USH2121H1 - High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof - Google Patents
High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof Download PDFInfo
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- USH2121H1 USH2121H1 US09/689,700 US68970000A USH2121H US H2121 H1 USH2121 H1 US H2121H1 US 68970000 A US68970000 A US 68970000A US H2121 H USH2121 H US H2121H
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- United States
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- manganese oxide
- gel
- oxide material
- organic solvent
- birnessite
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 112
- 239000011148 porous material Substances 0.000 title claims abstract description 38
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000004964 aerogel Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims 5
- 239000002086 nanomaterial Substances 0.000 claims 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 46
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 81
- 229910052744 lithium Inorganic materials 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- -1 CoO2 Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910016978 MnOx Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000004375 physisorption Methods 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical class [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 239000004967 Metal oxide aerogel Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000495 cryogel Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910003007 LixMnO2 Inorganic materials 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000001744 Sodium fumarate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MSJMDZAOKORVFC-SEPHDYHBSA-L disodium fumarate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C\C([O-])=O MSJMDZAOKORVFC-SEPHDYHBSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940005573 sodium fumarate Drugs 0.000 description 1
- 235000019294 sodium fumarate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
Definitions
- the present invention relates to methods for making high surface area, nanoscale, mesoporous manganese oxide materials with controlled solid-pore architecture.
- manganese oxide materials have been studied as intercalation hosts for lithium batteries (Thackeray, 1997), which can provide voltages of 3 to 5 volts.
- the intense interest in manganese oxide as a battery material is because of its low cost and low toxicity relative to other high performance metal oxide battery materials such as NiO 2 , CoO 2 , and V 2 O 5 .
- the discharge processes at MnO 2 are accomplished by the intercalation of either protons or lithium cations into the MnO 2 structure. This process is accompanied by a simultaneous reduction of the manganese sites to maintain charge balance:
- the protons or lithium ions intercalated into the MnO 2 structure are supplied by the electrolyte at the electrode/electrolyte interface. Charge storage is further facilitated by diffusion of protons or lithium cations though the bulk of the structure.
- MnO 2 materials are relatively inexpensive and are currently used in commercial batteries, some problems remain, particularly with respect to lithium battery applications.
- electrodes made from manganese oxide spinels have poor conductivity and require the addition of conductive fillers such as carbon to enhance conductivity.
- adding such fillers reduces the energy density of the electrode.
- recharging the cells requires applying a voltage which exceeds the discharge terminal voltage of the cell.
- the result, for cells having such manganese-oxide spinel cathodes is that it takes at least 4.1 volts (and preferably more) to de-intercalate lithium from the electrode during charging of the cell. Above about 4.5 volts, however, the solvents used as the electrolyte oxidize and decompose. It is, therefore, necessary to control the charging voltage of these cells below the decomposition potential of the solvent in order to prevent its degradation.
- the reversible capacity and cycle life of spinel-based cathodes are sensitive to overcharge and over-discharge.
- Discharge of the manganese oxide spinel cells must be cut off when the terminal voltage falls to about 3.4 volts (thus limiting the capacity of the material, which typically peaks at about 140 mAh/g).
- the spinel form of the manganese oxide undergoes structural transformation when additional lithium is inserted into LiMn 2 O 4 and it converts to the orthorhombic form which has very poor cycle ability, and is very unstable, causing the formation of other manganese oxides which are not electrochemically active.
- Charge/discharge rates and the capacity achieved at those rates are in part determined by the transport of protons or lithium cations through the MnO 2 structure.
- Sol-gel-derived manganese oxides are typically microporous, based on the tendency of MnO2 to form tunnel or layered structures. Intercalating cations must also be transported through the micropores. The small pore size can limit the accessability of electrolyte to the MnO 2 interface, particularly for the large (relative to the proton) lithium cations.
- Manganese oxide can be produced in a variety of forms, the most common form for battery materials being electrolytic manganese dioxide (EMD) (Chabre et al., 1995). EMD is prepared by anodic electrodeposition from manganese (II) salts. Although EMD has been used in alkaline batteries for many years, recent investigations have shown that it is not optimal for lithium battery applications (Bach et al., 1992). Some efforts have been made to improve the surface area and porosity of EMD (Kurimoto et al., 1995).
- Manganese oxides have also been prepared by a variety of sol-gel approaches (Manthiram et al., 1998).
- Sol-gel chemistry provides a flexible, low temperature process for preparing metal oxides.
- Another advantage of sol-gel chemistry is that dopant ions can be mixed uniformly in the manganese sol to improve the electrochemical and structural properties of the manganese oxide. Under the appropriate reaction conditions, the sol-to-gel transition can occur so that the metal oxide sol forms a highly porous three-dimensional network. Removal of the pore fluid exclusively by evaporation typically collapses the porous structure due to the large capillary forces exerted on the gel structure at the liquid-gas interface.
- Aerogels are prepared by taking the pore fluid supercritical, wherein there is no longer a liquid-gas interface (Huesing et al., 1998). When supercritical CO 2 drying is preferred, the pore liquid of the wet gel is replaced with liquid CO 2 , which is then taken supercritical. Aerogels of V 2 O 5 have been prepared that exhibit both high surface areas and high porosities (Salloux et al., 1995; Le et al., 1996; Le et al., 1995).
