CA2479790C - Batteries comprising alkali-transition metal phosphates and preferred electrolytes - Google Patents
Batteries comprising alkali-transition metal phosphates and preferred electrolytes Download PDFInfo
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- CA2479790C CA2479790C CA2479790A CA2479790A CA2479790C CA 2479790 C CA2479790 C CA 2479790C CA 2479790 A CA2479790 A CA 2479790A CA 2479790 A CA2479790 A CA 2479790A CA 2479790 C CA2479790 C CA 2479790C
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- battery according
- carbonate
- carbon
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- 229910000319 transition metal phosphate Inorganic materials 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 188
- -1 alkylene carbonate Chemical compound 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 69
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 67
- 150000003624 transition metals Chemical class 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 23
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 105
- 229910052799 carbon Inorganic materials 0.000 claims description 97
- 239000011149 active material Substances 0.000 claims description 79
- 230000003647 oxidation Effects 0.000 claims description 68
- 238000007254 oxidation reaction Methods 0.000 claims description 68
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 238000009830 intercalation Methods 0.000 claims description 14
- 230000002687 intercalation Effects 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052790 beryllium Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000004770 chalcogenides Chemical class 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical class O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 claims description 2
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical class O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 2
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 41
- 239000010450 olivine Substances 0.000 abstract description 8
- 229910052609 olivine Inorganic materials 0.000 abstract description 8
- 239000002228 NASICON Substances 0.000 abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 77
- 239000007858 starting material Substances 0.000 description 72
- 238000006243 chemical reaction Methods 0.000 description 70
- 230000001603 reducing effect Effects 0.000 description 43
- 239000007772 electrode material Substances 0.000 description 38
- 235000021317 phosphate Nutrition 0.000 description 38
- 210000004027 cell Anatomy 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 239000010452 phosphate Substances 0.000 description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 229910052783 alkali metal Inorganic materials 0.000 description 28
- 239000002904 solvent Substances 0.000 description 28
- 150000001340 alkali metals Chemical class 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 22
- 239000011368 organic material Substances 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 19
- 239000003638 chemical reducing agent Substances 0.000 description 19
- 230000009467 reduction Effects 0.000 description 19
- 239000011230 binding agent Substances 0.000 description 18
- 229910052909 inorganic silicate Inorganic materials 0.000 description 18
- 150000002739 metals Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 150000001720 carbohydrates Chemical class 0.000 description 17
- 235000014633 carbohydrates Nutrition 0.000 description 17
- 238000003780 insertion Methods 0.000 description 17
- 230000037431 insertion Effects 0.000 description 17
- 230000000737 periodic effect Effects 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 230000002829 reductive effect Effects 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 150000003623 transition metal compounds Chemical class 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 8
- 239000000347 magnesium hydroxide Substances 0.000 description 8
- 235000012254 magnesium hydroxide Nutrition 0.000 description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
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- 239000000758 substrate Substances 0.000 description 6
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- 239000004254 Ammonium phosphate Substances 0.000 description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 5
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- 235000019289 ammonium phosphates Nutrition 0.000 description 5
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Classifications
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/116,276 US20030190527A1 (en) | 2002-04-03 | 2002-04-03 | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
| US10/116,276 | 2002-04-03 | ||
| PCT/US2003/009634 WO2003085757A1 (en) | 2002-04-03 | 2003-03-27 | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2479790A1 CA2479790A1 (en) | 2003-10-16 |
| CA2479790C true CA2479790C (en) | 2012-06-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2479790A Expired - Fee Related CA2479790C (en) | 2002-04-03 | 2003-03-27 | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US20030190527A1 (enExample) |
| EP (1) | EP1490917A4 (enExample) |
| JP (1) | JP4758610B2 (enExample) |
| KR (1) | KR101107423B1 (enExample) |
| CN (1) | CN1650450B (enExample) |
| AU (1) | AU2003224801A1 (enExample) |
| CA (1) | CA2479790C (enExample) |
| WO (1) | WO2003085757A1 (enExample) |
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| US6964827B2 (en) * | 2000-04-27 | 2005-11-15 | Valence Technology, Inc. | Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials |
| US7524584B2 (en) * | 2000-04-27 | 2009-04-28 | Valence Technology, Inc. | Electrode active material for a secondary electrochemical cell |
| US8057769B2 (en) * | 2000-04-27 | 2011-11-15 | Valence Technology, Inc. | Method for making phosphate-based electrode active materials |
| US8367036B2 (en) * | 2000-04-27 | 2013-02-05 | Valence Technology, Inc. | Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials |
| US6777132B2 (en) * | 2000-04-27 | 2004-08-17 | Valence Technology, Inc. | Alkali/transition metal halo—and hydroxy-phosphates and related electrode active materials |
| CA2776362A1 (en) * | 2002-12-19 | 2004-06-19 | Valence Technology, Inc. | Batteries with alkali metal phosphate electrodes |
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| US7041239B2 (en) * | 2003-04-03 | 2006-05-09 | Valence Technology, Inc. | Electrodes comprising mixed active particles |
| US20070141468A1 (en) * | 2003-04-03 | 2007-06-21 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
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- 2002-04-03 US US10/116,276 patent/US20030190527A1/en not_active Abandoned
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2003
- 2003-03-27 CN CN038100339A patent/CN1650450B/zh not_active Expired - Fee Related
- 2003-03-27 EP EP03721492A patent/EP1490917A4/en not_active Withdrawn
- 2003-03-27 AU AU2003224801A patent/AU2003224801A1/en not_active Abandoned
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2005
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| JP2005522009A (ja) | 2005-07-21 |
| KR20040111470A (ko) | 2004-12-31 |
| US20050181283A1 (en) | 2005-08-18 |
| CN1650450B (zh) | 2010-04-28 |
| CA2479790A1 (en) | 2003-10-16 |
| EP1490917A4 (en) | 2008-12-03 |
| EP1490917A1 (en) | 2004-12-29 |
| WO2003085757A1 (en) | 2003-10-16 |
| CN1650450A (zh) | 2005-08-03 |
| KR101107423B1 (ko) | 2012-01-19 |
| JP4758610B2 (ja) | 2011-08-31 |
| US8318352B2 (en) | 2012-11-27 |
| AU2003224801A1 (en) | 2003-10-20 |
| US20030190527A1 (en) | 2003-10-09 |
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