US20040202934A1 - Li4Ti5O12, Li(4-alpha)Zalpha Ti5O12 or Li4ZbetaTi(5-beta)O12 particles, processes for obtaining same and use as electrochemical generators - Google Patents
Li4Ti5O12, Li(4-alpha)Zalpha Ti5O12 or Li4ZbetaTi(5-beta)O12 particles, processes for obtaining same and use as electrochemical generators Download PDFInfo
- Publication number
- US20040202934A1 US20040202934A1 US10/830,240 US83024004A US2004202934A1 US 20040202934 A1 US20040202934 A1 US 20040202934A1 US 83024004 A US83024004 A US 83024004A US 2004202934 A1 US2004202934 A1 US 2004202934A1
- Authority
- US
- United States
- Prior art keywords
- carbon
- particles
- type
- dispersion
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002245 particle Substances 0.000 title claims abstract description 124
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 85
- 230000008569 process Effects 0.000 title claims abstract description 77
- 229910009866 Ti5O12 Inorganic materials 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 122
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 112
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 110
- 239000006185 dispersion Substances 0.000 claims description 39
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 10
- 239000011368 organic material Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- -1 Shawinigan black Substances 0.000 claims description 6
- 229910010252 TiO3 Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 229910003087 TiOx Inorganic materials 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 28
- 229910052596 spinel Inorganic materials 0.000 abstract description 23
- 239000011029 spinel Substances 0.000 abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052758 niobium Inorganic materials 0.000 abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 abstract description 7
- 238000003801 milling Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000010936 titanium Substances 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 11
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 11
- 230000002000 scavenging effect Effects 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 7
- 230000002687 intercalation Effects 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 238000007669 thermal treatment Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000002161 passivation Methods 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 238000003722 High energy mechanical milling Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 4
- 238000002083 X-ray spectrum Methods 0.000 description 4
- 239000011872 intimate mixture Substances 0.000 description 4
- 238000010902 jet-milling Methods 0.000 description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 4
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910052845 zircon Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ADHFMENDOUEJRK-UHFFFAOYSA-N 9-[(4-fluorophenyl)methyl]-n-hydroxypyrido[3,4-b]indole-3-carboxamide Chemical compound C1=NC(C(=O)NO)=CC(C2=CC=CC=C22)=C1N2CC1=CC=C(F)C=C1 ADHFMENDOUEJRK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910011956 Li4Ti5 Inorganic materials 0.000 description 1
- 229910011229 Li7Ti5O12 Inorganic materials 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910013888 LiPF5 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- ICQNTQSOMLDARR-UHFFFAOYSA-N carbonic acid;1,3-dioxolan-2-one;prop-1-ene Chemical compound CC=C.OC(O)=O.O=C1OCCO1 ICQNTQSOMLDARR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- VVGJCPWXLHFMPR-UHFFFAOYSA-N n-(diethylsulfamoyl)-n-ethylethanamine;1,3-dioxolan-2-one Chemical compound O=C1OCCO1.CCN(CC)S(=O)(=O)N(CC)CC VVGJCPWXLHFMPR-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/745—Expanded metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to new particles based on Li 4 Ti 5 O 12 , based on Li (4 ⁇ ) Z ⁇ Ti 5 O 12 , or based on Li 4 Z ⁇ Ti (5 ⁇ ) O 12 .
- the present invention also relates to processes that make it possible to prepare these particles and to their use, especially in the area of electrochemical devices such as electrochemical generators.
- Li-ion batteries Marketing of the lithium-ion battery by Sony, in 1990, was reported by Naguara and Tozawa, Prog. Batt. Solar Cells, 9 (1990), 209. It made possible an expansion and a significant breakthrough of batteries into the area of portable devices (telephone, computer).
- the technology of Li-ion batteries is based on lithium intercalation electrodes, in particular the anode which is made of graphite.
- a passivation film is formed on the carbon surface.
- the chemistry and the composition of this passivation film are complex.
- the electrochemical formation protocol for this film remains an industrial secret.
- there is a volume variation of 10% which induces a discontinuity between the particles causing loosening of the interfaces between the electrode and the electrolyte, and between the electrode and the current collector.
- Titanium oxide spinel Li 4 Ti 5 O 12 is a material for anodes promising for lithium-ion batteries due to its intercalation potential (K. Zaghib et al., 190 th Electrochemical Society Meeting, San Antonio, Abs. no. 93, 1996), cyclability, rapid charging-discharging at high current such as described by K. Zaghib et al. in Proceeding on Lithium Polymer Batteries, PV96-17, p. 223) in The Electrochemical Society Proceeding Series (1996), (K. Zaghib et al., J. Electro chem. Soc. 145, 3135, (1998) and in J. Power Sources, 81-82 (1999) 300-305).
- the coefficient of diffusion of lithium in Li 4 T 5 O 12 is of a higher order of magnitude than the coefficient of diffusion of lithium in carbons (regarding this subject, see K. Zaghib et al., J. Power Sources, 81-82 (1999) 300-305). This characteristic distinguishes Li 5 Ti 5 O 12 from the other potential candidates for power applications, such as PNGV and GSM pulses.
- the structure of Li 4 Ti 5 O 12 does not vary in volume, which makes this electrode very stable and thus safe.
- This study was carried out by Ozhuku and reported in J. Electrochem. Soc., 140, 2490 (1993) by X-ray diffraction and by scanning microscopy in situ by Zayhib et al. (and reported in Proceeding on Lithium Polymer Batteries, PV96-17, p. 223 in The Electrochemical Society Proceeding Series (1996) and in J. Electro chem. Soc. 145, 3135, (1998).
- the material Li 4 Ti 5 O 12 because of its lack of volume expansion (also called as zero volume expansion (ZEV)) has been easily used in polymer, ceramic or glass electrolyte batteries, which ensures good cycling stability.
- ZV zero volume expansion
- the good behavior of this anode at 1.5 V promotes the use of any type of liquid electrode, such as ethylene carbonate (EC), propylene carbonate (PC) or mixtures of these two.