- Lynch in U.S. Pat. No. 3,977,993, discloses preparing metal oxide aerogels by introducing an aqueous slurry of a hydrogel into an organic solvent such as ethanol until substantially all of the water in the hydrogel is displaced by the organic solvent. The organic solvent is then treated to render it rigorously anhydrous. The organic solvent is removed therefrom by heating the mixture to above the critical point and releasing the organic solvent therefrom at a pressure at least equal to the critical pressure of the organic solvent.
- an organic solvent such as ethanol
- Tillotson et al. in U.S. Pat. Nos. 5,275,796 and 5,409,683; describe a two-step hydrolysis condensation method to form metal oxide aerogels.
- a high purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. Aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and directly extracting the nonalcoholic solvent.
- Hupe et al. in U.S. Pat. No. 4,894,357, disclose that the structural and/or surface characteristics of metal oxides can be adjusted by dehydrating a water-containing oxide gel under supercritical conditions by extracting the water with an extraction agent such as carbon dioxide at a pressure above the critical pressure of the extraction agent.
- Dasgupta et al., 5,601,952 disclose preparing lithium-manganese oxide compounds which can be used in a non-aqueous rechargeable lithium battery.
- a gel of lithium manganese oxide is prepared in a water-miscible organic solvent such as an alcohol. The gel is dried and, depending upon the method of liquid removal a xerogel, aerogel, sonogel, or cryogel is obtained.
- manganese oxide materials are prepared using sol-gel chemistry.
- MnO 2 gels derived from the same sol exhibit markedly different final structure, based upon how the pore fluid is removed from the gel.
- MnO 2 materials Two new classes of MnO 2 materials have been prepared, in which the mesoporous structure of the initial gel is maintained by removing the pore liquid under conditions where the capillary forces that result from removal or pore liquid are either low, forming a MnO 2 ambigel, or extremely low, forming a MnO 2 aerogel. These materials are particularly useful in alkaline and lithium batteries.
- FIGS. 1 and 3 show the pore diameter versus incremental surface area of the various gels prepared according to the present invention for the cryptomelane and birnessite polymorphs of manganese oxide ambigels and aerogels. Manganese oxide xerogel results have been included for: prior art comparison purposes only.
- FIGS. 2 and 4 show the pore diameter versus incremental pore volume of the various gels prepared according to the present invention for the cryptomelane and birnessite polymorphs of manganese oxide ambigels and aerogels. Manganese oxide xerogel results have been included for prior art comparison purposes only.
- MnO 2 gels Different types can be prepared from MnO 2 gels by removing the pore liquid from the gels by methods that differ in the magnitude of liquid-vapor forces that are established in the pores, i.e., the-magnitude of capillary pressures that develop (Long et al., 2000).
- the choice of method for removing the pore liquid from the MnO 2 gels allows one to control the final pore structure of the MnO 2 gel.
- Classically prepared MnO 2 xerogels of cryptomelane and birnessite have very high specific surface areas ( ⁇ 200 m 2 g ⁇ 1 ) that are concentrated in pores less than 10nm in size.
- the MnO 2 aerogels and ambigels, as described in the present invention, have similarly high surface areas but which are distributed in a mesoporous structure with pore sizes from about 3 nm to about 100 nm. These MnO 2 aerogels and ambigels also exhibit higher specific pore volumes relative to the xerogel.
- the structure of the mesoporous network of the MnO 2 aerogels and ambigels will optimize the supply of proton or lithium cation from the supporting electrolyte filling the pores to the nanoscale MnO 2 domains in the gel network.
- Data in the electrochemical literature indicate that ionic conductivity into micropores is lower by orders of magnitude than that in open electrolyte [Koresh and Soffer, 1977].
- Microporous surface area in RuO 2 -based anodes does not contribute to electroactivity [Ardizzone et al., 1982].
- MnO 2 ambigels can be obtained in the form of stable monoliths, which, although collapsed to about 30% of their original dimensions; still retain a large cumulative pore volume relative to the aerogel.
- Nanoscale MnO 2 materials are typically prepared using a sol-gel method that includes reducing a permanganate or substantially equivalent compound by an organic reducing agent in aqueous solution,. as disclosed by Bach et al., 1990.
- the permanganate used to form MnO 2 has a standard potential of about +1.7 V (versus H 2 /H + at 0.0 V). Therefore, any organic reducing agent with a potential less negative than +1.7 V could be used in this process, such as fumaric acid, sodium fumarate, or glucose. Dopant ions may also be dissolved in the sol.
- the resulting sol is then degassed under a moderate vacuum, allowed to gel-and then age.
- the resulting gels are rinsed with H 2 O and then rinsed in an oxidizing acid, such as sulfuric acid, followed by multiple rinses with water.
- an oxidizing acid such as sulfuric acid
- the gels can be prepared in ambigel or aerogel forms, depending on the drying procedure, as follows.
- the water in the MnO 2 gels, as obtained above, is exchanged for a polar solvent such as acetone or any other solvent miscible with liquid CO 2 , H 2 O, and hydrocarbons, such as amyl acetate.
- a polar solvent such as acetone or any other solvent miscible with liquid CO 2 , H 2 O, and hydrocarbons, such as amyl acetate.
- the MnO 2 gels are then placed into a supercritical CO 2 autoclave, where the solvent in the MnO 2 structure is exchanged for liquid CO 2 with several rinses.
- the CO 2 is finally removed from the MnO 2 gel by taking the CO 2 to supercritical conditions.
- CO 2 is preferred because it is not flammable and can be taken to the supercritical state more easily than most other compounds.
- the water in the MnO 2 gel, as obtained above, is exchanged with a polar solvent such as acetone by rinsing several times with the polar solvent.
