WO1997037394A1 - GALLIUM DOPED LITHIUM MANGANESE OXIDE SPINELS (LiGaxMn2-xO4) AS ACTIVE CATHODE MATERIAL FOR LITHIUM OR LITHIUM-ION RECHARGEABLE BATTERIES WITH IMPROVED CYCLING PERFORMANCE - Google Patents
GALLIUM DOPED LITHIUM MANGANESE OXIDE SPINELS (LiGaxMn2-xO4) AS ACTIVE CATHODE MATERIAL FOR LITHIUM OR LITHIUM-ION RECHARGEABLE BATTERIES WITH IMPROVED CYCLING PERFORMANCE Download PDFInfo
- Publication number
- WO1997037394A1 WO1997037394A1 PCT/IT1997/000048 IT9700048W WO9737394A1 WO 1997037394 A1 WO1997037394 A1 WO 1997037394A1 IT 9700048 W IT9700048 W IT 9700048W WO 9737394 A1 WO9737394 A1 WO 9737394A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- rechargeable battery
- battery according
- cathode
- spinel
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Classifications
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- 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
- H01M10/052—Li-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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention concerns a lithium or lithium-ion rechargeable battery with improved cycling performance. More specifically, the invention relates to a kind of high energy density secondary cell which can be employed in several fields, in place of conventional rechargeable batteries such as lead acid and nickel-cadmium batteries. Said secondary cell is based on the use of a lithium anode or of an anode capable of intercalating lithium ions, in combination with a non-aqueous electrolyte system, and of a cathode material whose nature is the specific subject of this invention.
- Lithium batteries which have been developed quite recently and are on the market since a relatively short time, have attracted much attention in view of the high levels of voltage and energy that they can offer in a quite reduced volume. This makes lithium batteries particularly promising for use in the field of consumer electronics (such as cellular telephones, camcorders, portable computers), in fixed appliances (such as telephone exchanges, alarm systems) or for various kinds of electrical vehicles.
- the anode element of a lithium secondary cell is made of lithium metal, alone or in alloy with other metals, while the anode of a lithium-ion secondary cell is made of an electrically conductive material, e.g.
- a carbonaceous material wherein lithium is intercalated in ionic form.
- the latter type of cell is also called “rocking- chair” cell or “swing system” cell, with reference to the oscillating rhythm with which lithium is removed from the anode intercalation compound for being intercalated in the cathode material in the discharge phase, and vice-versa in the charge phase.
- LiCoO 2 and LiNiO 2 may be cited (originally disclosed in US-A-4,302,518), as well as the manganese spinel LiMn 2 O 4 (identified in US-A-4, 312,930 as a lithium intercalation compound, from which lithium may be removed by acid treatment without altering the crystalline structure thereof).
- LiMn 2 O 4 identified in US-A-4, 312,930 as a lithium intercalation compound, from which lithium may be removed by acid treatment without altering the crystalline structure thereof.
- remarkable amounts of lithium may be reversibly intercalated.
- both LiCoO 2 and LiNiO 2 may deliver more than 140 Ah/kg by reversibly inserting lithium (Ohzuku et al., Chemistry Express, 7, 193 (1992)).
- the manganese spinel, LiMn 2 O is considered to be the most attractive cathode material for practical applications, in view of some advantageous features thereof, such as low cost, reduced pollution potential, high voltage and high power.
- said material is characterised by a limited specific capacity (110-120 Ah/kg), which, in addition, tends to decease with cycling.
- Tarascon et al. J.M. Tarascon, E. Wang, F.K. Shokoohi, W.R. McKinnon, and S. Colson, J. Electrochem. Soc, 138, No. 10, 2859-2864, 1991
- secondary lithium cells with LiMn 2 O 4 cathode working at an average voltage of 4,1 V with theoretical values of specific energy of 480 Wh/kg lose about 10% of their initial capacity over 50 cycles.
- materials of the kind of the manganese spinel wherein a portion of manganese is replaced by cobalt, chromium or iron have reduced lattice constants with respect to the starting spinel, and this would result in an increased stability of the resulting crystal structure. Said enhanced stability would cause a better ability to undergo a high number of charge and discharge cycles without great losses in the performance.
- D is a mono- or multivalent metal cation; and b is the oxidation state of D.
- cathode material for secondary lithium or lithium-ion batteries which is derived from the LiMn 2 O 4 spinel, wherein a portion of manganese is replaced by an element having the effect of maintaining the battery capacity sufficiently constant during the cycling, but without causing any significant initial loss in said capacity.
- the cathode material proposed may thus be represented by the formula: LiGa x Mn 2 -, ⁇ O 4 , wherein x does not go above the value of 0.1.