- EC ethylene carbonate
- PC propylene carbonate
- This operation potential increases the life span of the battery, especially for stand-by type applications because of its character as electrode without passivation film.
- the use of Li 4 Ti 5 O 12 as an anode does not require any prior forming of the battery.
- the Li 4 Ti 5 O 12 is mentioned as being able to be obtained by a binary mixture of a mixture of LiOH and TiO 2 where the synthesis temperature is greater than 600° C. Residual impurities of the TiO 2 , Li 2 TiO 3 and/or other type in the mixture limit the electrode capacity and limit the size of the particles.
- the patent U.S. Pat. No. 6,221,531 describes a structure of the spinel type with the general formula Li[Ti 1.67 Li 0.33 ⁇ y M y ]O 4 , wherein Y ⁇ 0 ⁇ 0.33 with M representing magnesium and/or aluminum.
- This structure is presented as useful for making up a negative electrode for a non-aqueous electrochemical cell and in a non-aqueous battery comprising a plurality of cells, connected electrically, each cell comprising a negative electrode, an electrolyte and a positive electrode, the negative electrode being made up of this spinel structure.
- FIG. 1 illustrates the different applications of the Li 4 Ti 5 O 12 particles (coated with carbon or not) as anode or as cathode for batteries and supercapacitors.
- FIG. 2 illustrates comparative performances of a process according to the invention compared with those of a classic process such as described in Prog. Batt. Solar Cells, 9 (1990), 209.
- FIG. 3 illustrates the double role of carbon in the preparation process for new particles and in the composition of the carbon layer that coats them.
- FIG. 4 illustrates a classic formation process for Li 4 Ti 5 O 12 (macroscopic particle), in the absence of carbon; this process makes it possible to obtain a spinel structure in the presence of impurities of a TiO 2 or other type. This structure is limited for electrochemical performance, to currents less than 2C.
- FIG. 5 illustrates the same process illustrated in FIG. 4, with the exception of the reagent LiOH which is substituted by Li 2 CO 3 ; this type of process yields a formation of agglomerates of the Li 4 Ti 5 O 12 type.
- FIG. 6 illustrates a process according to the invention for the formation of nano-particles of Li 4 Ti 5 O 12 from a ternary mixture LiOH-C-TiO 2 , intimately mixed at high energy, this mixture is heated at 400° C. then to 600° C. This type of process gives rise to the formation of nano-agglomerates of Li 4 T 5 O 12 .
- FIG. 7 illustrates a process similar to the one shown in FIG. 6, with the exception that LiOH is substituted by Li 2 CO 3 ; this type of process leads to the formation of Li 4 Ti 5 O 12 nano-agglomerates.
- FIG. 8 illustrates a process similar to the one illustrated in FIG. 7, by adding Li 2 CO 3 to the initial product; this type of process makes it possible to obtain Li 4 Ti 5 O 12 nano-agglomerates.
- FIG. 9 illustrates a process similar to those shown in FIGS. 6 and 7, with the exception that calcination is carried out in an inert atmosphere; this type of process makes it possible to obtain Li 4 Ti 5 O 12 nano-agglomerates of Li 4 Ti 5 O 12 coated with carbon. This structure gives exceptional electrochemical performance at high current density (12C).
- FIG. 10 illustrates the advantages of a pretreatment of the mixture milled at high energy. Dry process. Homogeneous precursor. Homogeneous specific surface area. Coating of particles with carbon. Direct contact of particle with carbon. Direct contact via carbon with the reactive particles. Carbon is a very good thermal conductor. Low contamination. Homogeneous dispersion. Acceleration or rapid synthesis. Obtaining a mixture of nanostructures after the thermal treatment.
- FIG. 11 illustrates the mechanism and the role of carbon coating, the latter coating making it possible to obtain a large diffusion of lithium in Li 4 Ti 5 O 12 and obtain 90% of the nominal capacity at 12C.
- FIG. 12 illustrates the mechanism of the technology of hybrid supercapacitors using an anode of the nano- Li 4 Ti 5 O 12 type.
- FIG. 13 is the TGA curve of a mixture of TiO 2 +Li 2 CO 3 + carbon after milling at high energy for 2 hours, in air and in argon; the reaction starts at 400° C. (in argon and in air).
- FIG. 14 is a SEM photo of microscopic particles of Li 4 Ti 5 O 12 obtained from a mixture of Li 2 CO 3 +TiO 2 .
- FIG. 15 is a SEM photo of nanoscopic particles of Li 4 Ti 5 O 12 obtained using a mixture of Li 2 CO 3 +TiO 2 + carbon.
- FIG. 16 illustrates a manufacturing process for nanoparticles of Li 4 Ti 5 O 12 coated with carbon and obtained by coating the particles of TiO 2 with organic formulations of the polyol type and/or of the PE-PO type; the thermal treatment carried out in inert atmosphere transforms the organic part into carbon. This process is carried out in the step of mixed Jar milling with solvent or dry.
- FIG. 17 illustrates a manufacturing process for nanoparticles of Li 4 Ti 5 O 12 coated with carbon and obtained by coating the particles of TiO 2 with inorganic formulations of the Al 2 O 3 , ZrO 2 type, the thermal treatment carried out in inert atmosphere transforming the organic part to carbon. This process is carried out in the step of mixed Jar milling with solvent or dry.
- FIG. 18 illustrates a manufacturing process for nanoparticles of Li 4 Ti (5 ⁇ ) AlO 12 coated with carbon and obtained by coating the particles of TiO 2 using a hybrid inorganic-organic formulation.
- the present invention concerns a synthesis process for new particles of the formula Li 4 Ti 5 O 12 , of the formula Li (4 ⁇ ) Z ⁇ Ti 5 O 12 or of the formula Li 4 Z ⁇ Ti (5 ⁇ ) O 12 , wherein ⁇ represents a number greater than zero and less than or equal to 0.33, ⁇ represents a number greater than 0 and less than or equal to 0.5, Z represents a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co. These particles are coated with a layer of carbon. Use of these particles in electrochemical systems also constitutes an object of the present invention.
