US3689320A - Method for making a battery plate using cellulosic material - Google Patents
Method for making a battery plate using cellulosic material Download PDFInfo
- Publication number
- US3689320A US3689320A US20870A US3689320DA US3689320A US 3689320 A US3689320 A US 3689320A US 20870 A US20870 A US 20870A US 3689320D A US3689320D A US 3689320DA US 3689320 A US3689320 A US 3689320A
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- United States
- Prior art keywords
- metal
- nickel
- inch
- minutes
- porosity
- Prior art date
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- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title abstract description 34
- 238000000034 method Methods 0.000 title description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 61
- 239000002184 metal Substances 0.000 abstract description 61
- 239000004744 fabric Substances 0.000 abstract description 38
- 150000003839 salts Chemical class 0.000 abstract description 25
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 230000001427 coherent effect Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 239000012266 salt solution Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 27
- 229920000742 Cotton Polymers 0.000 description 24
- 229910052759 nickel Inorganic materials 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000005245 sintering Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 244000198134 Agave sisalana Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000011777 Corchorus aestuans Nutrition 0.000 description 4
- 235000010862 Corchorus capsularis Nutrition 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 240000008564 Boehmeria nivea Species 0.000 description 3
- 240000000491 Corchorus aestuans Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 240000004792 Corchorus capsularis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 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
- 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
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/10—Filter screens essentially made of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2027—Metallic material
- B01D39/2031—Metallic material the material being particulate
- B01D39/2034—Metallic material the material being particulate sintered or bonded by inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/002—Manufacture of articles essentially made from metallic fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
Definitions
- metal bodies in the form of knitted, woven or felted bodies such as mesh is desirable for many purposes including filters, catalyst supports, fuel cell electrodes, battery plates, etc.
- Porous sintered bodies can be produced from metal powders and mesh can be produced by weaving fine wire but such processes have been attended by commercial disadvantages, including high cost, insufficient strength and conductivity, limitations as to size and shape and other difficulties.
- the present invention is based upon the discovery of a relatively quick and inexpensive procedure adaptable to high production of porous metal bodies having a knitted, Woven or felted configuration.
- the invention comprises impregnating a natural cellulosic fibrous material or thread with a solution of one or more thermally decomposable metal salts, drying the impregnated material or thread, and by a single heating in a reducing atmosphere destroying the cellulosic material or thread, decomposing the salt or salts to metal and sintering the resultant metal to a coherent body.
- the invention is applicable to the production of porous sheets or threads of many different metals, but particularly to nickel, cobalt, iron and copper and alloys of these metals.
- suitable metals are tungsten, molybdenum, gold, silver, and metals of the platinum group.
- the metal salt must decompose completely and must not form any stable oxide, that is to say, one which is not reduced in the sintering atmosphere used.
- Suitable salts of nickel, iron, cobalt and copper are halides, for example, nickel chloride. Nitrates or complex salts of these metals may also be used.
- salts of dilferent metals are mixed together in solution. Generally, aqueous impregnating solutions are employed, so the im- 3,6893'20 Patented Sept. 5, 1972 pregnating salts should have substantial solubility in water.
- the fibrous material or thread must have adequate absorptive power for the impregnating salt solution, and it is essential for this reason that it must be a natural cellulosic material. Equivalent results are not obtained with synthetic cellulosic or polymeric fibers. Cotton and paper are particularly suitable, but jute, linen, ramie and sisal may also be used.
- the invention is particularly applicable to the production of very thin sheets of open-mesh metal, for which purpose the starting material may be any natural cellulosic fibrous material that is in the form of sheet, for example, a fabric, which may be woven, knitted or non-woven, or blotting paper; or again the natural cellulosic fibrous material may be cotton wool or paper pulp compressed into a sheet.
- a fabric which may be woven, knitted or non-woven, or blotting paper
- the natural cellulosic fibrous material may be cotton wool or paper pulp compressed into a sheet.
- the invention is also useful in the production of metal thread.
- it may be used in the production of other shaped porous bodies, for example, a catalyst support, the cellulosic material then advantageously being cotton, wool or paper pulp compressed into the' shape of the body.
- the fibrous body must be of such thickness and shape that the cellulosic material is completely removed by the heating in the reducing atmosphere.