- many of the spinel properties, such as, in particular, the low cost and the low toxicity remain unchanged, while at the same time the performance of the cathode material improves, since the initial capacity of the spinel is maintained more constant with cycling.
- the gallium-containing spinel has a better electrochemical behaviour than the spinel with no gallium, some hypotheses may be made, based on the knowledge of the structural variations caused by the lithium ion in the spinel structure when the battery is cycled.
- lithium ion is extracted from the spinel structure, and during the removal of Li * the Mn ion having oxidation state +3 is oxidised to Mn *4 .
- the Mn *4 ion so formed in the charge phase is again reduced to Mn *3 .
- the latter has, as pointed out above, a radius of 0.62 A, while the radius of Mn *4 is 0.53 A.
- the Ga *3 ion by replacing part of the Mn *3 ion, limits the possibility that the Mn *3 /Mn *4 ratio exceeds the value 1.
- This function could also be carried out by other ions, such as those that have already been studied in the prior art cited in the foregoing.
- some of the said ions may involve problems, either due to a ionic radius too different from that of Mn *3 (for instance, Fe *2 : 0.78 A) or to the fact that said ions may show, in turn, the Jahn-Teller effect (for instance, Cu *27*1 o Ni * * *3 ).
- Mg 2* and Z ⁇ 2* as pointed out before, the stability to cycling is achieved at the expense of the capacity, owing to the quantitative ratios employed.
- the present invention specifically provides a lithium or lithium-ion rechargeable battery with improved cycling performance, with nominal voltage of 4 V, comprising an anode made of lithium optionally alloyed with other metals, or an anode made of an electrically conductive material wherein lithium is intercalated in ionic form, a non-aqueous electrolyte and a cathode based on a modified manganese spinel, characterised in that said spinel is modified by the substitution of a portion of manganese with an equal amount of gallium, according to the following formula:
- LiGa x Mn 2 . x O wherein: 0 ⁇ x ⁇ 0.1.
- the cathode material according to the invention may be produced by carrying out the spinel synthesis in the presence of a gallium compound (such as, e.g., Ga 2 O 3 ), according to a reaction scheme that may be summarised as follows:
- the synthesis procedure is quite similar to the procedure for obtaining the conventional manganese spinel, LiMn 2 O 4 .
- the starting products for instance LiOH, Ga 2 O 3 e MnO 2 , are thoroughly mixed together to give a homogeneous powder. Then, the mixture is heated to a temperature from 650°C to 850°C (preferably 700-750°C), and is kept to such temperature for 2-3 days. A black powder is thus obtained, non toxic and non hygroscopic, which may be easily manipulated to form the electrode for use in the battery according to the invention.
- the amount of gallium which is substituted to manganese is such that x has the value 0.05, and the formula of the resulting cathode material is LiGao.osMn1.95O4.
- the cathode material according to the invention is mixed with electrically conductive additives, such as, for instance, carbon-black or graphite, in an amount equal to 5-20% by weight, based on the total weight of the mixture.
- electrically conductive additives such as, for instance, carbon-black or graphite
- Binding agents are also added, such as, for instance, polyethylene, polytetrafluoroethylene, polyvinylidene difluoride, ter-monomer ethylene propylene diene, in an amount equal to 3-10% by weight, based on the total weight of the mixture.
- This composite powder is compressed, at 3-10 tons/cm 2 , on a metal support (stainless steel or aluminium, in leaf or net form) to form the electrode.
- the anode in lithium batteries the anode may be made of lithium metal, alone or in alloy with other metals, while in lithium-ion batteries the anode is often made of a carbonaceous material capable of intercalating lithium ions during the charge and of releasing again said ions during the discharge. Said material is preferably partially or totally graphitised carbon.
- the electrolyte may be made of a liquid solution obtained by dissolving a lithium salt (for instance: LiPF 6 , LiBF 4 , LiCIO 4l LiAsF 6 ) in an organic solvent or in a mixture of organic solvents (for instance: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl formate, methyl acetate).
- a lithium salt for instance: LiPF 6 , LiBF 4 , LiCIO 4l LiAsF 6
- organic solvent for instance: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl formate, methyl acetate.
- the electrolyte may be solid, and, specifically, it may be a ion-conductive polymer of the kind of LiCIO 4 -polyethylene oxide, or a polymer matrix (e.g., polyacrylonitrile, polyvinyl chloride, polymethyl meth ⁇ acrylate) soaked with a liquid electrolyte of the kind referred to above.
- a polymer matrix e.g., polyacrylonitrile, polyvinyl chloride, polymethyl meth ⁇ acrylate
- the battery may assume quite different shapes, ranging from a small button battery to a large parallelepipedal battery.
