which it is kept for approximately 14 hours.
ao 8.3 - Preparation of the composite cathode 11 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 2s subsequently converted into a sintered cathode 11 by application of a pressure of 1400 MPa.
8.4 - Examples of preparation of the polymers for the electrolyte Example B.4.1 Commercially available polyethylene glycols with molecular weights from 200 up to 30 1000 may be used.
Example B.4.2 For the preparation of the polymer, it is possible to use commercially available polymers, such as polycarbonates, or equivalent ones.
Example B.4.3 - (Synthesis of polyethylene glycol-polydimethyl polysiloxane copolymers) An aliquot of approximately 3 grams of dimethyl dichlorosilane is made to react in s toluene with 50 mol% of polyethylene glycol 400. The reaction is conducted in nitrogen for approximately 10 hours. A transparent polymer is obtained having a high viscosity. After eliminating the toluene and the residue of dimethyl dichlorosilane in vacuum conditions (10-3 bar) at a temperature of approximately 120°C, a thick liquid polymer is obtained that resembles honey in appearance. The to analyses have shown that the material thus synthesized is a copolymer with blocks of polyethylene oxide and polydimethyl siloxane.
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 is 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 2o that the product is the anhydride of pure ethylene-diaminotetra-acetate acid.
Example B.4.5 - (Synthesis of copolymer with blocks of ethylene-diaminotetra-acetate - polyethylene glycol) 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.
2s 8. 5 - Example of preparation of 8 magnesium chloride One gram of metallic magnesium is introduced into a 250-ml flask in a rigorously inert argon atmosphere. The flask is prepared in an argon dry box with reflux drip and vacuum cocks. Approximately 100 ml of n-chlorobutane are added to the magnesium using the drip. The mixture thus obtained is made to react for 3o approximately 8 hours under argon flow at the boiling temperature of the chlorobutane. After two hours' reaction, a greyish solid is obtained having a floury appearance. After vacuum-drying for six hours, a white powder is obtained.
Analyses have shown that this is magnesium chloride in 8 form.
8.6 - Examples of preparation of magnesium-based polymeric electrolytes Example B.6.1 - (Preparation of the polymeric electrolyte polyethylene glycol/(MgCl2)x) s The magnesium salt is previously dissolved in ethyl acetate. In the same solvent, 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 to 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 is alcohol perfectly anhydrous. Separately in the same solvent is prepared a solution of b 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 2o 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 8 magnesium 2s chloride) The polyether polymers of various molecular weights (200 to 200.000) are directly treated with 8-MgCl2. The heterogeneous system thus obtained is homogenized for complete dissolution of the salt in the polymer by means of heating and continuous stirring.
3o Example B.6.5. - (Direct synthesis, i.e., without solvents, of polymeric electrolytes having a base of polyethylene glycols or polyethylene oxides and 8 magnesium chloride, acidified with P205) Ofi-09-2001 CA 02380509 2002-O1-28 EP0007221 The polymeric electrolyte obtained according to the foregoing Example B.6.4 is treated with 8 wt% of P20$. The time required for obtaining a polymeric electrolyte by means of stirring and complete dissolution of the P205 is approximately 4 hours. The addition of P205 increases the viscosity of the polymer.
s B.7 - Example of preparation of the polymeric electrolyte 72 reinforced, with glass fibres The 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.
~ o C - Examples of prototvaes produced Practical tests carried out on prototypes revealed that the task and purposes set had been achieved.
In particular, in one first case (single-element button battery with polymeric electrolyte reinforced with a porous paper filter), an anodic disk (anode 10) made is of sintered metallic magnesium and having a diameter of 8 mm was interfaced with a film of polymeric electrolyte PEG 400 (MgCl2)X reinforced with a paper disk having the same diameter, after prior heating of the two compounds. On top of the polymeric-electrolyte film was laid a composite cathodic film (cathode 11 ) having a base of intercalation material consisting of metal oxides with graphite in liquid 2o suspension subsequently dried, prepared according to the previous examples.
The element thus obtained was housed on a system consisting of two current collectors 13. A few instants after assembly, 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 2s were carried out at a constant current of between 5 and 150 p.A, the prototype presented a threshold voltage between 2 and 3 V. After discharge, the voltage returned to 1.8 V.
In a second case (single-element button battery with polymeric electrolyte reinforced with glass fibre), the anode 10 and cathode 11 were prepared according 3o to the same procedures as for the first prototype. In the present case, as reinforcement for the polymeric electrolyte 12, glass fibre having a thickness of 0.02 mm was used. The characteristics of this prototype were the same as for AMENDED SHEET
those of the first prototype, but the reversibility was considerably superior.
In a third case (single-element button battery with polymeric electrolyte acidified with P205 and reinforced with glass fibres), the anode 10 and cathode 11 were prepared following the same procedures as for the first prototype.
Acidification of s the polymeric electrolyte 12 by means of P205 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.
From the examples given above there clearly emerge the advantages that may be obtained using magnesium for the production of the batteries that form the object io of the present invention. In addition, when compared to lithium, 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 is 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 2o 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 2s 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.
Polymeric electrolytes doped with magnesium salts are cited, which, when tested, yielded resistivities higher than 10' ohm~cm at room temperature, whereas in order to be able to make the batteries it. is necessary for the resis_ tivity values to s drop below than 105 ohm~cm.