- the heating to decompose the salt and sinter the metal is effected in a reducing atmosphere and it is surprising that the cellulosic material is completely removed during this heating. It is important that the carbon be removed, otherwise one does not achieve adequate strength in the porous metal sheet or thread, nor does one obtain the optimum conductivity. Heating may be conducted at a rapid rate, e.g., 800 C. per hour, With heating rates of 5 C. to about 35 C. per minute being satisfactory. The permissible rapid heating rate in a reducing atmosphere makes the process simple and adaptable to high production rates of porous metal in knitted, woven or felted configuration.
- Heating in an oxidising atmosphere to destroy the cellulosic material followed by heating in a reducing atmosphere to reduce the metal oxide formed leads to inferior products in terms of strength, conductivity, etc. Moreover, the overall time is much less when the metal is directly formed by decomposition of the salt in a reducing atmosphere.
- a sintering temperature of at least 900 C. is desirable, but the period during which the material is exposed to a temperature of 900 C. or more need not, and preferably does not, exceed 60 minutes.
- the product may, if desired, be resintered in order to increase its strength.
- sinter bonds are formed at the points where the metal fibers intersect and are in con-tact.
- the impregnation step may also be short, immersion for a few minutes, e.g., 5 or 10 minutes up to one or two hours, in a solution of the salt being enough, especially when the metal salt employed is soluble to the extent of about 50 grams (gm.) or more in cc. of water.
- Some cellulosic materials available as the starting materials are slightly greasy and, advantageously, these are first washed in water containing a surfactant.
- nickel chloride As the salt, Nickel sulfate, for example, does not yield so strong a product.
- the strength of the impregnating solution is not critical but we prefer a solution containing gm. of NiCl -6H O per 100 cc. of water, which will be referred to as the 120 gm. nickel chloride solution.
- the invention leads to products of high porosity, remarkable strength for such porous products and low electrical resistivity.
- the strengths are reported hereinafter as the force in grams required to break a strand or a strip 1 centimeter (cm.) wide when subjected to a straight tensile test.
- the porosities of the products are reported hereinafter as a percentage derived from a determination of the density of the product in a mercury balance, the balance being sensitive to all pores below 300 microns.
- Plaques made according to the invention have good bend strength and low electrical resistivity. These factors contribute good handling characteristics to the plaques and enable the production of cells having low internal resistance. Their porosity depends on the nature of the starting material and the processing conditions, but even when it is not so high as that of plaques of sintered powder, their electrical properties when converted into battery plates are better.
- the electrical resistance of a plaque according to the invention is less than that of one of the sheets from which it is made but, nevertheless, is essentially related to it, so the suitability of sheets for the production of plaques can be determined by ascertaining their resistivity.
- plaques it is preferred to bond the assembly of sheets together with both compacting and sintering.
- a plaque made by compactant alone, or by sintering an uncompacted assembly of sheets, may tend to delaminate in use, and battery plates made from such plaques may need to be specially supported to counteract this tendency.
- a preferred aspect of the invention is the production of plaques for alkaline batteries wherein porous metal sheets of nickel, iron, copper or cobalt produced in accordance with the invention are placed together in face to face relation and bonded together by compacting or sintering or both. It is found that such plaques, after suitable impregnation with active material, have surprisingly advantageous properties. Plaques of nickel are particularly useful in the production of plates for nickel-cadmium and nickel-iron batteries.
- the thermal treatment may comprise heating under oxidizing conditions to destroy the organic material, followed by a heating under reducing conditions, but better prod ucts are obtained when the thermal treatment comprises a single heating of metal salt impregnated natural cellulosic material in a reducing atmosphere to decompose the salt directly to metal, sintering the metal, and destroying the organic material at the same time.
- the organic material is preferably cotton or other natural cellulosic fibrous material, but when the metal is first oxidized and then reduced in the thermal treatment, the organic material is preferably a synthetic cellulosic material such as rayon, although much longer soaking times in the impregnating salt solution are then required.
- active mass may be introduced into nickel plaques by impregnating them with solutions of nickel salts and subsequently converting these to hydroxide by immersion with or without electrolysis in a solution of caustic alkali.
