CA2058431C - Method for producing a li(a1) anode for a lithium battery - Google Patents
Method for producing a li(a1) anode for a lithium battery Download PDFInfo
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- CA2058431C CA2058431C CA002058431A CA2058431A CA2058431C CA 2058431 C CA2058431 C CA 2058431C CA 002058431 A CA002058431 A CA 002058431A CA 2058431 A CA2058431 A CA 2058431A CA 2058431 C CA2058431 C CA 2058431C
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- lithium
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- aluminium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 13
- 238000010924 continuous production Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052759 nickel Inorganic materials 0.000 abstract description 11
- 238000003825 pressing Methods 0.000 abstract description 6
- 238000005275 alloying Methods 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- 210000004027 cell Anatomy 0.000 description 14
- 229910007008 Li(Al) Inorganic materials 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- -1 for example VZSS Inorganic materials 0.000 description 6
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910003092 TiS2 Inorganic materials 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- 239000004291 sulphur dioxide Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 229920006355 Tefzel Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GXCDLJXPZVCHBX-UHFFFAOYSA-N 3-methylpent-1-yn-3-yl carbamate Chemical compound CCC(C)(C#C)OC(N)=O GXCDLJXPZVCHBX-UHFFFAOYSA-N 0.000 description 1
- FDQGNLOWMMVRQL-UHFFFAOYSA-N Allobarbital Chemical compound C=CCC1(CC=C)C(=O)NC(=O)NC1=O FDQGNLOWMMVRQL-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910012761 LiTiS2 Inorganic materials 0.000 description 1
- 229910016003 MoS3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004890 malting Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0411—Methods of deposition of the material by extrusion
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
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- H—ELECTRICITY
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
- H01M4/0461—Electrochemical alloying
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
- H01M4/0488—Alloying
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/40—Alloys based on alkali metals
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
- H01M50/469—Separators, membranes or diaphragms characterised by their shape tubular or cylindrical
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/26—Cells without oxidising active material, e.g. Volta cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
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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
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
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- Chemical & Material Sciences (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
A method for producing a Li(A1) anode for a lithium battery comprises the steps of pyrometallurgically alloying Li and A1 in inert atmosphere, grinding the formed alloy after cooling to a homogeneous powder, pressing or extruding the powder to an elongated anode element around a current conductive thread, preferably of nickel, and providing the anode element with an enclosure of microporous separator material.
Description
1 PCT/SE90/00~"'-WC~ '010'46 METHODS FOR PRODUCING A Li(;Al) ANODE
FOR A LITHIUM BATTERY
Technical Field ,This invention relates to a method for producing a Li ( A1 ) anode fo=- a lithium , battery, in Which Li and A1 are pyrometallurgically alloyed in inert atmosphere and the formed alloy after~~ , cooling is ground to a homogeneous pouder.
Technical Background ~ , ' At the present time there is a growing interest for lithium batteries. The interest is not limited to primary batteriEa, which so far have been most common ' on the market, but is increasingly focused also on ' secondary batteries. Lithium metal is attractive as a battery ~ anode material 1 because of its light weight, high voltage, high electrochemical equivalence, and good conductivity.
' However, the use of pure lithium as anode material creates numerous and difficult problems, which are well known in the art. Especially, the difficulty with rechargeability and low malting point should be mentioned. The safety problems with batteries having pure lithium negative electrodes.can certainly not be neglected. ~ . '""
For improv:Lng the qualities of negative electrodes having lithium ~ as the ~ active material the . use __.of different lithium alloys has been investigated.
Especially the use of aluminium as host metal for the highly reactivelithium has been found to provide certain advantages, for .example with regard to the absence of dend:rite.formation and a high melting point.
" The present invention accordingly relates to a new and '~~ improved method for producing a Li(A1) anode for use in a primary or secondary battery.
WO 91/01046 ~ ~ ~ ~ PCT/S E90/00473 The production of a Li(A1) powder in the way set forth in the introduction above is known from Ge-A-1 484 650, but this powder is then pressed on a current conductive mesh. -In Journal of Electrochemical Society, Volume 124, No 10, 1977, M.L. Rao et al, "Lithium-Aluminium Electrode", p 1490-1492, a method to sinter Li(A1) powder on current conductive grids is disclosed.
In Journal of Electrochemical Society, Volume 131, No 8, 1984, A.S. Haranski et al, "The Cycling Effici-ency of Lithium-Aluminium Electrodes in Nonaqueous Media", p 1750-1755, the electrodeposition of lithium on aluminium or nickel wires is dosclosed.
By US-A-4 Oll 372 it is known to cast a Li(A1) alloy on a conductive thread.
.Also DE-A-1 049 949 regarding.the production cf a certain electrode by pressing active lead paste on a lead thread, followed by the step of providing the electrode with a separator should be mentioned as another example of the prior art.
All these publications fail ,to disclose ,any totally satisfactory method of practically producing a Li(Al) anode for a lithium battery with the properties and qualities now sought for. , The Invention Such a method is according to the, invention obtained in that the Li(A1) powder produced in the way set forth above is pressed or extruded to an elongated anode element around a. current conductive thread, prefezably of nickel, and that the anode element is provided with ,an enclosure of mlcroporous .separator material. ---The,enclosure can according to a further aspect of the~invention be provided in a,least two different caays: A separator material sheet. can be placed.' at either side of an anode complex, comprising anode elements and, connector rails, and pressed and line welded around the separate anode elements.
W~ 91101046 ~ ~ ~ ~ 4 ~ ~ PCTlSE90/00473 Alternatively and preferably, a plurality of separate anode elements at certain intervals on a current conductive thread is formed in a continuous process, including the provision of the enclosures of microporous separator material.
The utilized microporous separator material is quite sensitive. Accordingly, each anode element may be provided with a protective web or net outside the separator material, especially when the anodes are to be used for a secondary battery.
Brie~ Description of the Drawings ' The invention will be described in further detail below reference being made to the , accompanying drawings, in which Fig 1 illustrates a thread length with anode elements according to the invention thereon, Fig 2 shows an anode element to a larger scale, Fig 3 is a plan view of an embodiment of an anode according to the invention, Fig 4 is an exploded view illustrat-ing the formation of a certain battery, Fig 5 illustrates this battery with two lids prior to their attachment, Fig 6 is a cross-sectional view of another battery, and Fig 7 is a graph showing the volumetric capacity of lithium versus the relative volume change of an aluminium host.
Detailed Description of Preferred Embodiments Generally speaking, the invention is described in its application to a liquid electrolyte lithium'battery and especially a battery based on either of the following two lithium/sulphur dioxide systems:
1) Li / S02 + LiAlCl4 + C / C
2) Li / S02 ~ LiAlCl4 / TiS2 These systems have the important advantages of .providing high energy and power density. The first mentioned system is.best suited for a primary battery, whereas the second one can also~well be' used for a secondary,.i.e. rechargeable battery.