The main task of the present invention is to succeed in developing primary (non-rechargeable) batteries andlor secondary (rechargeable) batteries that overcome the problems of reactivity and reversibility typical of lithium-based batteries.
In the framework of the above-mentioned task, a consequent primary purpose is to io 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.
1 s A further important purpose is to arrive at the almost total elimination of environmental impact.
Summary of the invention These and other purposes, which will appear more clearly in what follows, are achieved by primary (non-rechargeable) and secondary (rechargeable) batteries 2o 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 preferentially also the electrolyte contain magnesium. Also the cathode of the batteries that form the object of the present invention may optionally incorporate magnesium.
Zs The anode included in the present invention is characterized in that it uses magnesium in the various states of oxidation Mg"+ t°5"~I, 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 3o good ionic conductivity and capable of solvation of the said ionic species.
When 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 AMENDED SHEET
0~-09-20'01 CA 02380509 2002-O1-28 EP000722 s 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 s 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 the electrolyte contain magnesium and even the cathode can optionally contain magnesium.
Further characteristics and advantages will emerge more clearly from the ensuing io detailed description of the invention, an embodiment of which is illustrated, merely for the purpose of providing a non-limiting example, in the attached plate of drawing.
Brief description of the figure Figure 1 is a schematic sectional view of a battery built according to the present is invention, where:
designates an anode which has the characteristics and is made as is described in detail in what follows;
- 11 designates a cathode which has the characteristics and is made as is described in detail in what follows; and - 12 designates an electrolyte which has the characteristics and is made as is described in detail in what follows.
Detailed description of the invention Notwithstanding the fact that the attempts referred to above failed to lead to promising results, the present inventors have now surprisingly found that 2s magnesium is an element that can be usefully employed in making primary and secondary batteries.
Following on extensive and ample research, the present inventors have in fact found that, for the purposes of the present invention, i.e., for obtaining primary and secondary batteries with technical performance comparable, if not superior, to that of lithium batteries at present in use or known, reference being made to the AMENDED SHEET
06'-09-2001 CA 02380509 2002-O1-28 EP000722 aforementioned Figure, 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 s the anode and preferentially also the electrolyte contain magnesium.
In the batteries that form the object of the present invention also the cathode may optionally incorporate magnesium.
When the cathode does not contain magnesium, it is a conventional cathode, and hence is in itself known, and consequently will not be described further herein.
~o The primary and secondary batteries that form the object of the present invention may moreover comprise possible dielectric spacers, not illustrated in the Figure.
In particular, 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"+~osns2)~ optionally combined with metallic magnesium.
~s In said anode, 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.
2o in particular, the anode 10 may consist of metallic magnesium as such, and in this case the magnesium may be used in laminated or sintered form.
In the case, instead, where the magnesium has 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, Zs 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.
3o Also in the case where intercalation or embedding materials are used for the anode, this may be either organic or inorganic. The intercalation or embedding AMENDED SHEET
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 (WYOx), ferric s oxides (FeyOX), titanium sulphides (TiySx), cobalt oxides (CoYOX), nickel oxides (NiyOX), manganese oxide (MnyOX), 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 io capable of englobing, by intercalation or embedding into their own matrices, magnesium crystallites of reduced dimensions or magnesium monocrystals.
Furthermore said anode 10 may be optionally oxidized with oxidizing agents such as oxygen gas or peroxide, such as H202, or organic peroxides and stabilized by treatment with stabilizing agents such as alkoxides, (e.g. tetra-alkoxy titanium, is 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+.
In the case where the cathode contains magnesium, the latter may have a Zo 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.
2s 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.
Also 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 3o preparation or, unlike the anode, the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to its preparation.
When the cathode 11 does not contain magnesium, it is a conventional cathode and is in itself known; consequently, it is not further described herein. In this case, anyway, the cathode contains electrochemically active materials having a base of metallic mixtures in appropriate proportions in a reduced or oxidized form.
For this s purpose, as is known from the prior art, materials containing transition metals may be used, such as, but not exclusively, manganese with state of oxidation ranging from 7+ 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 io 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)yX2_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 is C~-C~ chains, whilst X may be chosen from among halides, CI04, (CF3)~+XSO3_X , with Osx<_2, SCN', P043', or chlorides in 8 form, or other equivalents.
The compounds of the general formula Mg(R)yX2_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.
2o 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.
2s In the case of 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. These solvents may therefore be chosen from among ethers, alcohols, di-alcohols, esters, amines and amides, thioethers, thioalcohols, thioesters, alkyl carbonates 3o and alkyl thiocarbonates, or other equivalents.
In the case where 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, s 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.
Also usable for the purpose are polyphosphazene polymers functionalized with the 1o polymers and/or copolymers mentioned previously.
To provide examples, among 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 is 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.
2o Also usable for the purpose are copolymers derived from the polyalkylene oxides and polyalkylene glycols, polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate; polyalkylene glycols and polycarbonates, polyalkyl siloxanes, polyethylene diaminotetra-acetate; polycarbonates and polyalkyl siloxanes, polyethylene diaminotetra-acetate; polyalkyl siloxanes and polyethylene 2s diaminotetra-acetate such as, as example, polyethylene oxide-polypropylene oxide, polymethylene oxide-polyethylene oxide, and polymethylene oxide polypropylene oxide; polyethylene oxide-polymethylene carbonate, polypropylene oxide-polyethylene carbonate, and polyethylene oxide- polypropylene carbonate;
polyethylene glycol- polymethyl polysiloxane, polyethylene oxide-polymethyl 3o siloxane, and polyethylene oxide- polyethylene diaminotetra-acetate, etc.