- the plaques may be filled initially with nickel hydroxide active mass, either by pressing the material into the plaques or treating the plaques with a slurry of nickel hydroxide which is taken up by the pores of the plaques. It will be understood that cadmium hydroxide may be put into the plaque to form a negative plate.
- the heating step in the production of the sheets was effected in a tube furnace ten feet long with an internal diameter of rectangular section 6.5 X 3 through which the impregnated and dried material was carried on a belt.
- Knitted cotton fabric was soaked in a solution of nickel chloride consisting of 60 gm.
- NiCl 6H O in 100 cc. water was then dried and passed continuously at a speed of one inch per minute through a sintering furnace in which the hot zone was held at a temperature of 1000 C., the residence time in this zone being 12 minutes. An atmosphere of cracked ammonia was maintained in the furnace.
- the product was a strong and flexible porous sheet of substantially pure nickel.
- the diameter of the cotton thread was from 0.01 to 0.02 inch and the aperture size of the original knitted fabric from 0.06 to 0.09 inch.
- the corresponding figures were 0.002 to 0.005 inch and 0.03 to 0.05 inch, respectively.
- the product had a porosity of 95.1%, a breaking strength of 170 gm. and a resistivity of 449 microhm-cm.
- EXAMPLE 2 A woven cotton cloth was impregnated in the same way as in Example 1 and sintered at 1.25 inches per minute at 1050 C., residence time 9.7 minutes.
- the diameter of the cotton thread was from 0.008 to 0.010 inch and the aperture size of the original cotton fabric was from 0.007 to 0.010 inch.
- the corresponding figures were each from 0.002 to 0.005 inch.
- the product porosity was 89.3%, the breaking strength 260 gm. and the resistivity 197 microhm-cm.
- EXAMPLE 3 Sheets of blotting paper approximately 12" x 6" x 0.019" were impregnated by immersion in nickel chloride solution gm. NiCl 6H O in 100 cc. water) for 5 minutes, removed from the solution, allowed to drain for 10 minutes to remove excess solution and then dried at 70 C. for 30 minutes.
- the dried sheets were sintered in the furnace at one inch per minute at 10.50 C. to give nickel sheets 0.0065 inch thick with a porosity of 81.8% and a resistivity of 159 microhm-cm. Seven of these sheets were assembled face to face and sintered for one hour at 1150 C. in hydrogen under a load of 0.10 gm./cm. to give a plaque 0.0354 inch thick with a porosity of 72.8% and a bend strength of 258 kg./cm.
- EXAMPLE 4 A sheet of cotton wool approximately 12" x 6" x 1.25" was immersed in the 120 gm. nickel chloride solution for 5 minutes, removed and pressed between two plates under a weight of 14 pounds (0.194 pound per square inch) for 5 minutes to remove excess solution. The pressed sheet was dried at 70 C. for 22 hours to give a final thickness of 0.181 inch. The dried sheet was then sintered at one inch per minute at 1050 C. in the furnace to give a porous nickel plaque 0.074 inch thick with a porosity of 88%, bend strength over two supports 0.75 inch apart 33 kg./cm. resistivity 320 microhm-cm. After resintering at one inch per minutes at 1150 C. to increase the strength, the porosity fell to 86%, the bend strength was 44.7 kg./cm. and the resistivity 193 microhm-cm.
- Impregnated paper pulp was produced by agitating flock used for chemical filtration in the 120 gm. nickel chloride solution. A mat produced from the pulp was pressed between two plates under a load of 0.204 pound per square inch for 5 minutes to remove excess solution. The sheet of pressed mat was dried for 16 hours at 70 C. to give a final thickness of about 0.200 inch and then sintered for 30 minutes at 1050 C. in cracked ammonia to give a nickel plaque 0.056 inch thick with a porosity of 90.6%.
- Cotton string 0.091 inch diameter was impregnated by immersion in the 120 gm. nickel chloride solution for minutes, dried and sintered at 1050 C. (9.7 minutes in the hot zone).
- the resultant nickel thread had a diameter of 0.053 inch, a porosity of 85.5%, a breaking Strength of 232 gm. and a resistivity of 634 microhm-cm.
- EXAMPLE 7 Sisal string 0.190 inch diameter treated in the same way as the cotton string in Example 6 had a diameter of 0.085 inch, a porosity of 91.8%, a breaking strength of 671 gm. and a resistivity of 104 microhm-cm.