W~ 91/01046 ~ ~ ~ ~ ~ ~ pC~/g~90/00473 The reversible chemical reaction in a respective battery of any of these types has the following overall scheme:
1) 3 Li + 3 C + 3 S02 + LiAlCl4 ~-"~'-- LiCl-A1(S02)3-3C
+ 3LiC1 2) Li + TiS2~ LiTiS2 (in this case SO + LiA1C19 is a pure electrolyte not participating in the reaction) Due to the difficult problems with pure lithium as negative electrode or anode in any of these batteries the use of a host metal forming an alloy with the highly reactive lithium has been investigated: It -has been found that the use of aluminium as host metal gives advantages, especially the absence of dendrite formation. and a high melting point. Accordingly a lithium-aluminium alloy is used as anode in practical embodiments.. Further aspects of this choice will be dealt with below, but already now it may be stated that an Li(A1) alloy containing about 30 atom$ Li is pre-ferred in the' second system due to its unique r.e-chargeability.: . , . With Li(Al) as~anode a practical~cell voltage of 2.6 V is obtained in the first system and 1.8 V in the second system.
The cathode or positive electrode in a~ battery in 'thg first system is a high surface carbon black in combination with the liquid S02-LiA1C14~complex. Carbon black has a two-fold function in the battery: it acts as a complex binder for the reduced dorm of 502~(ef the reaction formula above) and.as an adsorbing agent for the 802-LiAlCl~ complex but also as the current collector in the cathode. In order to satisfy the demands the carbon material should have a high surface area, high density, a great number of active sites for the complex binding and aw good electric conductivity.
dt should further have a'high porosity providing space for the reaction products.
WO 91/01046 ~ ~ ~ ~ PCT/SE907b0473 Garbon black materials have been~found to fulfil ' these requirements, and the presently ' preferred material is .the commercially available product Ket~en Slack from Akzo. ~ ' In the second system the cathode is electrically conducting TiS2 or any other suitable metal sulphide, for example VZSS, MoS3 etC.
The electrolyte is 6S02-LiAlCl4, which requires a pressure of; some 2.atmospheres to become liquid. The electrolyte .Functions as an ion conductor in both systems and also as a depolarizer in the ~ primary system, which . poses special stoichiometric ~~and physical-chemical requirements. Thus, the quantity of S02 'is stoichiometrically .twice as big as that of ,LiAlCl4, which is necessary both toy ensure that the electrolyte ~.s ~ liquid down to -30oC ' ' and has an ,adequately low viscosity and can avoid drying out at . discharge in a primary system.
xhe separator in the battery shall effectively prevent electrical contact between anode and cathode but shall allow penetration of electrolyte and de-polarizer. It shall in this case be able to contain or store certain amounts of electrolyte. A commercially available microporous polypropylene plastic film having up to 70 % porosity, being free'of pinholes and posses-sing good physical strength,~has initially~been used.
It can also be possible to use a polyethylene ,,separator, but more promising results have been ,, obtained with the copolymer material ethylene-tetra fluoro-ethylene (ETFE). Practically, microporous Tefzel ~ (with a porosity of 40 %) from Soimat~Ltd, UK
has bean tested.. The material is stable in the battery environment, whereas its physical strength is~inferior to that of polypropylene. ' As will~appear more clearly below, ttje sbparator has. the form of hollow fibres in the anode complex of . the battery. Hollow fibres can also'be used For the cathode.
WO 91/01046 w ~ ~ ~ ~ ~ j ,~ PCT/SE90/00473 Summarizing, the battery according to the inven-tion works in the Li(A1)/SOZ system. It has an anode of Li(Al) alloy in hollow fibre separator. In the primary battery the electrolyte/cathode is LiA1C14~, ~ S02 and C.
., The discharge process for this battery system comprises oxidation of lithium, reduction of~sulphur dioxide and complex formation between electrolyte salt, sulphur dioxide and carbon. In the secondary battery the .. cathode is TiS2 or the likA, whereas the electrolyte, . .which does not take part in the~xeaction,~ is SO2 and LiA1C14. , . . ~ . . .
,. . The capacity of the first mentioned system is higher than that of the second one, but due to a certain risk for thermal run-away during charging of the first system it is only used for primary batteries.
A critical factor for the utilization'of the~anode electrode material in a battery is the active electrode surface. The cell power increases with increasing ,,,contact surface between electrode and electrolyte. In ,,, the present battery, a large surface has been accomp lashed .by the use of the so called "hollow fibre"
concept for 'the anode. Thisiaoncept~~is revealed in WO-A-87/01516 and can be characterized in that the anode: material is'shaped as a cylinder ~or~ similar elongated body with optional cross-section .and is encapsulated in an elastical, miaroporous separator material forming a hollow tube and that the anode elements are connected to an electrically conductive ., material '(for example nickel)'not taking part in the ., cell reaction. The cross-sectional dimension of the ,., hollow tube or fibre is preferably less than 3 mm.
Aa already mentioned 'an' anode material con ,, stituting about 30 ~atom% 'lithium in an alloy with aluminium~~has (together with the hollow fibre-concept) proven advantageous for .a ~rechargable battery. ~mhe reasons can be summarized as follows:
. , this alloy shows only small volume changes during charging and discharging, WO 91/01046 ~ ~ ~ ~ ~ ~ ~ P~I'/SE90/00473 - ~ the cylindrical shape enables volume changes to occur in two dimensions, so that lthe anode ' ' structure is not disintegrated, - the separator, design gives a physical compress~.on, - leading, to an increased integrity. for the anode structure during charge and discharge, and the Li(A1) alloy has a melting point over 600°C, which means that liquid and, strongly aggressive lithium cannot be set free. ,..
These factors are of special importance for the anode integrity, which is necessary to ensure that the anode material is rechargeable and secure.' '' The anode material can be manufactured in at least two -different ways, namely either electrochemical loading of lithium into aluminium (electroforming)..~~or pyrometallurgical fusion together of lithium and aluminium at n temperature of about 700°C or more.
. Although the first-mentioned method has certain advantages, the second one is presently preferred. -.-.
The fusion together of lithium and aluminium at 700°C requires an inert atmosphere (argon),' as both metals ,are aggressive relative to OZ and H20 and to a . ,lesser extent N2. The molten alloy is cooled off, ., whereafter it is ground in dry atmosphere (preferably less than 2 % humidity). The resulting powder can then be pressed (at a pressure of 6-ZO ton/cm2) 'in a hydraulic press around a central' nickel' wire to a parallelepipedical or cylindrical shape. An example of practical measurements are 1.4 x 1.8 x 50.0 mm. The anode is thereafter enclosed in a hollow fibre separator . , , , . . , , . , Further. particulars about the procedure are given below.
As an alternative to .pressing the powder into the ,desired shape a.sintering~process is feasible. Casting or extrusion is also possible.
WO 91!01046 ,. ~ c~ ~ fCf/SE90100473 In order to obtain the desired properties, for . example with regard to. high density, for the cathode material in the first system carbon black is mixed with Teflon ~ in proportions appr 80:20. In practice carbon powder, isopropanol, water and Teflon, suspension is mixed. The mixture is extruded, .dried and sintered.