It is also possible to use for the purpose, for instance, 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 s latter.
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.
In the case where the electrolyte is acidified, however, the preferential acidifying to agents for the electrolyte are compounds with a base of phosphorus, polyphosphates, P205, or equivalents of the orthophosphoric-acid type. In the case where the electrolyte is alkalinized, 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.
is 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.
2o This process is, however, to be preferred in the case where non-stabilized electrodes are used.
- Spacers (not shown in the Figure) 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 2s groups that may be present on the surfaces of the fibres. For the purpose it is possible to use, 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 3o electrons and for electrical connection of the poles of the battery element. For the purpose, it is possible, for example, to use 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:
s - preparation of an anode characterized in that it comprises magnesium in the various states of oxidation Mg"+ co<-"sz~, 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;
to - 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;
- preparation of an electrolyte characterized in that it comprises any ionic species is 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 2o 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.
To obtain batteries with adequate performance, the same technologies may be zs adopted as those used for the preparation of the already known lithium batteries.
In particular, it is possible to:
- use single-layer or multi-layer button battery technology;
- connect the multi-layer films in parallel (parallel stacking), or else connect the multi-layer films in series (bipolar stacking), for non-folded structures;
30 - use flat-roll design technology or jelly-roll design technology, or flat-stack design technology for folded structures.
Described in detail in what follows are the methodologies for the preparation of the individual components when these contain magnesium, and hence are not conventional and so known, both in terms of characteristics and in terms of production methodologies, to any person skilled in the branch.
A - General methodolocties for the preparation of the components s A.1 - Preparation of the anode 10 For the purposes of the present invention, three types of 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 to 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. In addition, the magnesium may also be sintered.
is 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 2o magnesium. Particularly 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 2s 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.
Other methods of intercalation, in addition to the ones described previously, for 30 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 H202, or organic peroxides. The anode may, moreover, be subjected to a further and possible stabilization treatment. As stabilizing agents may be used alkoxides, such as tetra-alkoxy titanium, tetra-s alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide, or other equivalent compounds.
With the above further processes it is possible to obtain an anode that presents better characteristics of stability, reversibility, and exchange currents.
A.2 - Preparation of the cathode 11 to 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, is but not exclusively, with a base of carbon, graphite, titanium disulphide (TiS2), cobalt dioxide (Co02), nickel dioxide (Ni02), manganese dioxide (Mn02), or other equivalents chosen from among the ones already mentioned previously.
Like the anode, also the cathode may undergo further processes of oxidation in situ and following on its preparation, these processes having already been 2o described previously. Unlike the anode, however, the cathode may be prepared with electrochemically active materials that have been partially oxidized prior to the preparation of the cathode.
A.3 - Preparation of the intercalation material The intercalation material is chosen from among the materials that may be used 2s 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 3o 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.4 - Preparation of the electrolyte 12 The electrolyte 12 according to the present invention may be prepared using s 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)YX2_Y, with 0<_y_<2, having a very low charge/volume ratio. The radical R
may to be chosen from the group consisting, for example, of alkyls with C~-C7 chains, whilst X may be chosen from among halides, CI04, (CF3)~+XSO3_X, with 0<_x_<2, SCN-, PO43~, or chlorides in b form. The compounds of the general formula Mg(R)YX2_y, with Osy<_2, usable for doping the electrolyte, may moreover be preferentially magnesium salts or ionic complexes of magnesium with lattice Is 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 2o 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 2s high conductivity and which are based on polymeric electrolytes having a high degree of crosslinking. In these circumstances, 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.
3o 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 dissociate the 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, s 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.
to Among the magnesium salts or complexes that may be used for the purposes of the present invention, particularly advantageous is 8-MgCl2, 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.
is 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. In the case where 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 P205, or other equivalents, under stirring and up to 2o complete dissolution. 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 2s having good characteristics of insulating strength and dielectric constant.
In the case where the material has polar groups on its surface, chemical inertization is performed by means of appropriate functionalization to prevent interaction with the magnesium ions or with ionic complexes of magnesium. In the case of glass fibres, for example, the hydroxyl groups present on the surface are de-activated by 3o reaction with triethoxyalkyl silane, thus rendering the surface of the spacer highly apolar.
B - General examples for the production of the components The invention is hereinafter further clarified in its general aspects and through a few examples of practical implementation, which have the sole purpose of illustrating the invention without limiting the scope thereof in any way.
8.1 - Example of preparation of the anode 10 by sintering s 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.
B.2 - Preparation of graphite thermally pre-intercalated with magnesium to A mixture of magnesium oxide and graphite, in a weight ratio ca of 3% is rendered disordered using a ball mill. This mechanical mixing proceeds for approximately thirty minutes and has the purpose of intimately homogenizing the two components. The mechanical action of the min moreover increases the crystallographic disorder of the graphite. The material thus obtained is next is introduced into a quartz tube and subjected to six nitrogen-vacuum cycles to eliminate any traces of air.
Subsequently, the tube is subjected to a vacuum by means of a diffusion pump at a pressure of 10'6 mbar and brought up to a temperature of 700°C, at which it is kept for approximately 14 hours.
ao 8.3 - Preparation of the composite cathode 11 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 2s subsequently converted into a sintered cathode 11 by application of a pressure of 1400 MPa.