- the polar solvent is then exchanged for a non-polar solvent such as hexane.
- the MnO 2 gels are then dried under ambient pressure conditions or under reduced pressure.
- Manganese oxide gels were prepared by adding an organic reducing agent such as fumaric acid (i.e., an organic compound having a potential less negative than +1.7 V) to a vigorously stirred 0.20 M solution of NaMnO 4 .H 2 O or KMnO 4 in a 1:3 molar ratio.
- an organic reducing agent such as fumaric acid (i.e., an organic compound having a potential less negative than +1.7 V)
- the resulting brown sol (from either the potassium or sodium permangantes) was then degassed under a moderate vacuum for eight minutes to facilitate the evolution of CO 2 . This degassing step ensured that high quality monolithic gels were obtained.
- the sol was then poured into 5-mL polypropylene molds, where gelation occurred in about one to 1.5 hours. Following a 24-hour aging step, the gels were rinsed with multiple aliquots of H 2 O to remove unreacted starting materials or byproducts. The gels were then subjected to a 24-hour rinse in 1M sulfuric acid, which was then followed by multiple rinses with water to remove sulfuric acid and Mn(II) salts. At this point the gels can be prepared in ambigel or aerogel forms, depending on the drying procedure.
- Ambigels were prepared by first rinsing the gels with several aliquots of a polar solvent, in this case acetone, and then in multiple aliquots of a non-polar solvent, e.g., cyclohexane. Excess cyclohexane was poured off and the gels were either dried over two days at ambient pressure or vacuum dried at about 60° C. for 24 hours to yield very low density, fragile brown monoliths.
- a polar solvent in this case acetone
- a non-polar solvent e.g., cyclohexane
- the gels with water-filled pores were rinsed with multiple aliquots of acetone; the gels were then transferred to an autoclave where the acetone was replaced in several rinses with liquid CO 2 . The CO 2 was then taken to its supercritical point and slowly released from the autoclave. The resulting aerogels were fragile brown monoliths.
- All of the gels as prepared above were subsequently subjected to an annealing step in air by heating to 300° C. at 2° C./min, holding at about 300° C. for about two hours, and then cooling to room temperature.
- the following table shows micropore physisorption results for MnO 2 sol-gel derived materials.
- BET surface area denotes the Brunauer-Emmett-Teller theory for determining surface area from physisorption data.
- BJH denotes the Barrett-Joyner-Halenda method for determining pore volume from physisorption data.
- manganese oxide xerogel results have been included for prior art comparison purposes only.
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Abstract
Nanoscale, mesoporous manganese oxide materials aerogels and ambigels are prepared by altering the method for removing pore liquid from manganese oxide gels. By removing pore fluid under conditions where capillary forces are substantially absent, materials exhibiting a desired high mesoporosity and high surface area can be obtained.
Description
The present invention relates to methods for making high surface area, nanoscale, mesoporous manganese oxide materials with controlled solid-pore architecture.
Manganese oxide materials (as used herein, manganese oxide materials are denoted as MnO2, but refers to all species of manganese oxide compounds including, but not limited to: MnO2, MnOx, MnOx. yH2O, or MnOxHy, where x=1.5 to 2.5 and y=0.5 to 2, doped manganese oxides, and AMnO2 where A= alkali-metal or alkaline-earth cations) have long been explored for use as cathode materials for batteries, and manganese oxide is used in the familiar 1.5-volt commercial Zn/MnO2 alkaline cells (Chabre et al.,1995). More recently, manganese oxide materials have been studied as intercalation hosts for lithium batteries (Thackeray, 1997), which can provide voltages of 3 to 5 volts. The intense interest in manganese oxide as a battery material is because of its low cost and low toxicity relative to other high performance metal oxide battery materials such as NiO2, CoO2, and V2O5.
The discharge processes at MnO2 are accomplished by the intercalation of either protons or lithium cations into the MnO2 structure. This process is accompanied by a simultaneous reduction of the manganese sites to maintain charge balance:
-
- MnO2+xH++xe→HxMnO2
- MnO2+xLi++xe→LixMnO2
The protons or lithium ions intercalated into the MnO2 structure are supplied by the electrolyte at the electrode/electrolyte interface. Charge storage is further facilitated by diffusion of protons or lithium cations though the bulk of the structure.
Although MnO2 materials are relatively inexpensive and are currently used in commercial batteries, some problems remain, particularly with respect to lithium battery applications. For example, electrodes made from manganese oxide spinels have poor conductivity and require the addition of conductive fillers such as carbon to enhance conductivity. However, adding such fillers reduces the energy density of the electrode. Moreover, recharging the cells requires applying a voltage which exceeds the discharge terminal voltage of the cell. The result, for cells having such manganese-oxide spinel cathodes, is that it takes at least 4.1 volts (and preferably more) to de-intercalate lithium from the electrode during charging of the cell. Above about 4.5 volts, however, the solvents used as the electrolyte oxidize and decompose. It is, therefore, necessary to control the charging voltage of these cells below the decomposition potential of the solvent in order to prevent its degradation.
In addition, due to the crystalline structure of spinel manganese oxide, the reversible capacity and cycle life of spinel-based cathodes are sensitive to overcharge and over-discharge. Discharge of the manganese oxide spinel cells must be cut off when the terminal voltage falls to about 3.4 volts (thus limiting the capacity of the material, which typically peaks at about 140 mAh/g). Below about 3.4 volts, the spinel form of the manganese oxide undergoes structural transformation when additional lithium is inserted into LiMn2O4 and it converts to the orthorhombic form which has very poor cycle ability, and is very unstable, causing the formation of other manganese oxides which are not electrochemically active.