- a first object of the present invention consists of a process that makes possible the preparation of particles comprising:
- a core of Li 4 Ti 5 O 12 a core of Li (4 ⁇ ) Z ⁇ Ti 5 O 12 or a core of Li 4 Z ⁇ Ti (5 ⁇ ) O 12 , ⁇ representing a number greater than zero and less than or equal to 0.33, ⁇ representing a number greater than 0 and less than or equal to 0.5, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co; and
- this synthesis process makes possible the preparation of particles of Li 4 Ti 5 O 12 (preferably with spinel structure) coated with carbon, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li 4 Ti 5 O 12 particles;
- x represents a number between 1 and 2
- z represents 1 or 2
- Y represents a radical chosen among CO 3 , OH, O and TiO 3 or a mixture of them.
- the operating conditions more specifically the concentration conditions of components of the ternary mixture submitted to dispersion, being chosen in such a way as to yield a conversion, preferably a complete conversion, of the initial products into Li 4 Ti 5 O 12 .
- the process according to the invention makes possible the synthesis of particles of Li (4 ⁇ ) Z ⁇ Ti 5 O 12 (preferably with spinel structure) coated with carbon, ⁇ representing a number greater than zero and less than or equal to 0.33, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li (4 ⁇ ) Z ⁇ Ti 5 O 12 particles;
- x represents a number between 1 and 2
- z represents 1 or 2
- Y represents a radical chosen among CO 3 , OH, O and TiO 3 or a mixture of them;
- the operating conditions more specifically the concentration conditions of components of the ternary mixture submitted to dispersion, being chosen in such a way as to yield a conversion, preferably a complete conversion, of the initial products into Li (4 ⁇ ) Z ⁇ Ti 5 O 12 , and
- the source of at least one metal Z being added to the reaction mixture, preferably in step a) of said process in a content that is preferably from 0.1 to 2% by weight, expressed with respect to the mass of said ternary mixture.
- Operating conditions that make possible the specific preparation of particles of the formula Li (4 ⁇ ) Z ⁇ Ti 5 O 12 are, more specifically, a control of the initial quantities of each of the compounds present in the ternary mixture that is used for preparation of the dispersion.
- the process of the invention makes possible the synthesis of particles of the formula Li 4 Z ⁇ Ti (5 ⁇ ) O 12 (preferably with spinel structure), wherein ⁇ is greater than 0 and less than or equal to 0.5, coated with carbon, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li 4 Z ⁇ Ti (5 ⁇ ) O 2 particles;
- x represents a number between 1 and 2
- z represents 1 or 2
- Y represents a radical chosen among CO 3 , OH, O AND TiO 3 or a mixture of them;
- the operating conditions more specifically the concentration conditions of components of the ternary mixture submitted to dispersion, being chosen in such a way as to yield a conversion, preferably a complete conversion, of the initial products into Li 4 Z ⁇ Ti (5 ⁇ ) O 12 , and
- the source of at least one metal Z being added to the reaction mixture, preferably in step a) of said process in a content that is preferably from 0.1 to 2% by weight, expressed with respect to the mass of said ternary mixture,
- the operating conditions that make possible the specific preparation of particles of the formula Li 4 Z ⁇ Ti (5 ⁇ ) O 12 are, more specifically, a control of the initial quantities of each of the constituents present in the ternary mixture that is used for preparation of the dispersion.
- the dispersion of the ternary mixture is heated at a temperature of around 600° C.
- the dispersion is heated in two steps, the first step being carried out until the dispersion reaches a temperature of about 400° C., the second step being carried out at approximately 600° C.
- the first step is preferably carried out by rapid heating at around 400° C., preferably during a period of 1 to 4 hours.
- the second step is carried out by slow heating, preferably for at least four hours.
- At least one step which is preferably step a), is carried out in air.
- At least one step which is preferably step b), is carried out at least partially in inert atmosphere.
- the dispersion of the ternary mixture is advantageously prepared using water and/or at least one solvent that is preferably an organic solvent.
- This organic solvent is advantageously chosen from the group made up of ketones, saturated hydrocarbons, unsaturated hydrocarbons, alcohols and mixtures of them, still more preferably the dispersion of the ternary mixture is prepared using water, acetone, heptane, toluene or using a mixture of them.
- Said dispersion is also prepared dry, without solvent.
- a compound Li z Y which comprises at least one compound chosen from the group made up of Li 2 O, Li 2 CO 3 and LiOH, is chosen. Still more preferably, the Li z Y compound comprises exclusively Li 2 CO 3 , said Li 2 CO 3 preferably being present in a ratio of 25 to 30% by weight with respect to the total mass of the ternary mixture.
- the dispersion is carried out by mechanical milling, preferably by high-energy mechanical milling, preferably dry and/or by Jar milling, preferably with a solvent.
- a TiO x compound of the anatase or rutile TiO 2 type (preferably the anatase TiO 2 type), or a mixture of both, is chosen and TiO 2 is preferably present in said ternary mixture in concentrations of 58 to 71% by weight.
- the compound Li z Y preferably comprises Li 2 TiO 3 , this Li 2 TiO 3 preferably being present in a quantity of 43 to 48% by weight of Li 2 TiO 3 with respect to the total mass of the ternary mixture.
- the carbon used to carry out the process according to the invention may come from any source.
- the carbon is chosen from the group made up of natural or artificial graphite, carbon black (preferably acetylene black), Shawinigan black, Ketjen black and cokes (preferably petrolum coke) and is added to the reaction mixture, preferably at the beginning of the preparation of the dispersion of the ternary mixture.
- the carbon can also be produced in the course of said process, preferably from at least one free organic material, such as a polymer, present in the reaction mixture.
- the carbon can also be produced at the surface of the particles by calcination of an organic and/or inorganic material deposited, in the course of said process, on the surface of the Li 4 Ti 5 O 12 particles and/or on the surface of the particles based on Li 4 Ti 5 O 12 and/or on the surface of at least one of the reagents used (preferably the TiO 2 ) for the preparation of the dispersion of said ternary mixture.
- the carbon used is in the form of particles having a specific surface area greater than or equal to 2 m 2 /g, preferably in the form of particles having a specific surface area greater than or equal to 50 m 2 /g.