After finely ~ dividing ~ the cathode, material it is ' ~ pressed or rolled~~onto~a~ current collecting net or the '" like, for example of nickel. The finished cathodes are enclosed in separator material of the same kind as used for the anodes.
In a practical case carbon cathodes~with dimen sions 50 x 15 mm and a'thickness of 1 - 2 mm are made.
. They contain some 0.3 - 0.5 g' carbon each and have a .porosity of 75 %. ' The electrolyte as described above can be prepared ., in that equimolar amounts of LiCl ~ and AlCl3 are mixed in a pressure vessel, whereupon S02 is added.
So far' the general properties of the different elements constituting the battery ~or cell in the Li(Al)/802 system as well as their manufacture are described.. Now the time has come to describe the physical construction of especially the anode., Lithium may be deposited on metallic aluminiuml~by electrochemical loading.' As has already been stated, ,.~~pyrometallurgical fusion together' of lithium and aluminium into Li(Al) alloy is however preferred.
. Examples of ways of constructing anodes~containing such allay is now described with reference~to Figs 1 and 2. ~ . ~ ' The process of manufacturing 'powdered alloy followed by pressing or sintering this ~~lloy~ on a ... ,conductive wire of for' example~nickel~'has been de scribed above. ' ' im~ an industrial process a conductive wire 1 (Fig 1 ) can be stepwise fed through a ~ press or sinter equipment and provided'~with anode elements '2 ~at "V~ 91/Oi04G ~ ~ ~ ~ ~ '1 ~ PCT/SE90/00473 intervals suitable for the following creation of complete anodes.
Referring to Fig 2, each anode~element 2 may be provided.; with a separator 3 according to the "hollow fibre"-concept., Due to the comparatively low. physical strength of the Tefzel ~ separator material it may be advantageous, especially if the battery is to be of the secondary type, to cover each anode element enclosed in separator material with a ~rein~orcing web or net 4, preferably but not necessarily of the same material. In s a practical case a number of filaments are braided directly on'each element.' The number of filaments may be fourteen.' After separation the anode elements 2 may be placed as cross-bars betwen two collector rails 5, as shown in Fig 3, and their conductive wires 1 are attached to the collector rails 5 by soldering or the like. If the anode elements 2 are not already provided with separators time has now come to do so by pressing and line welding. The hollow fibre separators are indicated in Fig 3 by reference numeral 6. Hereafter the formed anode~ladder can be cut into desired lengths .~ for the intended purpose.
As a variation of ..this embodiment, a 'certain length of a thread 1 provided with anode elements 2 (according to Fig 2) can be laid in S-loops with the anode elements in parallel between the bends, whereupon 'two connector rails 5 are attached at the bends.. Also, such a length of thread 1 provided with anode elements 2 can be wound around two connector rails 5.(plaeed at the desired distance from each other) end attached thereto so as to form the anode ladder of the type .shown in Fig 3.
Alternatives to the processes described above are possible. For example it would be possible to stamp out a complete ladder with cross bars and~aollector rails from a nickel sheet and then to provide it with. anode elements by pressing or sintering as~described above.
~'O 91/01046 ~ ~ ~ ~ ~ ~ -~. PCflSE90/00473 Furher, a comb-like structure fox the anode is feasible. Also a grid of nickel or other conductive material could be provided with rod-like anode elements covered with separators for forming the hollow fibres.
The construction of a practical primary cell or battery is shown in Figs 4 and 5.w ,, A hollow .fibre anodew 7 and a carbon cathode 8 (possibly based on a nickel grid and enclosed in a separator material), both provided with current con-nectors,,are placed in a suitable cavity'in a carrier 9. Several anodes 7 and cathodes 8 may of course be stacked. The carrier 9 with its contents is placed in a battery container 10 with lids, to which the current connectors of the electrodes are connected.' Prior to sealing electrolyte under pressure is added to the container. ~ ' ,, A practical embodiment of a secondary battery according to the invention is shown in Fig 6. In a metal can or container 11 a shaped cathode "12 ( of for example TiS2),is placed. A number of Li(Al) anodes 13, for example of the type depicted in Fig 2, are inserted in the cathode. fihe number of anodes may be seven: one central and six peripherically arranged. The threads or current connectors from the anodes l3 extend through a plastic spacer 14 to a metal lid or terminal 15, which is .electrically parted from the container 11 by a plastic isolator 16. Afte~c mounting electrolyte may'~be . ~ introduced.. through a filling port i7 in the container ~~,11: this port, is thereafter permanently~closed.' ;, .
Other.shapes and.sizes of,:the final battery may of I course be accomplished without difficulties.
.,, ,~ .
. Now a more detailed discussion of the Li(A1) alloy will be made. ,, . , . .
Lithium forms alloys with aluminium in~'different metallurgical, phases with ,different properties and ; ;, patterns. Generally the different phases are as .follows: alpha 0-10 atom%, alpha-beta 10-48 atom%, beta WO 91!01046 ~ ~ /~ ~ ~ PCT/SE90/00473 48-60 atom%, and gamma 60-70 atom% of lithium in aluminium.
Aluminium as host material for lithium has some advantages and disadvantages (which are most relevant for a secondary battery but also to a certain extent for a primary battery).' 1. The beta phase of lithium in'aluminium has a ;reduced potential compared to lithium, which means that . the alloy is'less corrosive towards the electrolyte.
Mofeover, the lithium is' actually dissolved in the aluminium leading to a lower aggressiveness than expected from the potential.'Alsa the voltage from a battery is somewhat reduced '(in the present case to about 2.$ V). r 2. A lithium/aluminium anode is fully reversible in contrast to a;pure lithium anode, which can suffer s from surface deposition and loss of active material.
3. The melting point of the Li(A1) alloy is signi-ficantly higher than for pure lithium. This is a clear advantage because it eliminates the tendency to melt the lithium, forming a highly aggressive melt. At short-circuiting vary high temperatures can result, and far this reason a high melting point is of great advantage. " ' 4. ~Li(Al) alloy is som~what brittle and can fall apart in conventional designs. This problem is in the present case overcome by placing the alloy in hollow fibres; which keep the anode grains in intimate~contact ensuring sufficient electrical contact throughout the . , anode .
.~..~.~ It has earlier bean considered especially ad--vantageous to utilize the cubic beta phase of the ,~.r lithium/aluminium-alloy, existing in alloys containing 50 atom% lithium, due to its fast lithium diffusion co . efficient, high melting point and low tendency to form ,. dendrites at' recharging. The'problem encountered is . that at cycling of such an alloy a dramatic loss of capacity occurs, as the structure collapses and the WO 91/01046 ~ /~ ~ ~ PCf/5~90/00473 , anode. falls apart. Attempts to solve this problem with binding additives have not been completely unsuccess-ful, but the volumetric capacity of the anode has been reduced dramatically.
. Hy the use of the hollow fibre concept it is possible to a certain extent to recycle a Li(A1) alloy " without disintegration.