Moreover, insertion of more than one lithium ion per molecule into spinel manganese oxide results in cation mixing between octahedral and tetrahedral sites, which leads to continuous capacity decay. To avoid these problems, the cell voltage must be controlled electronically during the operation of the cell. Such control is-very difficult to manage when a number of large lithium cells are coupled together in series. Spinel-type manganese oxide electrodes typically have internal surface areas less than about 40 m2/g, which limits the rate at which they can be discharged.
Charge/discharge rates and the capacity achieved at those rates are in part determined by the transport of protons or lithium cations through the MnO2 structure. Sol-gel-derived manganese oxides are typically microporous, based on the tendency of MnO2 to form tunnel or layered structures. Intercalating cations must also be transported through the micropores. The small pore size can limit the accessability of electrolyte to the MnO2 interface, particularly for the large (relative to the proton) lithium cations.
Manganese oxide can be produced in a variety of forms, the most common form for battery materials being electrolytic manganese dioxide (EMD) (Chabre et al., 1995). EMD is prepared by anodic electrodeposition from manganese (II) salts. Although EMD has been used in alkaline batteries for many years, recent investigations have shown that it is not optimal for lithium battery applications (Bach et al., 1992). Some efforts have been made to improve the surface area and porosity of EMD (Kurimoto et al., 1995).
Manganese oxides have also been prepared by a variety of sol-gel approaches (Manthiram et al., 1998). Sol-gel chemistry provides a flexible, low temperature process for preparing metal oxides. Another advantage of sol-gel chemistry is that dopant ions can be mixed uniformly in the manganese sol to improve the electrochemical and structural properties of the manganese oxide. Under the appropriate reaction conditions, the sol-to-gel transition can occur so that the metal oxide sol forms a highly porous three-dimensional network. Removal of the pore fluid exclusively by evaporation typically collapses the porous structure due to the large capillary forces exerted on the gel structure at the liquid-gas interface.
If the pore fluid is removed under conditions in which capillary forces are low or extremely low, the inherent mesoporosity and high surface area of the initial gel can be retained. Aerogels are prepared by taking the pore fluid supercritical, wherein there is no longer a liquid-gas interface (Huesing et al., 1998). When supercritical CO2 drying is preferred, the pore liquid of the wet gel is replaced with liquid CO2, which is then taken supercritical. Aerogels of V2O5 have been prepared that exhibit both high surface areas and high porosities (Salloux et al., 1995; Le et al., 1996; Le et al., 1995).
An alternative to supercritical drying is replacing the pore fluid with a low surface tension liquid, such as an alkane, and evaporating at ambient conditions. Ambient pressure synthesis of V2O5 (Coustier et al., 1998; Harreld et al., 1998) and MoO3 (Harreld et al., 1998) gels (now denoted as ambigels) have been accomplished. Ambigels exhibit a porosity between that of xerogels and aerogels. V2O5 aerogels and ambigels have both shown improved lithium capacities relative to xerogels derived from the same sol-gel chemistry (Dong et al., 2000).
Le et al., in U.S. Pat. No: 5,674,642, describe xerogels, cryogels, and aerogels of V2O5 synthesized from sols and gels.
Lynch, in U.S. Pat. No. 3,977,993, discloses preparing metal oxide aerogels by introducing an aqueous slurry of a hydrogel into an organic solvent such as ethanol until substantially all of the water in the hydrogel is displaced by the organic solvent. The organic solvent is then treated to render it rigorously anhydrous. The organic solvent is removed therefrom by heating the mixture to above the critical point and releasing the organic solvent therefrom at a pressure at least equal to the critical pressure of the organic solvent.
Tillotson et al., in U.S. Pat. Nos. 5,275,796 and 5,409,683; describe a two-step hydrolysis condensation method to form metal oxide aerogels. A high purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. Aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and directly extracting the nonalcoholic solvent.
Anderson et al., in U.S. Pat. No. 5,227,342, disclose making porous ceramic materials with controlled porosity by manipulating the sol used to make the material by gradually removing protons from the metal oxide sol to a predefined threshold.
Hupe et al., in U.S. Pat. No. 4,894,357, disclose that the structural and/or surface characteristics of metal oxides can be adjusted by dehydrating a water-containing oxide gel under supercritical conditions by extracting the water with an extraction agent such as carbon dioxide at a pressure above the critical pressure of the extraction agent.
Dasgupta et al., 5,601,952, disclose preparing lithium-manganese oxide compounds which can be used in a non-aqueous rechargeable lithium battery. A gel of lithium manganese oxide is prepared in a water-miscible organic solvent such as an alcohol. The gel is dried and, depending upon the method of liquid removal a xerogel, aerogel, sonogel, or cryogel is obtained.
Passerini et al., (1999) describe the preparation of MnO2 Xerogels and ambigels (hexanogels in their terminology).
However, to date there has been no method to obtain high surface area, highly mesoporous MnO2 with a controlled, continuously intertwined solid-pore architecture on the nanoscale.
It is an object of the present invention to overcome the aforesaid deficiencies in the prior art.
It is another object of the present invention to provide a method for preparing nanoscale, mesoporous manganese oxide materials with controlled solid-pore architectures.
It is another object of the present invention to provide a method for preparing nanoscale, mesoporous manganese oxide materials in the form of aerogels and ambigels.