8.4 - Examples of preparation of the polymers for the electrolyte Example B.4.1 Commercially available polyethylene glycols with molecular weights from 200 up to 30 1000 may be used.
Example B.4.2 For the preparation of the polymer, it is possible to use commercially available polymers, such as polycarbonates, or equivalent ones.
Example B.4.3 - (Synthesis of polyethylene glycol-polydimethyl polysiloxane copolymers) An aliquot of approximately 3 grams of dimethyl dichlorosilane is made to react in s toluene with 50 mol% of polyethylene glycol 400. The reaction is conducted in nitrogen for approximately 10 hours. A transparent polymer is obtained having a high viscosity. After eliminating the toluene and the residue of dimethyl dichlorosilane in vacuum conditions (10-3 bar) at a temperature of approximately 120°C, a thick liquid polymer is obtained that resembles honey in appearance. The to analyses have shown that the material thus synthesized is a copolymer with blocks of polyethylene oxide and polydimethyl siloxane.
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 is 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 2o that the product is the anhydride of pure ethylene-diaminotetra-acetate acid.
Example B.4.5 - (Synthesis of copolymer with blocks of ethylene-diaminotetra-acetate - polyethylene glycol) 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.
2s 8. 5 - Example of preparation of 8 magnesium chloride One gram of metallic magnesium is introduced into a 250-ml flask in a rigorously inert argon atmosphere. The flask is prepared in an argon dry box with reflux drip and vacuum cocks. Approximately 100 ml of n-chlorobutane are added to the magnesium using the drip. The mixture thus obtained is made to react for 3o approximately 8 hours under argon flow at the boiling temperature of the chlorobutane. After two hours' reaction, a greyish solid is obtained having a floury appearance. After vacuum-drying for six hours, a white powder is obtained.
Analyses have shown that this is magnesium chloride in 8 form.
8.6 - Examples of preparation of magnesium-based polymeric electrolytes Example B.6.1 - (Preparation of the polymeric electrolyte polyethylene glycol/(MgCl2)x) s The magnesium salt is previously dissolved in ethyl acetate. In the same solvent, 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 to 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 is alcohol perfectly anhydrous. Separately in the same solvent is prepared a solution of b 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 2o 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 8 magnesium 2s chloride) The polyether polymers of various molecular weights (200 to 200.000) are directly treated with 8-MgCl2. The heterogeneous system thus obtained is homogenized for complete dissolution of the salt in the polymer by means of heating and continuous stirring.
3o Example B.6.5. - (Direct synthesis, i.e., without solvents, of polymeric electrolytes having a base of polyethylene glycols or polyethylene oxides and 8 magnesium chloride, acidified with P205) Ofi-09-2001 CA 02380509 2002-O1-28 EP0007221 The polymeric electrolyte obtained according to the foregoing Example B.6.4 is treated with 8 wt% of P20$. The time required for obtaining a polymeric electrolyte by means of stirring and complete dissolution of the P205 is approximately 4 hours. The addition of P205 increases the viscosity of the polymer.
s B.7 - Example of preparation of the polymeric electrolyte 72 reinforced, with glass fibres The 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.
~ o C - Examples of prototvaes produced Practical tests carried out on prototypes revealed that the task and purposes set had been achieved.
In particular, in one first case (single-element button battery with polymeric electrolyte reinforced with a porous paper filter), an anodic disk (anode 10) made is of sintered metallic magnesium and having a diameter of 8 mm was interfaced with a film of polymeric electrolyte PEG 400 (MgCl2)X reinforced with a paper disk having the same diameter, after prior heating of the two compounds. On top of the polymeric-electrolyte film was laid a composite cathodic film (cathode 11 ) having a base of intercalation material consisting of metal oxides with graphite in liquid 2o suspension subsequently dried, prepared according to the previous examples.
The element thus obtained was housed on a system consisting of two current collectors 13. A few instants after assembly, 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 2s were carried out at a constant current of between 5 and 150 p.A, the prototype presented a threshold voltage between 2 and 3 V. After discharge, the voltage returned to 1.8 V.
In a second case (single-element button battery with polymeric electrolyte reinforced with glass fibre), the anode 10 and cathode 11 were prepared according 3o to the same procedures as for the first prototype. In the present case, as reinforcement for the polymeric electrolyte 12, glass fibre having a thickness of 0.02 mm was used. The characteristics of this prototype were the same as for AMENDED SHEET
those of the first prototype, but the reversibility was considerably superior.
In a third case (single-element button battery with polymeric electrolyte acidified with P205 and reinforced with glass fibres), the anode 10 and cathode 11 were prepared following the same procedures as for the first prototype.
Acidification of s the polymeric electrolyte 12 by means of P205 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.
From the examples given above there clearly emerge the advantages that may be obtained using magnesium for the production of the batteries that form the object io of the present invention. In addition, when compared to lithium, 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 is 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 2o 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 2s 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.
Claims (46)
1. Primary (non-rechargeable) and secondary (rechargeable) 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 contains magnesium in the various states of oxidation Mg n+
(0<=n<=2), optionally combined with metallic magnesium - the electrolyte contains ionic species of magnesium in solvents capable of producing electrolytes having good ionic conductivity, and of solvating said species.