.. However, it has now been found that the volumetric capacity of a Li(A1) alloy in relation to the ~lithi.um contents in the alloy is of great interest for optimiz-ing the results. ' Fig 7 is a graph, showing the volumetric capacity of lithium, stated in mAh/cm3 of the mixed alpha'beta phase of Li(Al) alloy versus the relative volume change . of the aluminium host. .., ,.~ The graph shows that~up to appr. 30 etom% lithium in the alloy the capacity rises very quickly,' whereas the .volume change is modest; the~inclination is in .,other words rather steep. Thereafter, especially up to appr. 4p atom% Li, the curve is much more level, which means that the capacity change is relatively low in comparison to the volume change, w ' At.discharge of~a Li(A1) alloy anode it is left in a more or less porous state depending on the discharge ;.;degree or depth. In other words the outer dimensions of the alloy do not change during discharge. The'physical " integrity of the discharged electrode is essential for the ,following charge,.and dischargesteps, which means that volume changes should be minimized~to ensures host integrity. and electrical conductivity. Optimum con ditions would be no.volume changes combined with,a high ,t intercalation.degree of lithium. A~~compromize is a . , mixed alpha beta phase between 6 ~ and ~ 50 atom%,' the preferred range being 10-32 atom%~ lithium;' where the ,first Figures .indicate. discharged state and the second ., ones charged state and where the remainder of~the anode r is.essentially. aluminium. Differently speaking~it is not possible - using the mixed alpha beta~phase of WO 91/01046 ~ CJ' ~ ~ ~ ,~ PCTISE90100473 hi(Al) alloy - to obtain smaller volume changes with a corresponding Li-capacity than betweeri'32 and 10 atom%.
The -following examples illustrate the advantages in a secondary battery of a lithium content of apprw 30 atom% in a Li(Al) alloy with regard to"cyclability, energy density and energy output.
Example 1 ,~ An electrochemical cell (7 cm3) consisting of 2.7 g of 30 atom% Li(A1) alloy (surface area ca 65 cm2) anode covered with a ~~microporous polypropylene separator, 8 g electrolyte (LiAlCl4, S02 1:6) and 1.5 g Ket~en black (15 weight% Teflon) cathode was .assembled in sandwich fashion in an SS battery container: Leads " and'collectors were all~nickel. The cell delivered 300 cycles .of 300 mAh (40 ~% depth of discharge) at the .,, discharge rate 5D0 mA; closed cell voltage'2.6 V, open cell .voltage 2.8 V.
,..Example 2 A comparable cell with a 50 atom% lithium anode . replacing the 30 atom%anode of example 1 delivered . under the same conditions 3' discharges. The anode was disintegrated. ' Example 3 A comparable cell with a 40 atom% lithium anode ... replacing the 30 atom% anode of example 1 delivered under the same conditions 15 discharges. The anode was disintegrated. ' ' ' Example 4 ' ., ,. A comparable cell with a'20 atom%'lithium anode . replacing the 30 atom% anode of example ~1'delivered under the same conditions~~300 discharges with a reduced depth of discharge. ~' The following examples' describe'~the ~ general .. ~ ~ ,. features in the manufacture of the ~ desired alloys mentioned ~in the first ~f~ur examples. Li(Al) alloys ,. oontaining a mixed alpha beta phase'is made by~melting appropriate amounts of metals in a~olosed container.
WO 91/01046 ~ - ~ ~ c~ ~ ~ ~ ~ PCT/SE90/00473 - 19~
. The alloy is solidified by cooling and then ground to 200 mesh, making the alloy fully homogeneous.
"., Example 5 ~ ' g of lithium (Lithco, 99%)' and 90 g of aluminium (Merck, 99.9%) ire placed in a stainless steel container and heated above the 'melting point 700°C for 15 min. The resulting liquid is cooled to room .temperature, and the resulting eutectic solid (mixed alpha beta phase)ris ground to'200 mesh, This ,,. homogene alloy~containing appr. 30 atom% Li and 70 atom% Al.is pressed into'anodes of desired' shape and . .. ~ used in example ~.l .
Example 6 ~ ' ,~ . .7 g of lithium (Lithco; 99%) and 27 g of aluminium . . ( Merck, 99 . 9% ) are treated ' as in 'example , 5 . .The ....resulting solid (pure beta phase) is ground to 200 mesh. This homogene alloy containing appr.~50 atom% Li and 50 atom% A1 is pressed into anodes of desired shape " and . used in example 2 . ' '' ' . . The last example describes an alternative to the manufacture~of~the alloys of the first four examples. .
Here the Li(A1) alloy containing a mixed alpha beta phase is made by an electroforming process. ' Exam;~le 7 , - ~ . . , , Aluminium (Merck, 99.9%) of the desired shape, coveradwith a polyprogylene~ separator~'(Celanese, Hoechst), and lithium (Lithco, 99%)~is dipped in an anhydrous electrolyte (i.e. 1 M LiCF3S03 in THF,' tetra-hydroforan), and external electrical contact between Li ,,...and Al~is established: When the desired lithiumWmount . has been charged.into the aluminium host, the anode is washed in anhydrous THF and is then''ready for use in , . , . any of the examples 1-9 . ' .. ' ~ ' . . . . i .r. -.The results so far obtained with laboratory'cells based o:. the 'teachings ~' above' (hollow ' fibre ~ concept, i,.,,,Li(Al)/S02 system and so forth) are promising. This the ..., following data are typical of the achievements : ~ energy density 275 Wh/1, power density 160 W/1, discharge 5 '~ o ~ ~ (~ ~ ~ PCC/SE90/00473 current 7.5 mA/cm2. The laboratory cells used have the dimension 50 x 16 x 9 mm.' ~ In a primary battery other aspects of the lithium contents of the Li(A1) anode are more important than .., those referred to above. Accordingly; in such a battery the lithium contents may be as high as 80~atom%.
FOR A LITHIUM BATTERY
Technical Field ,This invention relates to a method for producing a Li ( A1 ) anode fo=- a lithium , battery, in Which Li and A1 are pyrometallurgically alloyed in inert atmosphere and the formed alloy after~~ , cooling is ground to a homogeneous pouder.
Technical Background ~ , ' At the present time there is a growing interest for lithium batteries. The interest is not limited to primary batteriEa, which so far have been most common ' on the market, but is increasingly focused also on ' secondary batteries. Lithium metal is attractive as a battery ~ anode material 1 because of its light weight, high voltage, high electrochemical equivalence, and good conductivity.
' However, the use of pure lithium as anode material creates numerous and difficult problems, which are well known in the art. Especially, the difficulty with rechargeability and low malting point should be mentioned. The safety problems with batteries having pure lithium negative electrodes.can certainly not be neglected. ~ . '""
For improv:Lng the qualities of negative electrodes having lithium ~ as the ~ active material the . use __.of different lithium alloys has been investigated.
Especially the use of aluminium as host metal for the highly reactivelithium has been found to provide certain advantages, for .example with regard to the absence of dend:rite.formation and a high melting point.