According to the present invention, nanoscale, mesoporous manganese oxide materials are prepared using sol-gel chemistry. As used herein, manganese oxide materials are denoted as MnO2, but this use refers to all species of manganese oxide compounds including, but not limited to: MnO2, MnOx. yH2O, or MnOxHy where x=1.5 to 2.5 and y=0.5 to 2, doped manganese oxides, and AMnO2 where A=alkali-metal or alkaline-earth cations. MnO2 gels derived from the same sol exhibit markedly different final structure, based upon how the pore fluid is removed from the gel.
Two new classes of MnO2 materials have been prepared, in which the mesoporous structure of the initial gel is maintained by removing the pore liquid under conditions where the capillary forces that result from removal or pore liquid are either low, forming a MnO2 ambigel, or extremely low, forming a MnO2 aerogel. These materials are particularly useful in alkaline and lithium batteries.
Different types of manganese oxide materials can be prepared from MnO2 gels by removing the pore liquid from the gels by methods that differ in the magnitude of liquid-vapor forces that are established in the pores, i.e., the-magnitude of capillary pressures that develop (Long et al., 2000). The choice of method for removing the pore liquid from the MnO2 gels allows one to control the final pore structure of the MnO2 gel. Classically prepared MnO2 xerogels of cryptomelane and birnessite have very high specific surface areas (˜200 m2g−1) that are concentrated in pores less than 10nm in size. The MnO2 aerogels and ambigels, as described in the present invention, have similarly high surface areas but which are distributed in a mesoporous structure with pore sizes from about 3 nm to about 100 nm. These MnO2 aerogels and ambigels also exhibit higher specific pore volumes relative to the xerogel.
The structure of the mesoporous network of the MnO2 aerogels and ambigels will optimize the supply of proton or lithium cation from the supporting electrolyte filling the pores to the nanoscale MnO2 domains in the gel network. Data in the electrochemical literature indicate that ionic conductivity into micropores is lower by orders of magnitude than that in open electrolyte [Koresh and Soffer, 1977]. Microporous surface area in RuO2-based anodes does not contribute to electroactivity [Ardizzone et al., 1982].
Another important feature of the present invention is that the MnO2 ambigels can be obtained in the form of stable monoliths, which, although collapsed to about 30% of their original dimensions; still retain a large cumulative pore volume relative to the aerogel.
Nanoscale MnO2 materials are typically prepared using a sol-gel method that includes reducing a permanganate or substantially equivalent compound by an organic reducing agent in aqueous solution,. as disclosed by Bach et al., 1990. The permanganate used to form MnO2 has a standard potential of about +1.7 V (versus H2/H+ at 0.0 V). Therefore, any organic reducing agent with a potential less negative than +1.7 V could be used in this process, such as fumaric acid, sodium fumarate, or glucose. Dopant ions may also be dissolved in the sol. The resulting sol is then degassed under a moderate vacuum, allowed to gel-and then age. The resulting gels are rinsed with H2O and then rinsed in an oxidizing acid, such as sulfuric acid, followed by multiple rinses with water. At this point the gels can be prepared in ambigel or aerogel forms, depending on the drying procedure, as follows.
The water in the MnO2 gels, as obtained above, is exchanged for a polar solvent such as acetone or any other solvent miscible with liquid CO2, H2O, and hydrocarbons, such as amyl acetate. The MnO2 gels are then placed into a supercritical CO2 autoclave, where the solvent in the MnO2 structure is exchanged for liquid CO2 with several rinses. The CO2 is finally removed from the MnO2 gel by taking the CO2 to supercritical conditions.
While any liquid taken supercritical can be used for this procedure, CO2 is preferred because it is not flammable and can be taken to the supercritical state more easily than most other compounds.
The water in the MnO2 gel, as obtained above, is exchanged with a polar solvent such as acetone by rinsing several times with the polar solvent. The polar solvent is then exchanged for a non-polar solvent such as hexane. The MnO2 gels are then dried under ambient pressure conditions or under reduced pressure.
- Example—MnO2 Ambigels and Aerogels
Manganese oxide gels were prepared by adding an organic reducing agent such as fumaric acid (i.e., an organic compound having a potential less negative than +1.7 V) to a vigorously stirred 0.20 M solution of NaMnO4.H2O or KMnO4 in a 1:3 molar ratio.
The resulting brown sol (from either the potassium or sodium permangantes) was then degassed under a moderate vacuum for eight minutes to facilitate the evolution of CO2. This degassing step ensured that high quality monolithic gels were obtained. The sol was then poured into 5-mL polypropylene molds, where gelation occurred in about one to 1.5 hours. Following a 24-hour aging step, the gels were rinsed with multiple aliquots of H2O to remove unreacted starting materials or byproducts. The gels were then subjected to a 24-hour rinse in 1M sulfuric acid, which was then followed by multiple rinses with water to remove sulfuric acid and Mn(II) salts. At this point the gels can be prepared in ambigel or aerogel forms, depending on the drying procedure.
Ambigels were prepared by first rinsing the gels with several aliquots of a polar solvent, in this case acetone, and then in multiple aliquots of a non-polar solvent, e.g., cyclohexane. Excess cyclohexane was poured off and the gels were either dried over two days at ambient pressure or vacuum dried at about 60° C. for 24 hours to yield very low density, fragile brown monoliths.
To obtain aerogels, the gels with water-filled pores were rinsed with multiple aliquots of acetone; the gels were then transferred to an autoclave where the acetone was replaced in several rinses with liquid CO2. The CO2 was then taken to its supercritical point and slowly released from the autoclave. The resulting aerogels were fragile brown monoliths.