- the anode contains magnesium in the various states of oxidation Mg n+
(0<=n<=2), optionally combined with metallic magnesium - the electrolyte contains ionic species of magnesium in solvents capable of producing electrolytes having good ionic conductivity, and of solvating said species.
2. Batteries according to Claim 1, characterized in that also the cathode contains magnesium.
3. Batteries according to Claim 1 in which the anode is oxidised with oxidising agents chosen from among oxygen gas, hydrogen peroxide, or organic peroxides.
4. Batteries according to Claim 1 and 3, in which the metallic magnesium is laminated or sintered.
5. Batteries according to Claim 1 and 3 in which the magnesium is on a substrate of highly conductive organic or inorganic material.
6. Batteries according to Claim 5, in which the highly conductive inorganic substrate materials are chosen from among metals, oxides, alloys or fabrics thereof.
7. Batteries according to Claim 5, in which the highly conductive inorganic or organic substrate materials are chosen from among carbon fibre and carbon fibre fabrics, graphite, or graphite-based composites.
8. Batteries according to Claim 1 and 3, in which the magnesium is intercalated or embedded in highly conductive organic or inorganic materials which intercalate or embed, in their own matrices, magnesium crystallites of reduced dimensions or magnesium monocrystals.
9. Batteries according to Claim 8, in which the intercalation or embedding inorganic materials are chosen from among oxides, sulphides, phosphates or phosphides of transition metals, alkaline metals, and alkaline-earth metals, as well as non-metal compounds.
10.Batteries according to Claim 8, in which the intercalation or embedding organic materials have a base of carbons with a highly crystalline or irregular structure or carbon-based polymers.
11.Batteries according Claims from 1 to 10 in which the anode is stabilized by treatment with alkoxides chosen from among tetra-alkoxy titanium, tetra-alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide.
12.Batteries according to Claim 1, in which the electrolyte comprises, as ionic species of magnesium, magnesium salts or complexes of the general formula Mg(R)y X2-y (0<=y<=2), where R is chosen from the group consisting of alkyls with C1-C7 chains, and X is chosen from among halides, ClO4, (CF3)1+x SO3-x (0<=x<=2), SCN-, PO4 3-, or chlorides in 8 form having lattice energy lower than 500 kcal/mol.
13.Batteries according to Claim 1, in which the electrolyte comprises as solvent any liquid or polymeric solvent material having polar groups or heteroatoms chosen from oxygen, nitrogen, silicon and phosporus which co-ordinate and dissociate the magnesium salts or complexes.
14.Batteries according to Claim 1 in which the electrolyte comprises as ionic species of magnesium .delta. MgCl2 and as polymeric solvent polyalkylene glycols and or polyalkylene oxides.
15.Batteries according Claims from 12 to and 14, in which the electrolyte is acidified.
16.Batteries according to Claim 15, in which the electrolyte is acidified with compounds having a base of phosphorus, polyphosphates, P2O5, or orthophosphoric acid.
17.Batteries according to Claims from 12 to and 14, in which the electrolyte is alkalinized.
18.Batteries according to Claim17, in which the electrolyte is alkalinized with compounds being a base or nitrogen such as amines and ammonia, or with basic derivatives of sulphur or phosphorus.
19.Batteries according to Claims 1 and 2 in which the cathode comprises magnesium on a substrate of highly conductive organic or inorganic materials.
20.Batteries according to Claim 18, in which the highly conductive inorganic substrate materials are chosen from among metals, oxides, alloys or fabrics made of the same.
21.Batteries according to Claim 18, in which the highly conductive inorganic or organic substrate materials are chosen from among carbon fibre and carbon-fibre fabrics, graphite or graphite-based composites.
22.Batteries according to Claims 1 and 2, in which the cathode comprises magnesium in organic or inorganic materials that intercalate or embed magnesium.
23.Batteries according to Claim 22, in which the intercalation or embedding inorganic materials are chosen from among oxides, sulphides, phosphates or phosphides of transition metals, alkaline metals, and alkaline-earth metals, as well as non-metal compounds.
24.Batteries according to Claims 1 and 2, in which the intercalation or embedding inorganic or organic materials have a base of carbons with a highly crystalline or irregular structure or carbon-based polymers.
25.Batteries according Claims from 19 to 24 in which the cathode is oxidised with oxidising agents chosen from among oxygen gas, hydrogen peroxide, or organic peroxides.
26.Batteries according Claims from 19 to 24 in which the cathode is prepared with electrochemically active material partially oxidised with oxidising agents chosen from among oxygen gas, hydrogen peroxide, or organic peroxides.
27.A method for the production of batteries according to Claims 1, characterized in that it envisages of the following step:
- preparation of an anode characterised 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, 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 and - preparation of an electrolyte characterised 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 and optionally - preparation of a cathode characterised in that it comprises species of magnesium having a substrate of highly conductive inorganic or organic materials or in inorganic or organic materials for intercalation or embedding of the magnesium.
- preparation of an anode characterised 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, 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 and - preparation of an electrolyte characterised 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 and optionally - preparation of a cathode characterised in that it comprises species of magnesium having a substrate of highly conductive inorganic or organic materials or in inorganic or organic materials for intercalation or embedding of the magnesium.
28.A method for the production of batteries according to Claims 27, in which the anode is prepared from laminated or sintered metallic magnesium.