- the shape may be chosen from the following group: button, cylindrical, prismatic and flat ultra-thin battery.
- the battery is cylindrical, and is produced by supporting the anode material on a copper band and the cathode material on an aluminium band, and by placing between the two said bands a separator band soaked with electrolyte (or, alternatively, a band made of a polymer electrolyte). Said bands, wound together so as to form a spiral, are placed into a stainless steel cylindrical container.
- aluminium and boron which belong to the same group of the Periodical Table of Elements as gallium.
- the performance as cathode materials of manganese spinels wherein part of the Mn is replaced by Al o B turned out to be unsatisfactory.
- the specific capacities in the case of boron-substituted spinels are considerably lower than those offered by the usual LiMn 2 O , and decrease with the number of cycles undergone by the battery.
- the behaviour of aluminium as substitutive element is better, but the initial specific capacities obtainable are still lower than 100 Ah/kg.
- the ionic radiuses are 0.54 A for Al *3 and 0.27 A for B *3 , it may be understood that said poor performances are to be ascribed to the structural stresses originated from the reduced size of the substitutive ions with respect to Mn *3 (which, as pointed out before, has a ionic radius of
- the two materials have the same morphological features, and they are both formed by porous particles having a diameter of 10-20 ⁇ m and a surface area of 3-6 m 2 /g.
- button cells were produced starting from both cathode materials.
- Each series of cells had a lithium anode, a liquid electrolyte (LiPF 6 in ethylene carbonate and dimethyl carbonate), a cathode supported on aluminium net and containing a total amount of 20% by weight of carbon black and polytetrafiuoroethyene.
- the charge/discharge conditions were the following: 1 mA/cm 2 (85 mA/g) between 3.5 and 4.3 V.
- the results of the comparison are illustrated in the enclosed figure, which shows the behaviour of the specific capacity (in Ah/kg) as the number of charge/discharge cycles increases.
- the A curve concerns the battery with LiGao.05Mn1.95O4 as the cathode material
- the B curve concerns the battery with LiMn 2 O 4 as the cathode material.
- the capacity retention is better in the battery according to the present invention, and this better performance does not involve any loss in the initial specific capacity. The latter has practically the same value typical of the conventional spinel.
- the battery with LiGao.05Mn1.95O4 underwent about 230 cycles with a capacity loss of -10%.
- the battery with LiMn 2 O 4 has shown a capacity loss of -25%, while the initial capacities of the two cathodes were almost the same (about 110 Ah/kg, in the example reported).
- the capacity loss observed after -250 cycles is due to the exhaustion of the lithium anode.
- the latter as it is known, has a limited cycle life due to corrosion phenomena.
- the replacement of the lithium anode with a carbonaceous anode may extend the cycle life to above 1000 cycles.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/155,592 US6274278B1 (en) | 1996-03-29 | 1997-03-05 | Gallium doped lithium manganese oxide spinels (LiGaxMn2−xO4) as cathode material for lithium or lithium-ion rechargeable batteries with improved cycling performance |
DK97907264T DK0925612T3 (en) | 1996-03-29 | 1997-03-05 | Gallium-doped lithium manganese oxide spinels (liGaxMn2-xO4) as active cathode material for lithium or lithium ion recovery |
DE69703117T DE69703117T2 (en) | 1996-03-29 | 1997-03-05 | GALLIUM-Doped LITHIUM-MANGANOXIDE SPINEL (LiGaxMn2-xO4) AS ACTIVE CATHODE MATERIAL FOR LITHIUM AND LITHIUM-ION SECONDARY BATTERIES WITH IMPROVED CHARGE-DISCHARGE CAPACITY |
EP97907264A EP0925612B1 (en) | 1996-03-29 | 1997-03-05 | GALLIUM DOPED LITHIUM MANGANESE OXIDE SPINELS (LiGaxMn2-xO4) AS ACTIVE CATHODE MATERIAL FOR LITHIUM OR LITHIUM-ION RECHARGEABLE BATTERIES WITH IMPROVED CYCLING PERFORMANCE |
AU19387/97A AU1938797A (en) | 1996-03-29 | 1997-03-05 | Gallium doped lithium manganese oxide spinels (ligaxmn2-xo4) as active cathode material for lithium or lithium-ion rechargeable batteries with improved cycling performance |