- the process of the invention is carried out in the presence of an atmosphere containing oxygen, a part of the carbon present in the reaction mixture then being consumed during said process.
- the coating of carbon is obtained from the presence, in the reaction mixture, of a powder of Shawinigan carbon and/or at least one polymer, which is preferably a polyol or a polyethylene-polyoxide ethylene copolymer.
- TiO 2 that is coated with at least one inorganic material with an inorganic material that preferably comprises an aluminum oxide and/or a zirconium oxide and still more preferably at least one organic material that comprises Al 2 O 3 and/or ZrO 2 , is used.
- TiO 2 that is coated with a hybrid inorganic-organic material is used.
- a second object of the present invention is made up of particles that can be obtained by use of one of the processes previously defined for the first object of the invention.
- These particles comprise a core coated with carbon, the core of said particles being:
- Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co.
- a preferred sub-family is made up of particles wherein the core mainly comprises preferably at least 65% of Li 4 Ti 5 O 12 , of Li (4 ⁇ ) Z ⁇ Ti 5 O 12 or Li 4 Z ⁇ Ti (5 ⁇ ) O 12 or a mixture of these.
- the complement notably being made up of TiO 2 Li 2 TiO 3 or the residues of solvents.
- the core of the particles according to the invention is exclusively made up of Li 4 Ti 5 O 12 , of Li (4 ⁇ ) Z ⁇ Ti 5 O 12 or Li 4 Z ⁇ Ti (5 ⁇ ) O 12 or a mixture of these.
- a preferred sub-family of particles of the present invention is made up of particles that have a reversible capacity, measured according to the method defined in the description, which is between 155 and 170 mAh/g.
- these particles are made up of a core of Li 4 Ti 5 O 12 coated with a layer of carbon.
- the particles according to the invention are preferably nanostructures. Their size, measured with scanning electron microscopy, is preferably comprised between 10 and 950 nanometers.
- the particles according to the present invention are also characterized by their core, which has a size measured using scanning electron microscopy that is preferably comprised between 10 and 500 nanometers.
- the carbon coating that covers these particles is characterized by a thickness that, also measured using scanning electron microscopy, is comprised between 10 and 450 nanometers, still more preferably the thickness of the coating varies between 20 and 300 nanometers.
- a third object of the present invention is made up of a cathode of an electrochemical generator (preferably a recyclable type electrochemical generator) comprising particles such as previously defined in the second object of the present invention and/or such that can be obtained by using any one of the processes according to the first object of the present invention.
- an electrochemical generator preferably a recyclable type electrochemical generator
- a fourth object of the present invention is made up of an anode for an electrochemical generator (preferably a recyclable type electrochemical generator) comprising particles such as previously defined in the second object of the present invention and/or such that can be obtained by using any one of the processes according to the first object of the present invention.
- an electrochemical generator preferably a recyclable type electrochemical generator
- a fifth object of the present invention is made up of an electrochemical generator (preferably of the rechargeable type) of the lithium type comprising an anode of the metallic lithium type and a cathode of the Li 4 Ti 5 O 12 type and/or of the Li (4 ⁇ ) Z ⁇ Ti 5 O 12 type and/or of the Li 4 Z ⁇ Ti (5 ⁇ ) O 12 type or mixtures of them, the cathode in this battery being such as previously defined in the third object of the present invention.
- a sixth object of the present invention is made up of an electrochemical generator (preferably of the rechargeable type) of the lithium-ion type comprising an anode of the Li 4 Ti 5 O 12 type and/or the Li (4 ⁇ ) Z ⁇ Ti 5 O 12 type and/or the Li 4 Z ⁇ Ti (5 ⁇ ) O 12 type or mixtures of them and a cathode of the LiFePO 4 , LiCoO 2 , LiCoPO 4 , LiMn 2 O 4 and/or LiNiO 2 type or mixtures of them wherein the anode is such as defined in the third object of the present invention.
- such a generator uses, in the anode and/or in the cathode, a current collector of solid aluminum or of the Exmet type (expanded metal).
- a preferred sub-family of the electrochemical generators according to the present invention is made up of generators that do not require any prior forming of the battery.
- a seventh object of the present invention is made up of a hybrid-type supercapacitor comprising an anode of the Li 4 Ti 5 O 12 type and/or the Li (4 ⁇ ) Z ⁇ Ti 5 O 12 type and/or the Li 4 Z ⁇ Ti (5 ⁇ ) O 12 type and a cathode of the graphite or carbon type with a large specific surface area, wherein the anode is as defined previously, not requiring any preliminary forming of the supercapacitor.
- the anode and/or the cathode of such a supercapacitor is (are) equipped with a current collector of solid aluminum or of the Exmet (expanded metal) type.
- the electrolyte used in the electrochemical generator or in the supercapacitor is dry polymer, gel, liquid or ceramic in nature.
- the present invention makes available a new synthesis method for Li 4 Ti 5 O 12 that is simple, fast and less costly.
- the synthesis is based on a ternary mixture of TiO 2 with anatase or rutile structure, of Li 2 CO 3 and carbon.
- the mixture is well dispersed, then submitted to a heating phase that comprises two steps.
- the first step is rapid heating to 400° C. in air. This temperature stage helps, on one hand, to eliminate the traces of heptane when this solvent is used and, on the other hand, to stimulate the release of CO 2 .
- the second step to 600° C. is longer and requires a minimum of 4 hours. This completes the transformation of the ternary mixture to Li 4 Ti 5 O 12 with spinel structure.
- the fineness of the particle size is obtained due to a longer heating time during the second step (see the illustration given in FIG. 2).
- the carbon is oxidized with the oxygen in the air, with oxygen coming from TiO 2 while releasing CO 2 .
- titanium reacts with lithium, forming lithiated titanium. The latter oxidizes with air.
- the synthesis reaction can be schematically illustrated as follows:
- An excess of carbon is used to ensure complete transformation. In fact, carbon burns in the presence of air, then its excess reduces TiO 2 and Li 2 CO 3 .