- EXAMPLE 9 This shows the use of another nickel salt as the source of the nickel.
- a woven cotton fabric with a warp count of 72 and a weft count of 60 was immersed for 10 minutes in 100 cc. of water containing 38 grams of nickel sulfate (NiSO -6H O), dried at 70 C. in air and sintered with a residence time of 9.7 minutes in the hot zone at 1050 C.
- the product was nickel mesh of 95.8% porosity but of very low strength, resistivity 5,000 microhm-cm. Increasing the impregnation time to 18 hours gave 94.2% porosity, breaking strength 26.4 gm. and resistivity 941 microhm-cm.
- EXAMPLE 10 This is an example of the production of an alloy mesh.
- a piece of the same 72/60 cotton fabric as in Example 9 was impregnated in a solution of 124.4 gm. NiCl -6H O and 35.6 gm. CuCl -2H O in 100 cc. of water for 10 minutes, dried at 70 C. in air and sintered with a residence time of 9.7 minutes in the hot zone at 1050 C.
- the product was mesh of an alloy containing 70% nickel and 30% copper with a porosity of 95.3%.
- the mesh was resintered at 1050 C. for 9.7 minutes to strengthen it, and the porosity fell to 88.2%, with breaking strength 226 gm. and a resistivity 3,020 microhm-cm. resulting.
- Cotton fabric having 72 warp threads and 60 weft threads to the inch was impregnated for 10 minutes at room temperature in a solution of 80 gm. ferric chloride in 100 cc. of water, dried in air at 70 C. and sintered with a residence time of 8 minutes in the hot zone at 6 1050 C.
- the product was iron mesh with a porosity of 96.9%.
- Twelve such sheets can be sintered together face to face at 1100 C. to form a battery plaque.
- Example 12 Fabric as in Example 11 was impregnated with a solution of 100 gm. copper chloride (CuCl -2H O) in 100 cc. of water. The product was copper mesh with a porosity of 95.6%. Twelve sheets of this mesh can be sintered together face to face at 1000 C. to form a plaque.
- CuCl -2H O copper chloride
- Example 13 Fabric as in Example 11 was impregnated in a solution consisting of 40 gm. ammonium molybdate in 100 cc. water. The product was a molybdenum mesh with a porosity of 96.9%, which fell to 92.2% when the product was sintered for 6 hours at 1300 C. in hydrogen. The breaking strength was 427 gm. and the resistivity 1,214 microhm-cm.
- EXAMPLE 14 Fabric as in Example 11 was impregnated in a solution consisting of 10 gm. of platinum as ammonium chloroplatinate in cc. of water. After soaking for 10 minutes at 70 C., the fabric was dried and sintered at 1050 C. in cracked ammonia while passing through the furnace at the rate of one inch per minute, so that its residence time in the hot zone was 12 minutes.
- the product was platinum mesh having a porousity of 97.3%, a breaking strength of 29 gm. and a resistivity of 1,937 microhm-cm.
- Example 15 Fabric as in Example 11 was impregnated for 10 minutes in a solution containing 60 gm. of silver nitrate in cc. of water. The dried fabric was sintered 30 minutes at 900 C. in a cracked ammonia atmosphere. The product was silver mesh 0.006 inch thick with a porosity of 94.7%, a resistivity of 28.6 microhm-cm., and a breaking load of 504.6 grams.
- EXAMPLE 16 Products were made by immersion of fabrics for 10 minutes in the gm. nickel chloride solution, air-drying at 70 C. and sintering with a residence time of 9.7 minutes in the hot zone at 1050 C. Further products were made by an oxidation-reduction thermal process wherein fabrics were immersed for 18 hours in nickel chloride solution (102.2 gm. NiCl '6I-I O in 100 ml. water), airdried at 70 C., heated in air at 10 C. per hour to 375 C., held at this temperature for 24 hours, heated in hydrogen for /2 hour at 400 C., raised at 25 C. per hour to 800 C., and held at this temperature for 30 minutes.