JP09535101A JP2000512064A (en) | 1996-03-29 | 1997-03-05 | Gallium-doped lithium manganese oxide spinel as active cathode material for lithium or lithium ion rechargeable batteries with improved cycling performance (LiGa-xMn-2-xO ▼) |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT96RM000200A IT1283968B1 (en) | 1996-03-29 | 1996-03-29 | RECHARGEABLE LITHIUM OR LITHIUM-ION BATTERY ABLE TO SUSTAIN PROLONGED CYCLING. |
ITRM96A000200 | 1996-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997037394A1 true WO1997037394A1 (en) | 1997-10-09 |
Family
ID=11404045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IT1997/000048 WO1997037394A1 (en) | 1996-03-29 | 1997-03-05 | GALLIUM DOPED LITHIUM MANGANESE OXIDE SPINELS (LiGaxMn2-xO4) AS ACTIVE CATHODE MATERIAL FOR LITHIUM OR LITHIUM-ION RECHARGEABLE BATTERIES WITH IMPROVED CYCLING PERFORMANCE |
Country Status (8)
Country | Link |
---|---|
US (1) | US6274278B1 (en) |
EP (1) | EP0925612B1 (en) |
JP (1) | JP2000512064A (en) |
AU (1) | AU1938797A (en) |
DE (1) | DE69703117T2 (en) |
DK (1) | DK0925612T3 (en) |
IT (1) | IT1283968B1 (en) |
WO (1) | WO1997037394A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6248477B1 (en) | 1999-09-29 | 2001-06-19 | Kerr-Mcgee Chemical Llc | Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same |
US6274278B1 (en) * | 1996-03-29 | 2001-08-14 | Consiglio Nazionale Delle Ricerche | Gallium doped lithium manganese oxide spinels (LiGaxMn2−xO4) as cathode material for lithium or lithium-ion rechargeable batteries with improved cycling performance |
Families Citing this family (10)
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JP3615415B2 (en) * | 1999-03-24 | 2005-02-02 | 三洋電機株式会社 | Non-aqueous secondary battery |
US7476467B2 (en) * | 2004-03-29 | 2009-01-13 | Lg Chem, Ltd. | Lithium secondary battery with high power |
EP2560229B1 (en) * | 2005-10-20 | 2019-06-05 | Mitsubishi Chemical Corporation | Lithium secondary batteries and nonaqueous electrolyte for use in the same |
CN103000876B (en) * | 2012-12-11 | 2014-12-24 | 奇瑞汽车股份有限公司 | Lithium nickel manganese oxide material precursor and preparation method thereof, lithium nickel manganese oxide material and preparation method thereof, and lithium ion battery |
CN104253265A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
US10763491B2 (en) | 2014-04-01 | 2020-09-01 | The Research Foundation For The State University Of New York | Low-temperature synthesis process of making MgzMxOy, where M is Mn, V or Fe, for manufacture of electrode materials for group II cation-based batteries |
JP6356333B2 (en) * | 2014-07-25 | 2018-07-11 | 台湾立凱電能科技股▲ふん▼有限公司 | Method for preparing cathode material for lithium nickel manganese oxide battery and cathode material for lithium nickel manganese oxide battery |
CN104091919B (en) * | 2014-07-29 | 2016-05-18 | 中国科学院福建物质结构研究所 | A kind of anode material for lithium-ion batteries and preparation method thereof |
CN104319392A (en) * | 2014-10-23 | 2015-01-28 | 天津理工大学 | Modified spinel type lithium battery cathode material and preparation method thereof |
CL2017002221A1 (en) * | 2017-09-01 | 2018-01-19 | Univ Antofagasta | Magnesium-doped manganese spinel, cathode material comprising it, preparation method, and lithium ion battery comprising it |
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1996
- 1996-03-29 IT IT96RM000200A patent/IT1283968B1/en active IP Right Grant
-
1997
- 1997-03-05 AU AU19387/97A patent/AU1938797A/en not_active Abandoned
- 1997-03-05 WO PCT/IT1997/000048 patent/WO1997037394A1/en active IP Right Grant
- 1997-03-05 US US09/155,592 patent/US6274278B1/en not_active Expired - Fee Related
- 1997-03-05 JP JP09535101A patent/JP2000512064A/en active Pending
- 1997-03-05 DE DE69703117T patent/DE69703117T2/en not_active Expired - Fee Related
- 1997-03-05 DK DK97907264T patent/DK0925612T3/en active
- 1997-03-05 EP EP97907264A patent/EP0925612B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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AU1938797A (en) | 1997-10-22 |
EP0925612B1 (en) | 2000-09-13 |
ITRM960200A0 (en) | 1996-03-29 |
IT1283968B1 (en) | 1998-05-07 |
DK0925612T3 (en) | 2000-11-13 |
JP2000512064A (en) | 2000-09-12 |
ITRM960200A1 (en) | 1997-09-29 |
US6274278B1 (en) | 2001-08-14 |
DE69703117T2 (en) | 2001-05-17 |
DE69703117D1 (en) | 2000-10-19 |
EP0925612A1 (en) | 1999-06-30 |
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