- carbons that contain oxygen groups at the surface are used. The latter react with the lithium oxide.
- the TiO 2 -carbon-Li 2 CO 3 mixture can be produced using two methods: in a solvent or in a dry mixture dispersed mechanically. Once the intimate homogeneous powder is obtained, the carbon will play the essential role established according to reaction (2) by obtaining a Li 4 Ti 5 O 12 product without impurities.
- the synthesis was also carried out with the TiO 2 —Li 2 CO 3 -carbon mixture dispersed by high-energy mechanical milling (HEMM).
- HEMM high-energy mechanical milling
- the main step before the passage to HEMM is to disperse the ternary mixture well in order to obtain a homogeneous mixture (FIG. 10), For this, first a co-milling for 15 minutes to 2 hours is used, in addition, this co-milling also helps to lower the synthesis temperature.
- This process produces particles on the nanostructure scale of Li 4 Ti 5 O 12 (FIGS. 6, 7 and 8 ), compared to the classic method that makes it possible to carry out the formation of the macroscopic particles (FIGS. 4 and 5).
- Li 4 Ti 5 O 12 applications are presented in FIG. 1.
- the battery produces 1.5 volts, due to the rechargeability of the Li 4 Ti 5 O 12 , this system becomes very interesting for the rechargeable battery markets, thus replacing the large market of primary alkaline batteries of 1.5 volt.
- Li 4 Ti 5 O 12 is a white insulating powder, in order to increase its electronic conductivity, it is co-milled with carbon.
- the latter coats the particles of Li 4 Ti 5 O 12 and gives a good conductivity to the electrode at the time of intercalation and disintercalation of lithium and keeps its capacity (mAh/g) stable at elevated currents (mA/g).
- carbon plays a double role in this invention, on one hand, it helps to synthesize a final pure product of the Li 4 Ti 5 O 12 type by lowering the synthesis temperature, and on the other, it increases the electronic conductivity by co-milling with Li 4 Ti 5 O 12 for manufacturing electrodes for an electrochemical generator.
- FIG. 12 uses an insertion anode of the Li 4 Ti 5 O 12 type placed face to face with a cathode of the graphite or carbon type with large specific surface area (double layer) with a polymer, gel, liquid or ceramic electrolyte.
- the advantage of nano- Li 4 Ti 5 O 12 coated with carbon (FIG. 11) promotes the diffusion of lithium inside the spinel structure, and in particular, at elevated currents like 12C (charge-discharge in 5 minutes). At these ratings, the HSC develops 90% of the nominal capacity.
- the presence of carbon provides good conductivity at the grain level and on the scale of the electrode, which limits the addition of large proportions of carbon to the electrode. This makes it possible to increase the energy density of the HSC.
- HSC technology uses two collectors of the Exmet (expanded metal) type in aluminum with an electrolyte having a salt mixture of LiTFSI+LiBF 4 or LiTFSI+LiPF 6 or LiTFSI+BETi+LiBF 4 .
- This mixture makes it possible to have good ionic conductivity and reduces the collector corrosion during high-voltage charging.
- the energy density of the HSC is around 60 Wh/kg and the capacity obtained is 90% at charging rates of 12C.
- HSC technology presents an energy density comparable to Pb-acid or Ni—Cd technologies, in addition this technology has a long cyclability.
- Li-ion technology graphite/LiCoo 2
- currents less than 2C (30 minutes) and by the number of cycles which is 1200.
- This ternary mixture is placed in a steel container and heptane is added in a powder/liquid ratio of around 35 g/150 ml.
- the heptane is used to reduce the heat and the friction between the particles of powder and the balls and leaves the product inert.
- Stainless steel balls are added to homogenize the ternary mixture.
- the success of the co-milling depends on lowering the synthesis temperature.
- the heating of this co-milled mixture is carried out in two steps. The first step is a rapid heating to 400° C. in air. This temperature stage promotes the elimination of traces of heptane and stimulates the start of CO 2 release.
- the second step consists of slow heating to 600° C. This completes the transformation of the product into Li 4 Ti 5 O 12 with spinel structure.
- the X-ray spectrum confirms the presence of peak characteristics of the spinel structure of the Li 4 Ti 5 O 12 .
- FIG. 15 which is a photograph obtained using scanning electron microscopy, shows that the particles of Li 4 Ti 5 O 12 are of nanoscopic size.
- FIG. 14 relates to a photo obtained in the same manner, but for particles prepared without the addition of carbon shows that the corresponding particles are of macroscopic size.
- the particles of Li 4 Ti 5 O 12 , of poly(vinylidene fluoride) (PVDF) and Ketjen black, present in a mass ratio of 87/10/3 are mixed.
- This mixture is applied to an exmet electrode of aluminum, then heated for 12 hours with nitrogen scavenging.
- the electrode thus prepared is then heated for 2 hours in vacuum.
- the electrode is then assembled in an electrochemical cell of around 4 cm 2 with a Celgard type separator facing the lithium metal.
- the solvent is of the TESA type (tetra ethyl sulfone amine) ethylene carbonate type with LiTFSI salt (lithium trifluoromethanesulfonimide).
- the cycling is carried out, at ambient temperature, between 1.2 and 2.5 V.
- the reversible capacity obtained is 155 mAh/g with an average voltage of 1.55 V.
- Li 4 Ti 5 O 12 and Ketjen black in a volume ratio 40/3, are co-milled in heptane in the presence of stainless steel balls.
- the mixture is dried, then mixed with a polymer solution based on a polyether marketed by the Baker Hughes Company, USA under the commercial name UNITHOX 750, in a volume ratio 43/57.
- This mixture is then applied to an aluminum collector, then heated for 12 hours with nitrogen scavenging.
- the collector thus processed is then heated for 2 hours in vacuum.
- the electrode is assembled in an electrochemical cell with about 4 cm 2 surface area with a separator of the polymer type based on salt containing polyether prepared in a laboratory, with LiTFSI salt (tetra fluoro sulfur lithium imide) placed face to face with the lithium metal as anode. Cycling is carried out at 80° C. between 1.2 and 2.5 V. The reversible capacity obtained is 155 mAh/g in C/24 and it is 96% of the nominal capacity obtained with a rapid rating in C/1. The cell thus prepared demonstrates good cycling stability, more than 1500 cycles in C/1.