- nickel chloride solution (102.2 gm. NiCl '6I-I O in 100 ml. water)
- A 40/40 cotton
- B a cotton fabric with 72 warp and 60 weft threads per inch
- C rayon fabric with 76 warp and 41 weft threads per inch
- the products A1, B1 and C1 were made by the direct heating in cracked ammonia atmosphere and the products A2, B2 and C2 by the oxidationreduction thermal process.
- TAB LE I Resistivity, Porosity, microhm- Strength percent cm. gm./cm.
- EXAMPLE 17 The improved properties obtained in plates according to the invention in comparison with those of plates of sintered nickel powder are shown in Table II below.
- Table II four plates 1 to 4 made according to the invention are compared with a plate 5 made by sintering nickel powder to both sides of woven nickel mesh.
- Plates 1 and 2 were made by sintering sheets themselves made from further pieces of the cotton fabric A, plates 3 and 4 from cotton fabric B, in the way described in Example 11 to produce sheets, and then sintering the sheets in face to face relation under a load of gm./cm. for one hour at 1150 C. in hydrogen, plates 1 and 2 being made from plaques comprising 10 sheets and plates 3 and 4 from plaques comprising 12 sheets.
- Plate 5 was made by sintering nickel powder on each side of a sheet of woven nickel mesh. The sintered plaques and the sintered powder were chemically impregnated with nickel hydroxide by a method involving seven cycles of conventional procedure.
- Table II shows the porosity, the bend strength, the resistivity and the thickness of the five plates. It also shows the electrical properties. Since the thicknesses differed, the table further shows the capacity adjusted to a thickness of 0.040 inch in each case, so that a proper comparison of the capacities may be made.
- threads may be used as metallic reinforcement in composite metal, plastic, glass and ceramic structures, or to provide a conductive path through plastics or other nonmetallic materials.
- the products of the invention may also be used as, or in, mechanicaland sound-damping materials, and magnetic screening materials.
- Decoration may be produced on metal strip by rolling mesh of the invention into it and developing contrasting colors by chemical treatment.
- a method of producing a porous metal product which comprises impregnating a natural cellulosic fibrous material with one or more thermally decomposable metal salts of a metal from the group consisting of nickel, cobalt, iron, copper, tungsten, molybdenum, gold, silver and platinum group metals by immersing said material in an aqueous solution of said metal salt, drying the impregnated material and heating the dried material at a rapid rate of at least about 5 C. per minute in a single operation to a temperature of at least about 900 C. in a flowing gaseous atmosphere reducing to said metal to destroy the cellulosic material and to completely remove the carbon, to decompose the salt or salts to metal and to sinter the resultant metal to a coherent body.
- a metal from the group consisting of nickel, cobalt, iron, copper, tungsten, molybdenum, gold, silver and platinum group metals
- the warp and the weft can be of threads of difierent sizes, and by using such a starting fabric, a metal fabric can be made in which, for example, the warp is of larger-diameter threads than the weft.
- the sheets can with advantage be so orientated that the largerdiameter metal threads of the warp run in the most advantageous direction of the current flow, since these will have superior conductance to the metal threads of the weft.
- the warp or the weft consists wholly or partially of a number of metal wires, the remainder of the fabric being of organic fibers.
- the original metal wires will have greater density than, and superior conductance to, those of the metal threads formed on the organic fibers.
- Threads or pieces of mesh produced by the invention may be incorporated in the active mass of pocket and tubular electrodes to replace graphite or metallic flake.
- sheets produced according to the invention are as eletrodes for fuel cells, catalyst supports and filters.
- the careful stacking of meshes of varying aperture can provide an electrode with conical pores.
- the meshes should have the same thread count but the threads will be of different diameters.
- Threads produced according to the invention may be woven into suitable products. Either the sheets or the 2.
- the cellulosic material is selected from the group consisting of cotton, paper, jute, linen, ramie and sisal.
- the method for producing a plaque for an alkaline battery plate which comprises impregnating a porous sheet of natural cellulosic material by immersing said material in a solution of a metal salt of at least one metal from the group consisting of nickel, iron, copper and cobalt, drying the impregnated sheet, decomposing the metal salt to metal by a single thermal treatment in a flowing gaseous atmosphere reducing to said metal, at a rapid heating rate of at least 5 C. per minute, at a temperature of at least about 900 C.
- cellulosic material is a natural material from the group consisting of cotton, paper, jute, linen, ramie and sisal.