" The present invention accordingly relates to a new and '~~ improved method for producing a Li(A1) anode for use in a primary or secondary battery.
WO 91/01046 ~ ~ ~ ~ PCT/S E90/00473 The production of a Li(A1) powder in the way set forth in the introduction above is known from Ge-A-1 484 650, but this powder is then pressed on a current conductive mesh. -In Journal of Electrochemical Society, Volume 124, No 10, 1977, M.L. Rao et al, "Lithium-Aluminium Electrode", p 1490-1492, a method to sinter Li(A1) powder on current conductive grids is disclosed.
In Journal of Electrochemical Society, Volume 131, No 8, 1984, A.S. Haranski et al, "The Cycling Effici-ency of Lithium-Aluminium Electrodes in Nonaqueous Media", p 1750-1755, the electrodeposition of lithium on aluminium or nickel wires is dosclosed.
By US-A-4 Oll 372 it is known to cast a Li(A1) alloy on a conductive thread.
.Also DE-A-1 049 949 regarding.the production cf a certain electrode by pressing active lead paste on a lead thread, followed by the step of providing the electrode with a separator should be mentioned as another example of the prior art.
All these publications fail ,to disclose ,any totally satisfactory method of practically producing a Li(Al) anode for a lithium battery with the properties and qualities now sought for. , The Invention Such a method is according to the, invention obtained in that the Li(A1) powder produced in the way set forth above is pressed or extruded to an elongated anode element around a. current conductive thread, prefezably of nickel, and that the anode element is provided with ,an enclosure of mlcroporous .separator material. ---The,enclosure can according to a further aspect of the~invention be provided in a,least two different caays: A separator material sheet. can be placed.' at either side of an anode complex, comprising anode elements and, connector rails, and pressed and line welded around the separate anode elements.
W~ 91101046 ~ ~ ~ ~ 4 ~ ~ PCTlSE90/00473 Alternatively and preferably, a plurality of separate anode elements at certain intervals on a current conductive thread is formed in a continuous process, including the provision of the enclosures of microporous separator material.
The utilized microporous separator material is quite sensitive. Accordingly, each anode element may be provided with a protective web or net outside the separator material, especially when the anodes are to be used for a secondary battery.
Brie~ Description of the Drawings ' The invention will be described in further detail below reference being made to the , accompanying drawings, in which Fig 1 illustrates a thread length with anode elements according to the invention thereon, Fig 2 shows an anode element to a larger scale, Fig 3 is a plan view of an embodiment of an anode according to the invention, Fig 4 is an exploded view illustrat-ing the formation of a certain battery, Fig 5 illustrates this battery with two lids prior to their attachment, Fig 6 is a cross-sectional view of another battery, and Fig 7 is a graph showing the volumetric capacity of lithium versus the relative volume change of an aluminium host.
Detailed Description of Preferred Embodiments Generally speaking, the invention is described in its application to a liquid electrolyte lithium'battery and especially a battery based on either of the following two lithium/sulphur dioxide systems:
1) Li / S02 + LiAlCl4 + C / C
2) Li / S02 ~ LiAlCl4 / TiS2 These systems have the important advantages of .providing high energy and power density. The first mentioned system is.best suited for a primary battery, whereas the second one can also~well be' used for a secondary,.i.e. rechargeable battery.
W~ 91/01046 ~ ~ ~ ~ ~ ~ pC~/g~90/00473 The reversible chemical reaction in a respective battery of any of these types has the following overall scheme:
1) 3 Li + 3 C + 3 S02 + LiAlCl4 ~-"~'-- LiCl-A1(S02)3-3C
+ 3LiC1 2) Li + TiS2~ LiTiS2 (in this case SO + LiA1C19 is a pure electrolyte not participating in the reaction) Due to the difficult problems with pure lithium as negative electrode or anode in any of these batteries the use of a host metal forming an alloy with the highly reactive lithium has been investigated: It -has been found that the use of aluminium as host metal gives advantages, especially the absence of dendrite formation. and a high melting point. Accordingly a lithium-aluminium alloy is used as anode in practical embodiments.. Further aspects of this choice will be dealt with below, but already now it may be stated that an Li(A1) alloy containing about 30 atom$ Li is pre-ferred in the' second system due to its unique r.e-chargeability.: . , . With Li(Al) as~anode a practical~cell voltage of 2.6 V is obtained in the first system and 1.8 V in the second system.
The cathode or positive electrode in a~ battery in 'thg first system is a high surface carbon black in combination with the liquid S02-LiA1C14~complex. Carbon black has a two-fold function in the battery: it acts as a complex binder for the reduced dorm of 502~(ef the reaction formula above) and.as an adsorbing agent for the 802-LiAlCl~ complex but also as the current collector in the cathode. In order to satisfy the demands the carbon material should have a high surface area, high density, a great number of active sites for the complex binding and aw good electric conductivity.
dt should further have a'high porosity providing space for the reaction products.
WO 91/01046 ~ ~ ~ ~ PCT/SE907b0473 Garbon black materials have been~found to fulfil ' these requirements, and the presently ' preferred material is .the commercially available product Ket~en Slack from Akzo. ~ ' In the second system the cathode is electrically conducting TiS2 or any other suitable metal sulphide, for example VZSS, MoS3 etC.
The electrolyte is 6S02-LiAlCl4, which requires a pressure of; some 2.atmospheres to become liquid. The electrolyte .Functions as an ion conductor in both systems and also as a depolarizer in the ~ primary system, which . poses special stoichiometric ~~and physical-chemical requirements. Thus, the quantity of S02 'is stoichiometrically .twice as big as that of ,LiAlCl4, which is necessary both toy ensure that the electrolyte ~.s ~ liquid down to -30oC ' ' and has an ,adequately low viscosity and can avoid drying out at . discharge in a primary system.
xhe separator in the battery shall effectively prevent electrical contact between anode and cathode but shall allow penetration of electrolyte and de-polarizer. It shall in this case be able to contain or store certain amounts of electrolyte. A commercially available microporous polypropylene plastic film having up to 70 % porosity, being free'of pinholes and posses-sing good physical strength,~has initially~been used.
It can also be possible to use a polyethylene ,,separator, but more promising results have been ,, obtained with the copolymer material ethylene-tetra fluoro-ethylene (ETFE). Practically, microporous Tefzel ~ (with a porosity of 40 %) from Soimat~Ltd, UK
has bean tested.. The material is stable in the battery environment, whereas its physical strength is~inferior to that of polypropylene. ' As will~appear more clearly below, ttje sbparator has. the form of hollow fibres in the anode complex of . the battery. Hollow fibres can also'be used For the cathode.
WO 91/01046 w ~ ~ ~ ~ ~ j ,~ PCT/SE90/00473 Summarizing, the battery according to the inven-tion works in the Li(A1)/SOZ system. It has an anode of Li(Al) alloy in hollow fibre separator. In the primary battery the electrolyte/cathode is LiA1C14~, ~ S02 and C.