- the electrochemical result obtained by introduction of this electrode in a cell without solvent (completely solid) comprising a polymer (polyether) at 80° C. is 150 mAh/g in C/24 while only 75% of the nominal value is found with fast loading in C/1. In fact, this is due to the poor dispersion between the oxide and the carbon black. In addition, the reproducibility of the results is uncertain.
- particles of Li 4 Ti 5 O 12 were prepared using a binary mixture of LiOH—TiO 2 (anatase) of 10.5 and 16 g, respectively, heated for 18 hours in air.
- the X-ray spectrum obtained for these particles establishes the presence of peak characteristics of the spinel structure of Li 4 Ti 5 O 12 as well as the presence of traces of TiO 2 (rutile) and Li 2 TiO 3 .
- the Li 4 Ti 5 O 12 powder obtained is mixed with PVDF and with Shawinigan black in a weight ratio 87/10/3. This mixture, which makes up the electrode, is applied to an aluminium Exmet support, then heated for 12 hours with nitrogen scavenging. The electrode thus obtained is then heated for 2 hours in vacuum. Said electrode is assembled in an electrochemical cell about 4 cm 2 with a Celgard type separator placed face to face with lithium metal as anode.
- the solvent used is of the TESA type (tetra ethylsulfamide)—ethylene carbonate (1:1 by volume) with 1 mol of LiTFSI (bis(trifluoromethane sulfonimide)).
- the reversible capacity obtained in this case is 140 mAh/g.
- the capacity obtained by the binary type synthesis is thus appreciably less than that obtained by the using ternary synthesis in the presence of carbon.
- Li 4 Ti 5 O 12 particles are mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied on an aluminium Exmet type electrode, then heated for 12 hours with nitrogen scanning. All of this is then heated for 2 hours in vacuum.
- Cobalt oxide LiCoO 2 is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. Then the mixture thus obtained is applied to an aluminum Exmet type electrode, the assembly thus obtained is then heated for 12 hours with nitrogen scanning, then in a second step is heated for 2 hours in vacuum.
- the Li 4 Ti 5 O 12 electrode is assembled in a lithium-ion battery face to face with the LiCoO 2 electrode as cathode with a Celgard type separator.
- the solvent used is of the ethylene carbonate—methyl ethylene carbonate type (1:1 by volume) with 1 mole of lithium bis(trifluoromethane sulfonimide).
- the battery voltage tends toward zero volts (33 mV).
- the battery is cycled between 1.2 V and 2.8 V.
- the average voltage is around 2.5 V.
- the irreversible capacity of the first cycle is around 2%. This irreversibility is minimum compared to the conventional carbon/LiCoO 2 system. Because of the fact that the two electrodes of the Li 4 Ti 5 O 12 /LiCoO 2 system have no passivation film, the reversible capacity of the battery is stable for more than 500 cycles. Knowing that 2.5 V yields 70% of the average voltage of the lithium-ion system of the carbon/LiCoO 2 type, a 30% deficit remains to be recaptured. The lack of energy to be obtained from the carbon/LiCoO 2 system can be filled by:
- an Exmet type collector based on aluminum on the anode that makes it possible to reduce the weight of the battery (conventional carbon/LiCoO 2 system using copper as current collector for the anode);
- Li 4 Ti 5 O 12 is mixed with PVDF and Shawinigan black in a weight 87/10/3. This mixture is applied to an aluminium Exmet type electrode.
- Natural graphite NG7 (Kansai Coke, Japan) is mixed with PVDF in a weight ratio 90/10. This mixture is applied to an aluminium Exmet type electrode. The assembly thus obtained is heated for 12 hours with nitrogen scavenging, then heated 2 hours in vacuum.
- the Li 4 Ti 5 O 12 electrode is mounted face to face with the graphite electrode separated by a Celgard.
- the solvent used is PC+EC+TESA (1:1:1 by volume) containing 1 mol of LiPF 5 +LiTFSI.
- the graphite electrode is used as cathode and the intercalation reaction is an electrolytic reaction of the double layer, of which the anion PF 6 is absorbed at the surface of the graphite.
- the voltage cycling limits are between 1.5 V and 3.0 V, for an average voltage of 2.25 V. This average voltage value increases the energy density by 50% with respect to values obtained with a conventional carbon-carbon system.
- Li 4 Ti 5 O 12 is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied to an aluminium Exmet electrode. All of this is heated for 12 hours with nitrogen scavenging, then for 2 hours in vacuum.
- the Li 4 Ti 5 O 12 electrode is mounted face to face with a carbon electrode as cathode, separated by a Celgard.
- the solvent used is EC+PC+DMC (1:1:1 by volume) containing 1 mole of LiTFSI+LiBF 4 .
- the carbon electrode is used as cathode.
- the intercalation reaction in this case is a double layer electrolytic reaction, wherein the PF6 and TFSI anions are absorbed at the carbon surface.
- the cycling voltage limits are between 1.5 V and 3.0 V with an average potential of 2.25 V. This average voltage value increases the energy density by 50% comparatively to the conventional carbon-carbon system.
- Li 4 Ti 5 O 12 is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied to an aluminium Exmet electrode. All of this is heated for 12 hours with nitrogen scavenging at a temperature of 120° C., then for 2 hours in vacuum at a temperature of 120° C.
- a conductive polymer of the polyaniline type is mixed with PVDF and Shawinigan black in a weight ratio 87:10:3.
- the mixture thus obtained is applied to an aluminium Exmet electrode, then heated for 12 hours with nitrogen scavenging at a temperature of 120° C., then for 2 hours in vacuum at a temperature of 120° C.
- the Li 4 Ti 5 O 12 electrode is mounted face to face with the carbon electrode as cathode separated by a Celgard.
- the solvent used is EC+PC+DMC (1:1:1 by volume), commonly called, containing 1 mole of LiTFSI+LiBF 4 .