29.A method for the production of batteries according to Claims 27 and 28, in which the anode having a base of magnesium on a substrate is prepared by chemical or thermal vapour deposition, or electrolytic deposition, or electrochemical deposition of the magnesium on inorganic materials chosen from among metals, oxides, alloys or fabrics made of the same.
30.A method for the production of batteries according to Claim 27, in which the anode having a base of magnesium on a substrate is prepared by chemical or thermal vapour deposition, or electrolytic deposition, or electrochemical deposition of the magnesium on inorganic or organic materials chosen from among carbon fibre carbon fibre fabrics, graphite, or graphite-based composites.
31.A method for the production of batteries according to Claim 27, in which the anode with a base of magnesium in intercalation or embedding material is prepared by (i) homogenization and pelletization of a mixture of an intercalation or embedding material, ground up to complete structural disorder, and magnesium carbonates or oxides brought up to a temperature of between 100 and 400°C for a period of time of between 1 and 3 hours, (ii) then heating up to temperatures of between 800 and 1200°C in an inert atmosphere, (iii) and finally kepting at this temperature for 1-5 days in vacuum conditions.
32.A method for the production of batteries according to Claim 27, in which the anode with a base of magnesium in intercalation or embedding material is prepared by solvent-casting of a solvent such as benzene, toluene, N-N
dimethyl acetamide, dimethyl formamide, or tetrahydrofuran, containing, in a homogeneous way, a mixture of polymers chosen from among polyethylene, polyvinyl chloride, polyacrylamide or polyacrylonitrile, or similar polymers, and the intercalation or embedding material chosen, previously extended up to complete homogenization with magnesium.
dimethyl acetamide, dimethyl formamide, or tetrahydrofuran, containing, in a homogeneous way, a mixture of polymers chosen from among polyethylene, polyvinyl chloride, polyacrylamide or polyacrylonitrile, or similar polymers, and the intercalation or embedding material chosen, previously extended up to complete homogenization with magnesium.
33.A method for the production of batteries according to Claim 27, in which the anode with a base of magnesium in intercalation or embedding material for intercalating or embedding magnesium is prepared by plasma spraying or sputtering of the magnesium into the intercalation or embedding material chosen.
34. A method for the production of batteries according any of Claims 28-33, in which the anode is oxidised with oxidising agents chosen from among oxygen gas, hydrogen peroxide, or organic peroxides.
35.A method for the production of batteries according any of Claims 28-34, in which the anode is stabilized by treatment with alkoxides chosen from among tetra-alkoxy titanium, tetra-alkoxy silanes, trialkoxy aluminium, tetra-alkoxy zirconium, or magnesium dialkoxide.
36.A method for the production of batteries according to Claim 27, in which the electrolyte is prepared by direct dissolution of the magnesium salt or complex in the liquid solvent or molten polymer.
37.A method for the production of batteries according to Claim 27, in which the electrolyte is prepared by solvent-casting of the common solvent of the polymer and of the magnesium salt or complex.
38.A method for the production of batteries according to Claim 27, in which the electrolyte is prepared by dissolution of the magnesium salt or complex in one or more monomers and by subsequent polymerization.
39.A method for the production of batteries according to Claim 27, in which the cathode having a base of magnesium on a substrate is prepared by chemical or thermal vapour deposition, or electrolytic deposition, or electrochemical deposition of the magnesium on inorganic materials chosen from among metals, oxides, alloys, or fabrics made of the same.
40.A method for the production of batteries according to Claim 27, in which the cathode having a base of magnesium on a substrate is prepared by chemical or thermal vapour deposition, or electrolytic deposition, or electrochemical deposition of the magnesium on inorganic or organic materials chosen from among carbon fibre, carbon fibre fabrics, graphite, or graphite-based composites.
41.A method for the production of batteries according to Claim 27, in which the cathode with a base of magnesium in intercalation or embedding material is prepared by: (i) homogenization and pelletization of a mixture of an intercalation or embedding material, ground up to complete structural disorder, and magnesium carbonates or oxides brought up to a temperature of between 100 and 400°C for a period of time of between 1 and 3 hours, (ii) then heating up to temperatures of between 800 and 1200°C in an inert atmosphere, (iii) and finally kepting at this temperature for 1-5 days in vacuum conditions.
42.A method for the production of batteries according to Claim 27, in which the cathode with a base of magnesium in intercalation or embedding material is prepared by solvent-casting of a solvent such as benzene, toluene, N-N
dimethyl acetamide, dimethyl formamide, or tetrahydrofuran, containing, in a homogeneous way, a mixture of polymers chosen from among polyethylene, polyvinyl chloride, polyacrylamide or polyacrylonitrile, or similar polymers, and the intercalation or embedding material previously extended up to complete homogenization with magnesium.
dimethyl acetamide, dimethyl formamide, or tetrahydrofuran, containing, in a homogeneous way, a mixture of polymers chosen from among polyethylene, polyvinyl chloride, polyacrylamide or polyacrylonitrile, or similar polymers, and the intercalation or embedding material previously extended up to complete homogenization with magnesium.
43.A method for the production of batteries according to Claim 27, in which the cathode with a base of magnesium in intercalation or embedding material is prepared by plasma spraying or sputtering of the magnesium into the intercalation or embedding material chosen.
44. A method for the production of batteries according any of Claims 39-43, in which the magnesium of the cathode is oxidized with oxidising agents chosen among from oxygen gas, hydrogen peroxide, or organic peroxides.