., The discharge process for this battery system comprises oxidation of lithium, reduction of~sulphur dioxide and complex formation between electrolyte salt, sulphur dioxide and carbon. In the secondary battery the .. cathode is TiS2 or the likA, whereas the electrolyte, . .which does not take part in the~xeaction,~ is SO2 and LiA1C14. , . . ~ . . .
,. . The capacity of the first mentioned system is higher than that of the second one, but due to a certain risk for thermal run-away during charging of the first system it is only used for primary batteries.
A critical factor for the utilization'of the~anode electrode material in a battery is the active electrode surface. The cell power increases with increasing ,,,contact surface between electrode and electrolyte. In ,,, the present battery, a large surface has been accomp lashed .by the use of the so called "hollow fibre"
concept for 'the anode. Thisiaoncept~~is revealed in WO-A-87/01516 and can be characterized in that the anode: material is'shaped as a cylinder ~or~ similar elongated body with optional cross-section .and is encapsulated in an elastical, miaroporous separator material forming a hollow tube and that the anode elements are connected to an electrically conductive ., material '(for example nickel)'not taking part in the ., cell reaction. The cross-sectional dimension of the ,., hollow tube or fibre is preferably less than 3 mm.
Aa already mentioned 'an' anode material con ,, stituting about 30 ~atom% 'lithium in an alloy with aluminium~~has (together with the hollow fibre-concept) proven advantageous for .a ~rechargable battery. ~mhe reasons can be summarized as follows:
. , this alloy shows only small volume changes during charging and discharging, WO 91/01046 ~ ~ ~ ~ ~ ~ ~ P~I'/SE90/00473 - ~ the cylindrical shape enables volume changes to occur in two dimensions, so that lthe anode ' ' structure is not disintegrated, - the separator, design gives a physical compress~.on, - leading, to an increased integrity. for the anode structure during charge and discharge, and the Li(A1) alloy has a melting point over 600°C, which means that liquid and, strongly aggressive lithium cannot be set free. ,..
These factors are of special importance for the anode integrity, which is necessary to ensure that the anode material is rechargeable and secure.' '' The anode material can be manufactured in at least two -different ways, namely either electrochemical loading of lithium into aluminium (electroforming)..~~or pyrometallurgical fusion together of lithium and aluminium at n temperature of about 700°C or more.
. Although the first-mentioned method has certain advantages, the second one is presently preferred. -.-.
The fusion together of lithium and aluminium at 700°C requires an inert atmosphere (argon),' as both metals ,are aggressive relative to OZ and H20 and to a . ,lesser extent N2. The molten alloy is cooled off, ., whereafter it is ground in dry atmosphere (preferably less than 2 % humidity). The resulting powder can then be pressed (at a pressure of 6-ZO ton/cm2) 'in a hydraulic press around a central' nickel' wire to a parallelepipedical or cylindrical shape. An example of practical measurements are 1.4 x 1.8 x 50.0 mm. The anode is thereafter enclosed in a hollow fibre separator . , , , . . , , . , Further. particulars about the procedure are given below.
As an alternative to .pressing the powder into the ,desired shape a.sintering~process is feasible. Casting or extrusion is also possible.
WO 91!01046 ,. ~ c~ ~ fCf/SE90100473 In order to obtain the desired properties, for . example with regard to. high density, for the cathode material in the first system carbon black is mixed with Teflon ~ in proportions appr 80:20. In practice carbon powder, isopropanol, water and Teflon, suspension is mixed. The mixture is extruded, .dried and sintered.
After finely ~ dividing ~ the cathode, material it is ' ~ pressed or rolled~~onto~a~ current collecting net or the '" like, for example of nickel. The finished cathodes are enclosed in separator material of the same kind as used for the anodes.
In a practical case carbon cathodes~with dimen sions 50 x 15 mm and a'thickness of 1 - 2 mm are made.
. They contain some 0.3 - 0.5 g' carbon each and have a .porosity of 75 %. ' The electrolyte as described above can be prepared ., in that equimolar amounts of LiCl ~ and AlCl3 are mixed in a pressure vessel, whereupon S02 is added.
So far' the general properties of the different elements constituting the battery ~or cell in the Li(Al)/802 system as well as their manufacture are described.. Now the time has come to describe the physical construction of especially the anode., Lithium may be deposited on metallic aluminiuml~by electrochemical loading.' As has already been stated, ,.~~pyrometallurgical fusion together' of lithium and aluminium into Li(Al) alloy is however preferred.
. Examples of ways of constructing anodes~containing such allay is now described with reference~to Figs 1 and 2. ~ . ~ ' The process of manufacturing 'powdered alloy followed by pressing or sintering this ~~lloy~ on a ... ,conductive wire of for' example~nickel~'has been de scribed above. ' ' im~ an industrial process a conductive wire 1 (Fig 1 ) can be stepwise fed through a ~ press or sinter equipment and provided'~with anode elements '2 ~at "V~ 91/Oi04G ~ ~ ~ ~ ~ '1 ~ PCT/SE90/00473 intervals suitable for the following creation of complete anodes.
Referring to Fig 2, each anode~element 2 may be provided.; with a separator 3 according to the "hollow fibre"-concept., Due to the comparatively low. physical strength of the Tefzel ~ separator material it may be advantageous, especially if the battery is to be of the secondary type, to cover each anode element enclosed in separator material with a ~rein~orcing web or net 4, preferably but not necessarily of the same material. In s a practical case a number of filaments are braided directly on'each element.' The number of filaments may be fourteen.' After separation the anode elements 2 may be placed as cross-bars betwen two collector rails 5, as shown in Fig 3, and their conductive wires 1 are attached to the collector rails 5 by soldering or the like. If the anode elements 2 are not already provided with separators time has now come to do so by pressing and line welding. The hollow fibre separators are indicated in Fig 3 by reference numeral 6. Hereafter the formed anode~ladder can be cut into desired lengths .~ for the intended purpose.
As a variation of ..this embodiment, a 'certain length of a thread 1 provided with anode elements 2 (according to Fig 2) can be laid in S-loops with the anode elements in parallel between the bends, whereupon 'two connector rails 5 are attached at the bends.. Also, such a length of thread 1 provided with anode elements 2 can be wound around two connector rails 5.(plaeed at the desired distance from each other) end attached thereto so as to form the anode ladder of the type .shown in Fig 3.
Alternatives to the processes described above are possible. For example it would be possible to stamp out a complete ladder with cross bars and~aollector rails from a nickel sheet and then to provide it with. anode elements by pressing or sintering as~described above.
~'O 91/01046 ~ ~ ~ ~ ~ ~ -~. PCflSE90/00473 Furher, a comb-like structure fox the anode is feasible. Also a grid of nickel or other conductive material could be provided with rod-like anode elements covered with separators for forming the hollow fibres.