- the polymer electrode conductor is used as cathode.
- the intercalation reaction is then a doping reaction of the PF 6 and TFSI anions across the conductive polymer chains.
- the cycling voltage limits are comprised between 1.5 V and 3.0 V with an average voltage of 2.25 V. The performance observed is comparable to that obtained in the preceding example.
- the particles according to the present invention present a surprisingly notable spreading capacity, an excellent nominal capacity, an excellent cycling stability and a remarkable high current power in electrochemical devices that use them, in particular at the electrode level, as well as flexibility regarding electrode thickness that can be produced using these particles.
- the particles in nano form yield 90% of the nominal capacity, while the corresponding macroparticles develop no more than 50% of the capacity.
- the macros also have a limitation with currents less then 5C.
- the nano-particles do not have any limitation.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/808,353 US20070243467A1 (en) | 2000-12-05 | 2007-06-08 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZbetaTi(5-beta)O12 particles, process for obtaining same and use as electrochemical generators |
US12/149,535 US8114469B2 (en) | 2000-12-05 | 2008-05-02 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-βO12 particles, processes for obtaining same and use as electrochemical generators |
US13/360,173 US9077031B2 (en) | 2000-12-05 | 2012-01-27 | Li4Ti5O12, Li(4-α)ZαTi5O12or Li4ZβTi(5-β)O12 particles, processes for obtaining same and their use in electrochemical generators |
US14/461,786 US9559356B2 (en) | 2000-12-05 | 2014-08-18 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12 particles, processes for obtaining same and use as electrochemical generators |
US15/252,944 US10734647B2 (en) | 2000-12-05 | 2016-08-31 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12, particles, processes for obtaining same and use as electrochemical generators |
US16/910,396 US20200373570A1 (en) | 2000-12-05 | 2020-06-24 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZßTi(5-ß)O12, PARTICLES, PROCESSES FOR OBTAINING SAME AND USE AS ELECTROCHEMICAL GENERATORS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002327370A CA2327370A1 (fr) | 2000-12-05 | 2000-12-05 | Nouvelle methode de fabrication de li4ti5o12 pur a partir du compose ternaire tix-liy-carbone: effet du carbone sur la synthese et la conductivite de l'electrode |
CA2,327,370 | 2000-12-05 |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10432999 Continuation | 2001-12-03 | ||
PCT/CA2001/001714 Continuation WO2002046101A2 (en) | 2000-12-05 | 2001-12-03 | LI4TI5O12, LI (4-α) ZαTI5O12, OR LI4ZβTI (5-β)O12 PARTICLES, METHODS FOR OBTAINING SAME AND USE AS ELECTROCHEMICAL GENERATORS |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/808,353 Continuation US20070243467A1 (en) | 2000-12-05 | 2007-06-08 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZbetaTi(5-beta)O12 particles, process for obtaining same and use as electrochemical generators |
US12/149,535 Division US8114469B2 (en) | 2000-12-05 | 2008-05-02 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-βO12 particles, processes for obtaining same and use as electrochemical generators |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040202934A1 true US20040202934A1 (en) | 2004-10-14 |
Family
ID=4167802
Family Applications (7)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/830,240 Abandoned US20040202934A1 (en) | 2000-12-05 | 2004-04-23 | Li4Ti5O12, Li(4-alpha)Zalpha Ti5O12 or Li4ZbetaTi(5-beta)O12 particles, processes for obtaining same and use as electrochemical generators |
US11/808,353 Abandoned US20070243467A1 (en) | 2000-12-05 | 2007-06-08 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZbetaTi(5-beta)O12 particles, process for obtaining same and use as electrochemical generators |
US12/149,535 Expired - Fee Related US8114469B2 (en) | 2000-12-05 | 2008-05-02 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-βO12 particles, processes for obtaining same and use as electrochemical generators |
US13/360,173 Expired - Fee Related US9077031B2 (en) | 2000-12-05 | 2012-01-27 | Li4Ti5O12, Li(4-α)ZαTi5O12or Li4ZβTi(5-β)O12 particles, processes for obtaining same and their use in electrochemical generators |
US14/461,786 Expired - Lifetime US9559356B2 (en) | 2000-12-05 | 2014-08-18 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12 particles, processes for obtaining same and use as electrochemical generators |
US15/252,944 Expired - Lifetime US10734647B2 (en) | 2000-12-05 | 2016-08-31 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12, particles, processes for obtaining same and use as electrochemical generators |
US16/910,396 Abandoned US20200373570A1 (en) | 2000-12-05 | 2020-06-24 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZßTi(5-ß)O12, PARTICLES, PROCESSES FOR OBTAINING SAME AND USE AS ELECTROCHEMICAL GENERATORS |
Family Applications After (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/808,353 Abandoned US20070243467A1 (en) | 2000-12-05 | 2007-06-08 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZbetaTi(5-beta)O12 particles, process for obtaining same and use as electrochemical generators |
US12/149,535 Expired - Fee Related US8114469B2 (en) | 2000-12-05 | 2008-05-02 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-βO12 particles, processes for obtaining same and use as electrochemical generators |
US13/360,173 Expired - Fee Related US9077031B2 (en) | 2000-12-05 | 2012-01-27 | Li4Ti5O12, Li(4-α)ZαTi5O12or Li4ZβTi(5-β)O12 particles, processes for obtaining same and their use in electrochemical generators |