All of the gels as prepared above were subsequently subjected to an annealing step in air by heating to 300° C. at 2° C./min, holding at about 300° C. for about two hours, and then cooling to room temperature.
Electron diffraction measurements and transmission electron microscopy confirmed that all sol-gel-derived MnO2 materials annealed to 300° C. were single-phase polymorphs, either nanocrystalline cryptomelane (KMn4 preparation) or birnessite (NaMnO4 preparation). Annealing to a temperature of 300° C., brings the gels to constant weight but does not expose them to temperatures where a crystallization transition at 550° C. to Mn2O3 occurs, as observed by differential scanning calorimetry. The surface areas and pores-size distributions were determined by N2 physisorption.
The following table shows micropore physisorption results for MnO2 sol-gel derived materials.
TABLE 1 |
Micropore physisorption results for MnO2 sol-gels-derived materials. |
BET Surface | BJH Pore Volume | BJH Average Pore | |
MnO2 sample | Area m2g−1 | cm3g−1 | Diamer/nm |
Xerogel, | 180 | 0.31 | 5 |
Cryptomelane | |||
Ambigel, | 190 | 1.1 | 25 |
Cryptomelane | |||
Aerogel | 210 | 0.80 | 16 |
Cryptomelane | |||
Xerogel, | 140 | 0.36 | 9 |
Birnessite | |||
Ambigel, | 210 | 1.6 | 29 |
Birnessite | |||
Aerogel, | 250 | 1.8 | 32 |
Birnessite | |||
BET surface area denotes the Brunauer-Emmett-Teller theory for determining surface area from physisorption data. BJH denotes the Barrett-Joyner-Halenda method for determining pore volume from physisorption data. Please note that manganese oxide xerogel results have been included for prior art comparison purposes only.
The foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without undue experimentation and without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. The means, materials, and steps for carrying out various disclosed functions may take a variety of alternative forms without departing from the invention.
Thus, the expressions “means to . . .” and “means for . . .”, or any method step language, as may be found in the specification above and/or in the claims below, followed by a functional statement, are intended to define and cover whatever structural, physical, chemical, or electrical element or structure, or whatever method step, which may now or in the future exist which carries out the recited :functions, whether or not precisely equivalent to the embodiment or embodiments disclosed in the specification above, i.e., other means or steps for carrying out the same function can be used; and it is intended that such expressions be given their broadest interpretation.
Claims (21)
1. A method for preparing high surface area, nanoscale, mesoporous manganese oxide material with controlled solid-pore architecture comprising:
removing pore fluid from a gel of manganese oxide material under conditions in which capillary forces are low or extremely low to thereby form said material.
2. The method according to claim 1 , wherein said material comprises a manganese oxide polymorph.
3. The method according to claim 2 , wherein said manganese oxide polymorph comprises cryptomelane or birnessite.
4. The method according to claim 1 , further comprising an initial step of preparing said gel of manganese oxide material with KmnO4 to thereby form a cryptomelane gel.
5. The method according to claim 1 , further comprising an initial step of preparing said gel of manganese oxide material with NaMnO4 to thereby form a birnessite gel.
6. The method according to claim 1 , wherein said step of removing pore fluid from a gel of manganese oxide material comprises:
exchanging pore fluid in said gel of manganese oxide material with a low surface tension non-polar liquid; and
evaporative drying said gel of manganese oxide material under ambient-pressure conditions thereby forming a ambigel.
7. The method according to claim 1 , wherein said step of removing pore fluid from a gel of manganese oxide material comprises:
exchanging pore fluid in said gel of manganese oxide material for an organic solvent which is miscible with liquid CO2, water, and hydrocarbons;
taking said carbon dioxide to a supercritical state; and
releasing the supercritical carbon dioxide fluid from the gel to thereby form an aerogel.
8. The method according to claim 7 , wherein said organic solvent is selected from the group consisting of amyl acetate and acetone.
9. The method according to claim 1 , wherein said step of removing pore fluid from a gel of manganese oxide material comprises:
exchanging pore fluid in said gel of manganese oxide material for a polar organic solvent;
exchanging said polar organic solvent for a non-polar organic solvent; and
removing said non-polar organic solvent to thereby form an ambigel.
10. The method according to claim 9 , wherein said polar organic solvent is acetone.
11. The method according to claim 9 , wherein said non-polar solvent is hexane.
12. The method according to claim 9 , wherein said non-polar solvent is cyclohexane.
13. The method according to claim 1 , further comprising the step of:
doping said gel with a dopant selected from Group I, Group II, a transitional metal, and Si, or any combination thereof.
14. An ambigel of a manganese oxide material, said material being prepared from a cryptomelane sol of manganese oxide materials.
15. An ambigel of a manganese oxide material, said material being prepared from a birnessite sol of manganese oxide materials.
16. An aerogel of a manganese oxide material, said material being prepared from a cryptomelane sol of manganese oxide materials.
17. An aerogel of a manganese oxide material, said material being prepared from a birnessite sol of manganese oxide materials.
18. A high surface area, nanoscale material suitable for use as a battery electrode, comprising an ambigel of a manganese oxide polymorph material.
19. A material as in claim 18 , wherein said ambigel of a manganese oxide polymorph material is selected from cryptomelane or birnessite.
20. A high surface area, nanoscale material suitable for use as a battery electrode, comprising an aerogel of a manganese oxide polymorph material.