45.A method for the production of batteries according any of Claims 39-43, in which the cathode is prepared with electrochemically active materials previously partially oxidized with oxidising agents chosen among from oxygen gas, hydrogen peroxide, or organic peroxides.
46.A method for setting magnesium batteries according to anyone of preceding claims, in which at least one anode, at least one cathode, at least one electrolyte, current collectors and optionally dielectric spacers are put in contact between one another, setting the electrolyte between anode and cathode at temperatures of between room temperature and approximately 150°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITPD99A000179 | 1999-07-29 | ||
| IT1999PD000179 IT1307220B1 (en) | 1999-07-29 | 1999-07-29 | PRIMARY (NON RECHARGEABLE) AND SECONDARY (RECHARGEABLE) BATTERIES BASED ON POLYMER ELECTROLYTES BASED ON MAGNESIUM IONS |
| PCT/EP2000/007221 WO2001009972A1 (en) | 1999-07-29 | 2000-07-27 | Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2380509A1 true CA2380509A1 (en) | 2001-02-08 |
Family
ID=11392702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002380509A Abandoned CA2380509A1 (en) | 1999-07-29 | 2000-07-27 | Magnesium-based primary (non-rechargeable) and secondary (rechargeable) batteries |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1205003A1 (en) |
| JP (1) | JP2003506832A (en) |
| KR (1) | KR20020032540A (en) |
| CN (1) | CN1365524A (en) |
| AU (1) | AU6278000A (en) |
| CA (1) | CA2380509A1 (en) |
| IL (1) | IL147873A0 (en) |
| IT (1) | IT1307220B1 (en) |
| RU (1) | RU2269841C2 (en) |
| WO (1) | WO2001009972A1 (en) |
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| CN100382212C (en) * | 2001-04-13 | 2008-04-16 | 三洋化成工业株式会社 | Electrolytic condenser |
| CN1708874A (en) * | 2002-10-29 | 2005-12-14 | 索尼株式会社 | Rechargeable electrochemical cell |
| JP4839573B2 (en) * | 2004-02-13 | 2011-12-21 | ソニー株式会社 | Electrochemical device and electrode |
| US7537682B2 (en) | 2004-03-17 | 2009-05-26 | California Institute Of Technology | Methods for purifying carbon materials |
| US8377586B2 (en) | 2005-10-05 | 2013-02-19 | California Institute Of Technology | Fluoride ion electrochemical cell |
| US8232007B2 (en) | 2005-10-05 | 2012-07-31 | California Institute Of Technology | Electrochemistry of carbon subfluorides |
| US7794880B2 (en) | 2005-11-16 | 2010-09-14 | California Institute Of Technology | Fluorination of multi-layered carbon nanomaterials |
| KR100714128B1 (en) * | 2005-12-08 | 2007-05-02 | 한국전자통신연구원 | Rechargeable battery having non-metallic current collector and method of manufacturing the same |
| US8658309B2 (en) | 2006-08-11 | 2014-02-25 | California Institute Of Technology | Dissociating agents, formulations and methods providing enhanced solubility of fluorides |
| CN101997107B (en) * | 2009-08-11 | 2012-12-26 | 中国电子科技集团公司第十八研究所 | Magnesium electrode for magnesium battery and preparation method thereof |
| JP2011142049A (en) * | 2010-01-08 | 2011-07-21 | Sumitomo Electric Ind Ltd | Electrode, magnesium ion secondary battery, and power system |
| KR101067115B1 (en) * | 2010-02-04 | 2011-09-22 | 삼성전기주식회사 | Cathode active material having magnesium and magnesium secondary battery having same |
| KR20130119333A (en) * | 2010-05-25 | 2013-10-31 | 펠리온 테크놀로지스 인크. | Electrode materials for magnesium batteries |
| US8877383B2 (en) | 2010-06-21 | 2014-11-04 | Toyota Motor Engineering & Manufacturing North America, Inc. | Magnesium-based battery |
| KR101353257B1 (en) * | 2010-08-09 | 2014-01-21 | 주식회사 엘지화학 | Positive Current Collector Comprising Carbon-based Material and Magnesium Secondary Battery Comprising the Same |
| KR101302076B1 (en) * | 2010-09-17 | 2013-09-05 | 주식회사 엘지화학 | Electrode for magnesium secondary battery and magnesium secondary battery comprising the same |
| CN102478200A (en) * | 2010-11-25 | 2012-05-30 | 西安中科麦特电子技术设备有限公司 | Solar energy storage streetlamp |
| JP5617131B2 (en) * | 2011-01-17 | 2014-11-05 | 埼玉県 | Electrolyte for magnesium secondary battery, magnesium secondary battery and method for producing electrolyte |
| CN102651485B (en) * | 2011-02-28 | 2016-03-30 | 丰田自动车株式会社 | The application in rechargeable magnesium cell of rechargeable magnesium cell, electrolyte and the electrolyte for rechargeable magnesium cell |
| US8361661B2 (en) * | 2011-03-08 | 2013-01-29 | Pellion Technologies Inc. | Rechargeable magnesium ion cell components and assembly |