- tel-y plaque is formed by bonding a plurality of porous 1,423,9 7 8 7/ 1922 Weintraub. sheet-form bodies together using both heat and pressure. 3,388,004 6/ 1968 Rosenblatt.
- Line 63 for "10.50 read --10 50--. Col. 5, line 8 for "minutes” read mimite- -r Line 29, for "232 gm” read 467 gmand for "634 microhm-cm” read l57 -microhm-cm--.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3803667 | 1967-08-17 | ||
GB08697/68A GB1183642A (en) | 1967-08-17 | 1967-08-17 | Manufacture of Porous Metal Products |
Publications (1)
Publication Number | Publication Date |
---|---|
US3689320A true US3689320A (en) | 1972-09-05 |
Family
ID=26253549
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US20870A Expired - Lifetime US3689320A (en) | 1967-08-17 | 1970-03-25 | Method for making a battery plate using cellulosic material |
Country Status (9)
Country | Link |
---|---|
US (1) | US3689320A (de) |
BE (2) | BE719581A (de) |
CH (2) | CH499887A (de) |
DE (1) | DE1758827C3 (de) |
ES (2) | ES357287A1 (de) |
FR (2) | FR1578407A (de) |
GB (1) | GB1183642A (de) |
NL (2) | NL6811574A (de) |
SE (1) | SE358662B (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6099880A (en) * | 1999-05-24 | 2000-08-08 | Nabisco, Inc. | Variable-width swirl pattern in candy |
WO2002062511A1 (en) * | 2001-02-05 | 2002-08-15 | Porvair Plc | Co-forming metal foam articles |
WO2006002834A2 (en) * | 2004-06-25 | 2006-01-12 | Inco Limited | Open porous metallic foam body and method for manufacturing |
US20080029919A1 (en) * | 2004-04-08 | 2008-02-07 | Tesa Ag | Method for Permanently Obturating Holes, Especially in Metal Sheets of Plastic Part of an Automobile |
US7328831B1 (en) | 2004-06-25 | 2008-02-12 | Porvair Plc | Method of making a brazed metal article and the article formed thereby |
WO2009016473A2 (en) * | 2007-08-01 | 2009-02-05 | Nagarjuna Energy Private Limited | A process for preventing polymerization of cracked volatile products during pyrolysis and gasification |
WO2019018489A1 (en) * | 2017-07-19 | 2019-01-24 | Battelle Energy Alliance, Llc | THREE-DIMENSIONAL STRUCTURE ANODE, DIRECT CARBON CONVERSION FUEL CELL COMPRISING THE THREE-DIMENSIONAL STRUCTURE ANODE, AND ASSOCIATED METHODS |
JP2020534434A (ja) * | 2017-09-19 | 2020-11-26 | アランタム ヨーロッパ ゲーエムベーハーAlantum Europe Gmbh | 表面改質された金属製の開孔成型体の製造方法、および該方法により製造された成型体 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1150542B (de) * | 1958-01-16 | 1963-06-20 | Zahn Hermann | Brennstoffbehaelter fuer ein Gasfeuerzeug |
US4175153A (en) * | 1978-05-16 | 1979-11-20 | Monsanto Company | Inorganic anisotropic hollow fibers |
-
1967
- 1967-08-17 GB GB08697/68A patent/GB1183642A/en not_active Expired
-
1968
- 1968-08-05 CH CH1169568A patent/CH499887A/fr not_active IP Right Cessation
- 1968-08-05 CH CH1169668A patent/CH485026A/fr not_active IP Right Cessation
- 1968-08-14 FR FR1578407D patent/FR1578407A/fr not_active Expired
- 1968-08-14 FR FR1579742D patent/FR1579742A/fr not_active Expired
- 1968-08-14 NL NL6811574A patent/NL6811574A/xx unknown
- 1968-08-14 NL NL6811536A patent/NL6811536A/xx unknown
- 1968-08-16 DE DE1758827A patent/DE1758827C3/de not_active Expired
- 1968-08-16 BE BE719581D patent/BE719581A/xx unknown
- 1968-08-16 BE BE719580D patent/BE719580A/xx unknown