The construction of a practical primary cell or battery is shown in Figs 4 and 5.w ,, A hollow .fibre anodew 7 and a carbon cathode 8 (possibly based on a nickel grid and enclosed in a separator material), both provided with current con-nectors,,are placed in a suitable cavity'in a carrier 9. Several anodes 7 and cathodes 8 may of course be stacked. The carrier 9 with its contents is placed in a battery container 10 with lids, to which the current connectors of the electrodes are connected.' Prior to sealing electrolyte under pressure is added to the container. ~ ' ,, A practical embodiment of a secondary battery according to the invention is shown in Fig 6. In a metal can or container 11 a shaped cathode "12 ( of for example TiS2),is placed. A number of Li(Al) anodes 13, for example of the type depicted in Fig 2, are inserted in the cathode. fihe number of anodes may be seven: one central and six peripherically arranged. The threads or current connectors from the anodes l3 extend through a plastic spacer 14 to a metal lid or terminal 15, which is .electrically parted from the container 11 by a plastic isolator 16. Afte~c mounting electrolyte may'~be . ~ introduced.. through a filling port i7 in the container ~~,11: this port, is thereafter permanently~closed.' ;, .
Other.shapes and.sizes of,:the final battery may of I course be accomplished without difficulties.
.,, ,~ .
. Now a more detailed discussion of the Li(A1) alloy will be made. ,, . , . .
Lithium forms alloys with aluminium in~'different metallurgical, phases with ,different properties and ; ;, patterns. Generally the different phases are as .follows: alpha 0-10 atom%, alpha-beta 10-48 atom%, beta WO 91!01046 ~ ~ /~ ~ ~ PCT/SE90/00473 48-60 atom%, and gamma 60-70 atom% of lithium in aluminium.
Aluminium as host material for lithium has some advantages and disadvantages (which are most relevant for a secondary battery but also to a certain extent for a primary battery).' 1. The beta phase of lithium in'aluminium has a ;reduced potential compared to lithium, which means that . the alloy is'less corrosive towards the electrolyte.
Mofeover, the lithium is' actually dissolved in the aluminium leading to a lower aggressiveness than expected from the potential.'Alsa the voltage from a battery is somewhat reduced '(in the present case to about 2.$ V). r 2. A lithium/aluminium anode is fully reversible in contrast to a;pure lithium anode, which can suffer s from surface deposition and loss of active material.
3. The melting point of the Li(A1) alloy is signi-ficantly higher than for pure lithium. This is a clear advantage because it eliminates the tendency to melt the lithium, forming a highly aggressive melt. At short-circuiting vary high temperatures can result, and far this reason a high melting point is of great advantage. " ' 4. ~Li(Al) alloy is som~what brittle and can fall apart in conventional designs. This problem is in the present case overcome by placing the alloy in hollow fibres; which keep the anode grains in intimate~contact ensuring sufficient electrical contact throughout the . , anode .
.~..~.~ It has earlier bean considered especially ad--vantageous to utilize the cubic beta phase of the ,~.r lithium/aluminium-alloy, existing in alloys containing 50 atom% lithium, due to its fast lithium diffusion co . efficient, high melting point and low tendency to form ,. dendrites at' recharging. The'problem encountered is . that at cycling of such an alloy a dramatic loss of capacity occurs, as the structure collapses and the WO 91/01046 ~ /~ ~ ~ PCf/5~90/00473 , anode. falls apart. Attempts to solve this problem with binding additives have not been completely unsuccess-ful, but the volumetric capacity of the anode has been reduced dramatically.
. Hy the use of the hollow fibre concept it is possible to a certain extent to recycle a Li(A1) alloy " without disintegration.
.. However, it has now been found that the volumetric capacity of a Li(A1) alloy in relation to the ~lithi.um contents in the alloy is of great interest for optimiz-ing the results. ' Fig 7 is a graph, showing the volumetric capacity of lithium, stated in mAh/cm3 of the mixed alpha'beta phase of Li(Al) alloy versus the relative volume change . of the aluminium host. .., ,.~ The graph shows that~up to appr. 30 etom% lithium in the alloy the capacity rises very quickly,' whereas the .volume change is modest; the~inclination is in .,other words rather steep. Thereafter, especially up to appr. 4p atom% Li, the curve is much more level, which means that the capacity change is relatively low in comparison to the volume change, w ' At.discharge of~a Li(A1) alloy anode it is left in a more or less porous state depending on the discharge ;.;degree or depth. In other words the outer dimensions of the alloy do not change during discharge. The'physical " integrity of the discharged electrode is essential for the ,following charge,.and dischargesteps, which means that volume changes should be minimized~to ensures host integrity. and electrical conductivity. Optimum con ditions would be no.volume changes combined with,a high ,t intercalation.degree of lithium. A~~compromize is a . , mixed alpha beta phase between 6 ~ and ~ 50 atom%,' the preferred range being 10-32 atom%~ lithium;' where the ,first Figures .indicate. discharged state and the second ., ones charged state and where the remainder of~the anode r is.essentially. aluminium. Differently speaking~it is not possible - using the mixed alpha beta~phase of WO 91/01046 ~ CJ' ~ ~ ~ ,~ PCTISE90100473 hi(Al) alloy - to obtain smaller volume changes with a corresponding Li-capacity than betweeri'32 and 10 atom%.
The -following examples illustrate the advantages in a secondary battery of a lithium content of apprw 30 atom% in a Li(Al) alloy with regard to"cyclability, energy density and energy output.
Example 1 ,~ An electrochemical cell (7 cm3) consisting of 2.7 g of 30 atom% Li(A1) alloy (surface area ca 65 cm2) anode covered with a ~~microporous polypropylene separator, 8 g electrolyte (LiAlCl4, S02 1:6) and 1.5 g Ket~en black (15 weight% Teflon) cathode was .assembled in sandwich fashion in an SS battery container: Leads " and'collectors were all~nickel. The cell delivered 300 cycles .of 300 mAh (40 ~% depth of discharge) at the .,, discharge rate 5D0 mA; closed cell voltage'2.6 V, open cell .voltage 2.8 V.
,..Example 2 A comparable cell with a 50 atom% lithium anode . replacing the 30 atom%anode of example 1 delivered . under the same conditions 3' discharges. The anode was disintegrated. ' Example 3 A comparable cell with a 40 atom% lithium anode ... replacing the 30 atom% anode of example 1 delivered under the same conditions 15 discharges. The anode was disintegrated. ' ' ' Example 4 ' ., ,. A comparable cell with a'20 atom%'lithium anode . replacing the 30 atom% anode of example ~1'delivered under the same conditions~~300 discharges with a reduced depth of discharge. ~' The following examples' describe'~the ~ general .. ~ ~ ,. features in the manufacture of the ~ desired alloys mentioned ~in the first ~f~ur examples. Li(Al) alloys ,. oontaining a mixed alpha beta phase'is made by~melting appropriate amounts of metals in a~olosed container.
WO 91/01046 ~ - ~ ~ c~ ~ ~ ~ ~ PCT/SE90/00473 - 19~
. The alloy is solidified by cooling and then ground to 200 mesh, making the alloy fully homogeneous.