21. A material as in claim 20 , wherein said aerogel of a manganese oxide polymorph is selected from cryptomelane or birnessite.
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US09/689,700 USH2121H1 (en) | 2000-10-13 | 2000-10-13 | High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof |
PCT/US2001/031629 WO2002030825A1 (en) | 2000-10-13 | 2001-10-10 | High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof |
AU2001296760A AU2001296760A1 (en) | 2000-10-13 | 2001-10-10 | High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof |
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Cited By (2)
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US20100195269A1 (en) * | 2009-02-03 | 2010-08-05 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor using surface-oxidized transition metal nitride aerogel |
US20100195268A1 (en) * | 2009-02-03 | 2010-08-05 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor using transition metal oxide aerogel |
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CN100558644C (en) * | 2006-09-27 | 2009-11-11 | 中国科学院理化技术研究所 | Layered mesoporous birnessite manganese dioxide cellular nanometer ball and its production and use |
CN103754936B (en) * | 2014-01-23 | 2015-10-21 | 山东科技大学 | The synthetic method of mesoporous manganese oxide |
CN104258845B (en) * | 2014-09-17 | 2016-10-12 | 中国科学院上海硅酸盐研究所 | A kind of amorphous Mn oxide and preparation method thereof |
RU2693200C1 (en) * | 2018-08-23 | 2019-07-01 | Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" | Method of producing nanoparticles of manganese oxides and aerogels based thereon and aerogel obtained by this method |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4246253A (en) | 1978-09-29 | 1981-01-20 | Union Carbide Corporation | MnO2 derived from LiMn2 O4 |
US4284618A (en) | 1978-11-06 | 1981-08-18 | Metallurgie Hoboken-Overpelt | Production of battery-grade manganese dioxide |
US4476104A (en) | 1982-12-21 | 1984-10-09 | Union Carbide Corporation | Manganese dioxide and process for the production thereof |
US4667417A (en) | 1984-08-11 | 1987-05-26 | Basf Aktiengesellschaft | Preparation of aerogels |
US4894357A (en) | 1984-11-02 | 1990-01-16 | Kali-Chemie Aktiengesellschaft | Process for adjusting the structural and/or surface character of oxides |
US5135732A (en) | 1991-04-23 | 1992-08-04 | Bell Communications Research, Inc. | Method for preparation of LiMn2 O4 intercalation compounds and use thereof in secondary lithium batteries |
US5156934A (en) | 1991-02-11 | 1992-10-20 | Rbc Universal Ltd. | Method of making a rechargable modified manganese dioxide material and related compound and electrode material |
US5196279A (en) | 1991-01-28 | 1993-03-23 | Bell Communications Research, Inc. | Rechargeable battery including a Li1+x Mn2 O4 cathode and a carbon anode |
US5227342A (en) | 1991-05-01 | 1993-07-13 | Wisconsin Alumni Research Foundation | Process of making porous ceramic materials with controlled porosity |
US5275796A (en) | 1990-08-23 | 1994-01-04 | Regents Of The University Of California | Method for producing metal oxide aerogels having densities less than 0.02 g/cc |
US5395805A (en) | 1993-03-25 | 1995-03-07 | Regents Of The University Of California | Method for making monolithic metal oxide aerogels |
US5409683A (en) | 1990-08-23 | 1995-04-25 | Regents Of The University Of California | Method for producing metal oxide aerogels |
US5601952A (en) | 1995-05-24 | 1997-02-11 | Dasgupta; Sankar | Lithium-Manganese oxide electrode for a rechargeable lithium battery |
US5604057A (en) | 1995-11-27 | 1997-02-18 | General Motors Corporation | Secondary cell having a lithium intercolating manganese oxide |
US5674642A (en) | 1995-06-02 | 1997-10-07 | Regents Of The University Of Minnesota | High capacity high rate materials |
US5963417A (en) | 1995-11-09 | 1999-10-05 | Wisconsin Alumni Research Foundation | Electrochemical capacitor |
US6071647A (en) | 1996-10-18 | 2000-06-06 | France Telecom | Lithium and manganese double oxides for the positive electrodes of electrochemical devices, preparation thereof, and electrodes including such oxides |
US6071486A (en) * | 1997-04-09 | 2000-06-06 | Cabot Corporation | Process for producing metal oxide and organo-metal oxide compositions |
-
2000
- 2000-10-13 US US09/689,700 patent/USH2121H1/en not_active Abandoned
-
2001
- 2001-10-10 WO PCT/US2001/031629 patent/WO2002030825A1/en active Application Filing
- 2001-10-10 AU AU2001296760A patent/AU2001296760A1/en not_active Abandoned
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4246253A (en) | 1978-09-29 | 1981-01-20 | Union Carbide Corporation | MnO2 derived from LiMn2 O4 |
US4284618A (en) | 1978-11-06 | 1981-08-18 | Metallurgie Hoboken-Overpelt | Production of battery-grade manganese dioxide |
US4476104A (en) | 1982-12-21 | 1984-10-09 | Union Carbide Corporation | Manganese dioxide and process for the production thereof |
US4667417A (en) | 1984-08-11 | 1987-05-26 | Basf Aktiengesellschaft | Preparation of aerogels |