| EP2738862B1 (en) * | 2011-07-28 | 2020-12-16 | FUJIFILM Wako Pure Chemical Corporation | Electrolyte solution for electrochemical devices |
| JP6011071B2 (en) * | 2012-01-16 | 2016-10-19 | 大日本印刷株式会社 | Battery pack |
| CN103703603B (en) | 2012-04-16 | 2017-02-08 | 松下电器产业株式会社 | Non-aqueous electrolyte for electrochemical element, production method therefor, and electrochemical element using same |
| WO2014098898A1 (en) * | 2012-12-21 | 2014-06-26 | Pellion Technologies, Inc. | Rechargeable magnesium ion cell components and assembly |
| CN103066326B (en) * | 2013-01-18 | 2015-07-15 | 上海交通大学 | Electrolyte for chargeable magnesium battery |
| CN104969406B (en) * | 2013-01-25 | 2018-11-02 | 富士胶片和光纯药株式会社 | Electrochemical device electrolyte and electrochemical device |
| KR101507497B1 (en) * | 2013-05-24 | 2015-03-31 | 한국과학기술연구원 | Anode foil for magnesium secondary battery and its fabrication method |
| CN103413905A (en) * | 2013-07-12 | 2013-11-27 | 复旦大学 | High-voltage magnesium charge-discharge battery |
| US9882245B2 (en) | 2013-08-23 | 2018-01-30 | Ut-Battelle, Llc | Alkoxide-based magnesium electrolyte compositions for magnesium batteries |
| JP6526970B2 (en) * | 2015-01-05 | 2019-06-05 | 公立大学法人大阪府立大学 | Polycarbonate-based solid electrolyte and magnesium ion secondary battery |
| WO2016160481A1 (en) * | 2015-04-03 | 2016-10-06 | Yan Ye | Solid state battery cells and methods for making and using same |
| US10873079B2 (en) * | 2015-06-29 | 2020-12-22 | Toyota Motor Engineering & Manufacturing North America, Inc. | Low resistance, multivalent metal anodes |
| JP6745474B2 (en) * | 2016-03-17 | 2020-08-26 | 国立大学法人静岡大学 | Electrolyte material for magnesium secondary battery and magnesium secondary battery using the same |
| CN110380150B (en) * | 2019-08-02 | 2022-01-11 | 中国科学院宁波材料技术与工程研究所 | Harmless recovery method of waste power battery electrolyte |
| DE102019219007A1 (en) * | 2019-12-05 | 2021-06-10 | Honda Motor Co., Ltd. | Magnesium powder anodes and electrochemical cells including such anodes |
| RU2732988C1 (en) * | 2020-03-26 | 2020-09-28 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина РАН (ИФХЭ РАН) | Anode of sodium-ion accumulator |
| CN113224337B (en) * | 2021-02-26 | 2022-07-19 | 青岛华高墨烯科技股份有限公司 | Graphene/cuprous chloride-magnesium flashing battery and preparation method thereof |
| CN113078373B (en) * | 2021-05-24 | 2022-09-09 | 中国科学技术大学 | Aqueous metal ion secondary battery and aqueous electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2157066B (en) * | 1984-04-04 | 1987-01-07 | Duracell Int | Solid state electrochemical devices |
| US4894302A (en) * | 1985-06-14 | 1990-01-16 | The Dow Chemical Company | Alkaline earth metal anode-containing cell having electrolyte of organometallic alkaline earth metal salt and organic solvent |
| US4650731A (en) * | 1985-06-18 | 1987-03-17 | The Dow Chemical Company | Electric current-producing cell and related composition |
| US4960655A (en) * | 1989-01-27 | 1990-10-02 | Hope Henry F | Lightweight batteries |
| FR2673769B1 (en) * | 1991-03-07 | 1993-06-18 | Centre Nat Rech Scient | POLYMERIC MATERIALS WITH ION CONDUCTION. |
| JPH06163080A (en) * | 1992-11-19 | 1994-06-10 | Sanyo Electric Co Ltd | Secondary battery |
| US5449575A (en) * | 1993-08-04 | 1995-09-12 | Moulton; Russell D. | Electrochemical cell with magnesium anode packaging |
-
1999
- 1999-07-29 IT IT1999PD000179 patent/IT1307220B1/en active
-
2000
- 2000-07-27 CA CA002380509A patent/CA2380509A1/en not_active Abandoned
- 2000-07-27 IL IL14787300A patent/IL147873A0/en unknown
- 2000-07-27 JP JP2001514499A patent/JP2003506832A/en active Pending
- 2000-07-27 WO PCT/EP2000/007221 patent/WO2001009972A1/en not_active Application Discontinuation
- 2000-07-27 RU RU2002102077A patent/RU2269841C2/en not_active IP Right Cessation
- 2000-07-27 KR KR1020027001244A patent/KR20020032540A/en not_active Application Discontinuation
- 2000-07-27 EP EP00949410A patent/EP1205003A1/en not_active Ceased
- 2000-07-27 CN CN00811017A patent/CN1365524A/en active Pending
- 2000-07-27 AU AU62780/00A patent/AU6278000A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU6278000A (en) | 2001-02-19 |
| CN1365524A (en) | 2002-08-21 |
| IT1307220B1 (en) | 2001-10-29 |
| KR20020032540A (en) | 2002-05-03 |
| IL147873A0 (en) | 2002-08-14 |
| RU2269841C2 (en) | 2006-02-10 |
| WO2001009972A1 (en) | 2001-02-08 |
| JP2003506832A (en) | 2003-02-18 |
| EP1205003A1 (en) | 2002-05-15 |
| ITPD990179A1 (en) | 2001-01-29 |
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| EEER | Examination request | ||
| FZDE | Discontinued |