- 1968-08-16 ES ES357287A patent/ES357287A1/es not_active Expired
- 1968-08-16 ES ES357286A patent/ES357286A1/es not_active Expired
- 1968-08-19 SE SE11120/68A patent/SE358662B/xx unknown
-
1970
- 1970-03-25 US US20870A patent/US3689320A/en not_active Expired - Lifetime
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6099880A (en) * | 1999-05-24 | 2000-08-08 | Nabisco, Inc. | Variable-width swirl pattern in candy |
WO2002062511A1 (en) * | 2001-02-05 | 2002-08-15 | Porvair Plc | Co-forming metal foam articles |
US6706239B2 (en) | 2001-02-05 | 2004-03-16 | Porvair Plc | Method of co-forming metal foam articles and the articles formed by the method thereof |
US20080029919A1 (en) * | 2004-04-08 | 2008-02-07 | Tesa Ag | Method for Permanently Obturating Holes, Especially in Metal Sheets of Plastic Part of an Automobile |
US7328831B1 (en) | 2004-06-25 | 2008-02-12 | Porvair Plc | Method of making a brazed metal article and the article formed thereby |
JP2008502798A (ja) * | 2004-06-25 | 2008-01-31 | シーブイアールディ、インコ、リミテッド | 開孔金属発泡体および製造方法 |
US20080031767A1 (en) * | 2004-06-25 | 2008-02-07 | Inco Limited | Open Porous Metallic Foam Body And Method For Manufacturing |
WO2006002834A3 (en) * | 2004-06-25 | 2006-06-22 | Inco Ltd | Open porous metallic foam body and method for manufacturing |
WO2006002834A2 (en) * | 2004-06-25 | 2006-01-12 | Inco Limited | Open porous metallic foam body and method for manufacturing |
KR100865431B1 (ko) * | 2004-06-25 | 2008-10-24 | 베일 인코 리미티드 | 열린 기공 금속 발포체 및 그 제조 방법 |
CN100510130C (zh) * | 2004-06-25 | 2009-07-08 | 维尔国际有限公司 | 开孔金属泡沫体及其制备方法 |
US7951246B2 (en) * | 2004-06-25 | 2011-05-31 | Alantum Corporation | Method for manufacturing open porous metallic foam body |
WO2009016473A2 (en) * | 2007-08-01 | 2009-02-05 | Nagarjuna Energy Private Limited | A process for preventing polymerization of cracked volatile products during pyrolysis and gasification |
WO2009016473A3 (en) * | 2007-08-01 | 2010-01-14 | Nagarjuna Energy Private Limited | A process for preventing polymerization of cracked volatile products during pyrolysis and gasification |
WO2019018489A1 (en) * | 2017-07-19 | 2019-01-24 | Battelle Energy Alliance, Llc | THREE-DIMENSIONAL STRUCTURE ANODE, DIRECT CARBON CONVERSION FUEL CELL COMPRISING THE THREE-DIMENSIONAL STRUCTURE ANODE, AND ASSOCIATED METHODS |
US11342564B2 (en) | 2017-07-19 | 2022-05-24 | Battelle Energy Alliance, Llc | Three-dimensional architectured anode, a direct carbon fuel cell including the three-dimensional architectured anode, and related methods |
JP2020534434A (ja) * | 2017-09-19 | 2020-11-26 | アランタム ヨーロッパ ゲーエムベーハーAlantum Europe Gmbh | 表面改質された金属製の開孔成型体の製造方法、および該方法により製造された成型体 |
Also Published As
Publication number | Publication date |
---|---|
BE719580A (de) | 1969-02-17 |
ES357286A1 (es) | 1970-03-16 |
NL6811574A (de) | 1969-02-19 |
BE719581A (de) | 1969-02-17 |
SE358662B (de) | 1973-08-06 |
ES357287A1 (es) | 1970-04-01 |
NL6811536A (de) | 1969-02-19 |
CH485026A (fr) | 1970-01-31 |
GB1183642A (en) | 1970-03-11 |
FR1579742A (de) | 1969-08-29 |
DE1758827B2 (de) | 1973-10-11 |
DE1758827A1 (de) | 1972-04-06 |
FR1578407A (de) | 1969-08-14 |
DE1758827C3 (de) | 1974-05-09 |
CH499887A (fr) | 1970-11-30 |
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