US4894357A (en) | 1984-11-02 | 1990-01-16 | Kali-Chemie Aktiengesellschaft | Process for adjusting the structural and/or surface character of oxides |
US5409683A (en) | 1990-08-23 | 1995-04-25 | Regents Of The University Of California | Method for producing metal oxide aerogels |
US5275796A (en) | 1990-08-23 | 1994-01-04 | Regents Of The University Of California | Method for producing metal oxide aerogels having densities less than 0.02 g/cc |
US5196279A (en) | 1991-01-28 | 1993-03-23 | Bell Communications Research, Inc. | Rechargeable battery including a Li1+x Mn2 O4 cathode and a carbon anode |
US5156934A (en) | 1991-02-11 | 1992-10-20 | Rbc Universal Ltd. | Method of making a rechargable modified manganese dioxide material and related compound and electrode material |
US5135732A (en) | 1991-04-23 | 1992-08-04 | Bell Communications Research, Inc. | Method for preparation of LiMn2 O4 intercalation compounds and use thereof in secondary lithium batteries |
US5227342A (en) | 1991-05-01 | 1993-07-13 | Wisconsin Alumni Research Foundation | Process of making porous ceramic materials with controlled porosity |
US5395805A (en) | 1993-03-25 | 1995-03-07 | Regents Of The University Of California | Method for making monolithic metal oxide aerogels |
US5601952A (en) | 1995-05-24 | 1997-02-11 | Dasgupta; Sankar | Lithium-Manganese oxide electrode for a rechargeable lithium battery |
US5674642A (en) | 1995-06-02 | 1997-10-07 | Regents Of The University Of Minnesota | High capacity high rate materials |
US5963417A (en) | 1995-11-09 | 1999-10-05 | Wisconsin Alumni Research Foundation | Electrochemical capacitor |
US5604057A (en) | 1995-11-27 | 1997-02-18 | General Motors Corporation | Secondary cell having a lithium intercolating manganese oxide |
US5674644A (en) | 1995-11-27 | 1997-10-07 | General Motors Corporation | Manganese oxide electrode and method |
US6071647A (en) | 1996-10-18 | 2000-06-06 | France Telecom | Lithium and manganese double oxides for the positive electrodes of electrochemical devices, preparation thereof, and electrodes including such oxides |
US6071486A (en) * | 1997-04-09 | 2000-06-06 | Cabot Corporation | Process for producing metal oxide and organo-metal oxide compositions |
Non-Patent Citations (21)
Title |
---|
A. Manthiram and J. Kim, Chemistry of Materials, 1998, 10, 2895-2909, no month. |
D.B. Le, S. Passerini, A. L. Tipton, B.B. Owens, and W.H. Smyrl, Journal of the Electrochemical Society, 1995, 142, L102-L103, June. |
D.B. Le, S. Passerini, J. Guo, J. Ressler, B.B. Owens, and W.H. Smyrl, Journal of the Electrochemical Society, 1996, 143, 2099-2104, July. |
F. Coustier, S. Passerine and W.H. Smyrl, Journal of the Electrochemical Society, 1998, 145, L73-L74, May. |
H. Kurimoto, K. Suzuoka, T. Murakami, Y. Xie, H. Nakamura, and M. Yoshio, Journal of the electrochemical Society, 1995, 142, 2150-2162, July. |
J. H. Harreld, W. Dong, and B. Dunn, Materials Research Bulletin 1998, 33, 561-567, no month. |
J. Koresh, et al., "Journal of the Electrochemical Society," 1977, 124, 1379-1385, no month. |
J. Luo and S. L. Suib, Journal of the Chemical Society-Chemical Communications, 1997, 1031-1032, no month. |
J.J. Xu, A. J. Kinser, B.B. Owens, and W.H. Smyrl, Electrochemical and Solid-State Letters, 1998, 1, 1-3, no month. |
J.W. Long, et al., "Electrochemical and Solid-State Letter," 2000, 3, 453-456, Aug. |
K. Salloux, F. Chaput, H.P. Wong, B. Dunn, and M. W. Breiter, Journal of the Electrochemical Society, 1995, 142, L191-L192, no month. |
Long, Swider-Lyons, Stroud, Rolison, Design of Pore and Matter Archetectures in Manganese Oxide Charge-Storage Materials, Electrochemical and Solid State Letters, 3 (100 453-456 (200). |
M. M. Thackeray, Progress in Solid State Chemistry, 1997, 25, 1-71, no month. |
N. Husing and U. Schubert, Angewandte Chemie-International Edition, 1998, 37, 22-45, no month. |
S. Ardizzone, et al., "Journal of Electrochemical Society," 1982, 129, 1689-1693, no month. |
S. Bach, J.P. Pereira-Ramos, N. Baffer, and R. Messina, Electrochimica Acta, 1992, 37, 1301, no month. |
S. Bach, M. Henry, N. Baffler, and J. Livage, Journal of Solid State Chemistry, 1990, 88, 325-333, no month. |
W. Dong, et al., "Electrochemical and Solid-State Letters," 2000, 3, 457-459, Aug. |
Y. Chabre and J. Pannetier, Progress in Solid State Chemistry, 1996, 23, 1-130, no month. |
Yamamoto, et al., "Micro-rings of Manganese Dioxide Nanocrystals on Mica", Chemistry Letters 1998, pp. 809-10. * |
Z.-R. Tian, W. Tong, J.-Y. Wang, N.-G. Duan, V. V. Krishnan, S. L. Suib, Science, 1997, 276, 926-930, May. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20100195269A1 (en) * | 2009-02-03 | 2010-08-05 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor using surface-oxidized transition metal nitride aerogel |
US20100195268A1 (en) * | 2009-02-03 | 2010-08-05 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor using transition metal oxide aerogel |
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