"., Example 5 ~ ' g of lithium (Lithco, 99%)' and 90 g of aluminium (Merck, 99.9%) ire placed in a stainless steel container and heated above the 'melting point 700°C for 15 min. The resulting liquid is cooled to room .temperature, and the resulting eutectic solid (mixed alpha beta phase)ris ground to'200 mesh, This ,,. homogene alloy~containing appr. 30 atom% Li and 70 atom% Al.is pressed into'anodes of desired' shape and . .. ~ used in example ~.l .
Example 6 ~ ' ,~ . .7 g of lithium (Lithco; 99%) and 27 g of aluminium . . ( Merck, 99 . 9% ) are treated ' as in 'example , 5 . .The ....resulting solid (pure beta phase) is ground to 200 mesh. This homogene alloy containing appr.~50 atom% Li and 50 atom% A1 is pressed into anodes of desired shape " and . used in example 2 . ' '' ' . . The last example describes an alternative to the manufacture~of~the alloys of the first four examples. .
Here the Li(A1) alloy containing a mixed alpha beta phase is made by an electroforming process. ' Exam;~le 7 , - ~ . . , , Aluminium (Merck, 99.9%) of the desired shape, coveradwith a polyprogylene~ separator~'(Celanese, Hoechst), and lithium (Lithco, 99%)~is dipped in an anhydrous electrolyte (i.e. 1 M LiCF3S03 in THF,' tetra-hydroforan), and external electrical contact between Li ,,...and Al~is established: When the desired lithiumWmount . has been charged.into the aluminium host, the anode is washed in anhydrous THF and is then''ready for use in , . , . any of the examples 1-9 . ' .. ' ~ ' . . . . i .r. -.The results so far obtained with laboratory'cells based o:. the 'teachings ~' above' (hollow ' fibre ~ concept, i,.,,,Li(Al)/S02 system and so forth) are promising. This the ..., following data are typical of the achievements : ~ energy density 275 Wh/1, power density 160 W/1, discharge 5 '~ o ~ ~ (~ ~ ~ PCC/SE90/00473 current 7.5 mA/cm2. The laboratory cells used have the dimension 50 x 16 x 9 mm.' ~ In a primary battery other aspects of the lithium contents of the Li(A1) anode are more important than .., those referred to above. Accordingly; in such a battery the lithium contents may be as high as 80~atom%.
Claims (3)
1. Method for producing a Li (A1) anode for a lithium battery, in which Li and Al are pyrometallurgically alloyed in inert atmosphere and the formed alloy after cooling is ground to a homogenous powder, characterized in that the powder is pressed or extruded to form an elongated anode element around a current conductive thread, which extends from at least one end of the anode element as a connector wire and in that the anode element is provided with an enclosure of microporous separator material wherein a plurality of separate anode elements at certain intervals on a current conductive thread are formed in a continuous process, including the provision of the enclosures of microporous separator material.
2. Method according to claim 1, wherein a plurality of separate anode elements are placed between two collector rails to form an anode complex characterized in that a separate material sheet is placed at either side of the anode complex and is pressed and line welded around the separate anode elements.
3. Method according to claim 1, characterized in that each anode element is provided with a protective web or net outside the separator material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8902461A SE8902461D0 (en) | 1989-07-06 | 1989-07-06 | METHOD FOR PRODUCING A LI (A1) ANODE FOR A LITHIUM BATTERY |
| SE8902461-6 | 1989-07-06 | ||
| PCT/SE1990/000473 WO1991001046A1 (en) | 1989-07-06 | 1990-07-02 | METHOD FOR PRODUCING A Li(Al) ANODE FOR A LITHIUM BATTERY |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2058431A1 CA2058431A1 (en) | 1991-01-07 |
| CA2058431C true CA2058431C (en) | 2000-12-05 |
Family
ID=20376503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058431A Expired - Fee Related CA2058431C (en) | 1989-07-06 | 1990-07-02 | Method for producing a li(a1) anode for a lithium battery |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5484461A (en) |
| EP (1) | EP0481010B1 (en) |
| JP (1) | JPH04506724A (en) |
| AT (1) | ATE113760T1 (en) |
| AU (1) | AU6156890A (en) |
| CA (1) | CA2058431C (en) |
| DE (1) | DE69013919T2 (en) |
| SE (1) | SE8902461D0 (en) |
| WO (1) | WO1991001046A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001284816A1 (en) * | 2000-08-10 | 2002-02-25 | Princeton University | Multifunctional battery and method of making the same |
| US9138831B2 (en) * | 2008-06-27 | 2015-09-22 | Lincoln Global, Inc. | Addition of rare earth elements to improve the performance of self shielded electrodes |
| RU2589742C1 (en) * | 2015-06-04 | 2016-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю.А." | Lithium-aluminium anode |
| US10199635B2 (en) * | 2016-09-22 | 2019-02-05 | Grst International Limited | Method of drying electrode assemblies |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1049949B (en) * | 1959-02-05 | Gottfried Hagen A.G., Köln-Kalk | Method for producing a tube filled with active material for accumulator tube plates and method for producing these plates | |
| US2251913A (en) * | 1938-04-01 | 1941-08-12 | Joseph B Brennan | Electrode for storage batteries |
| BE525687A (en) * | 1953-01-14 | |||
| US3957532A (en) * | 1974-06-20 | 1976-05-18 | The United States Of America As Represented By The United States Energy Research And Development Administration | Method of preparing an electrode material of lithium-aluminum alloy |
| US4011372A (en) * | 1975-12-09 | 1977-03-08 | The United States Of America As Represented By The United States Energy Research And Development Administration | Method of preparing a negative electrode including lithium alloy for use within a secondary electrochemical cell |
-
1989
- 1989-07-06 SE SE8902461A patent/SE8902461D0/en unknown
-
1990
- 1990-07-02 US US07/778,875 patent/US5484461A/en not_active Expired - Fee Related
- 1990-07-02 EP EP90911981A patent/EP0481010B1/en not_active Expired - Lifetime
- 1990-07-02 AT AT90911981T patent/ATE113760T1/en not_active IP Right Cessation
- 1990-07-02 JP JP2511248A patent/JPH04506724A/en active Pending
- 1990-07-02 AU AU61568/90A patent/AU6156890A/en not_active Abandoned
- 1990-07-02 CA CA002058431A patent/CA2058431C/en not_active Expired - Fee Related
- 1990-07-02 DE DE69013919T patent/DE69013919T2/en not_active Expired - Fee Related
- 1990-07-02 WO PCT/SE1990/000473 patent/WO1991001046A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU6156890A (en) | 1991-02-06 |
| WO1991001046A1 (en) | 1991-01-24 |
| EP0481010A1 (en) | 1992-04-22 |
| EP0481010B1 (en) | 1994-11-02 |
| JPH04506724A (en) | 1992-11-19 |
| ATE113760T1 (en) | 1994-11-15 |
| CA2058431A1 (en) | 1991-01-07 |
| SE8902461D0 (en) | 1989-07-06 |
| US5484461A (en) | 1996-01-16 |
| DE69013919T2 (en) | 1995-05-24 |
| DE69013919D1 (en) | 1994-12-08 |
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