US14/461,786 Expired - Lifetime US9559356B2 (en) | 2000-12-05 | 2014-08-18 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12 particles, processes for obtaining same and use as electrochemical generators |
US15/252,944 Expired - Lifetime US10734647B2 (en) | 2000-12-05 | 2016-08-31 | Li4Ti5O12, Li(4-α)ZαTi5O12 or Li4ZβTi(5-β)O12, particles, processes for obtaining same and use as electrochemical generators |
US16/910,396 Abandoned US20200373570A1 (en) | 2000-12-05 | 2020-06-24 | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZßTi(5-ß)O12, PARTICLES, PROCESSES FOR OBTAINING SAME AND USE AS ELECTROCHEMICAL GENERATORS |
Country Status (11)
Country | Link |
---|---|
US (7) | US20040202934A1 (da) |
EP (1) | EP1339642B1 (da) |
JP (2) | JP4790204B2 (da) |
AT (1) | ATE449035T1 (da) |
AU (1) | AU2002221410A1 (da) |
CA (2) | CA2327370A1 (da) |
DE (1) | DE60140564D1 (da) |
DK (1) | DK1339642T3 (da) |
ES (1) | ES2337026T3 (da) |
PT (1) | PT1339642E (da) |
WO (1) | WO2002046101A2 (da) |
Cited By (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030207178A1 (en) * | 2002-04-29 | 2003-11-06 | Zhendong Hu | Method of preparing electrode composition having a carbon-containing-coated metal oxide, electrode composition and electrochemical cell |
US20060234125A1 (en) * | 2005-04-15 | 2006-10-19 | Avestor Limited Partnership | Lithium Ion Rocking Chair Rechargeable Battery |
KR100686805B1 (ko) | 2005-04-25 | 2007-02-26 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
US20070148545A1 (en) * | 2005-12-23 | 2007-06-28 | The University Of Chicago | Electrode materials and lithium battery systems |
US20070259259A1 (en) * | 2004-02-12 | 2007-11-08 | Commissariat A L'energie Antomique | Lithium Battery Which is Protected in Case of Inappropriate Use |
WO2008067677A1 (en) * | 2006-12-07 | 2008-06-12 | Phostech Lithium Inc. | A method for preparing a particulate cathode material, and the material obtained by said method |
US20080261113A1 (en) * | 2006-11-15 | 2008-10-23 | Haitao Huang | Secondary electrochemical cell with high rate capability |
US20080315161A1 (en) * | 2004-07-28 | 2008-12-25 | Gs Yuasa Corporation | Electrochemical Device-Oriented Electrode Material and Production Method Thereof , as Well as Electrochemical Device-Oriented Electrode and Electochemical Device |
US20080318127A1 (en) * | 2002-12-19 | 2008-12-25 | Uchicago Argonne, Llc | Anode material for lithium batteries |
US20090004563A1 (en) * | 2007-06-28 | 2009-01-01 | Zhimin Zhong | Substituted lithium titanate spinel compound with improved electron conductivity and methods of making the same |
US20090253036A1 (en) * | 2004-04-13 | 2009-10-08 | Nanotecture Ltd. | Electrochemical Cell |
US20090297947A1 (en) * | 2008-05-30 | 2009-12-03 | Haixia Deng | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
WO2009126377A3 (en) * | 2008-03-04 | 2009-12-23 | Enerdel. Inc. | Anode for lithium-ion cell and method of making the same |
WO2010012076A1 (en) * | 2008-07-28 | 2010-02-04 | Hydro - Quebec | Composite electrode material |
US20100233538A1 (en) * | 2009-03-12 | 2010-09-16 | Belenos Clean Power Holding Ag | Open porous electrically conductive nanocomposite material |
US20100308277A1 (en) * | 2009-04-01 | 2010-12-09 | The Swatch Group Research And Development Ltd | Electrically conductive nanocomposite material comprising sacrificial nanoparticles and open porous nanocomposites produced thereof |
US20110008676A1 (en) * | 2008-03-04 | 2011-01-13 | Golovin M Neal | Anode for lithium-ion cell and method of making the same |
US20110012067A1 (en) * | 2008-04-14 | 2011-01-20 | Dow Global Technologies Inc. | Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
US20110189545A1 (en) * | 2008-06-03 | 2011-08-04 | Süd-Chemie AG | Process for the preparation of lithium titanium spinel and its use |
US20120100426A1 (en) * | 2006-05-01 | 2012-04-26 | Jim Kim | Lithium secondary battery of improved low-temperature power property |
US20120208066A1 (en) * | 2009-08-17 | 2012-08-16 | Li-Tec Battery Gmbh | Method for the production of an electrode stack |
US20130161558A1 (en) * | 2011-12-26 | 2013-06-27 | Taiyo Yuden Co., Ltd. | Lithium-titanium complex oxide, and battery electrode and lithium ion secondary battery containing same |
US20130244114A1 (en) * | 2010-08-31 | 2013-09-19 | Toda Kogyo Corporation | Lithium titanate particles and process for producing the lithium titante particles, MG-Containing lithium titanate particles and process for producing the MG-Containing lithium particles, negative electrode active substance particles for non-aqueous electrolyte secondary batteries, and non-aqeous electrolyte secondary battery |
CN103579600A (zh) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种过渡金属改性钛酸锂材料的制备方法 |
CN103594694A (zh) * | 2013-11-28 | 2014-02-19 | 扬州大学 | 一种球形钛酸锂离子电池负极材料的制备方法 |
CN103682298A (zh) * | 2013-11-27 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种掺镧钛酸锂复合材料及制备方法和应用 |
CN104039708A (zh) * | 2011-11-28 | 2014-09-10 | 雷诺股份公司 | 在碳的存在下通过碾磨来生产基于Li4Ti5O12的材料 |
US20140322609A1 (en) * | 2011-11-30 | 2014-10-30 | Posco Es Materials Co., Ltd. | Preparation method of lithium titanium composite oxide doped with dissimilar metal, and lithium titanium composite oxide doped with dissimilar metal prepared thereby |
US20140325807A1 (en) * | 2011-06-09 | 2014-11-06 | Meriem Anouti | Method for assembling a hybrid lithium supercapacitor |
TWI461366B (zh) * | 2008-10-07 | 2014-11-21 | Sued Chemie Ip Gmbh & Co Kg | 經碳塗覆之鋰鈦尖晶石 |
US20150140433A1 (en) * | 2013-11-20 | 2015-05-21 | Kabushiki Kaisha Toshiba | Battery active material, nonaqueous electrolyte battery and battery pack |
US20150333322A1 (en) * | 2014-05-13 | 2015-11-19 | Kabushiki Kaisha Toshiba | Composite |
US9242871B2 (en) | 2007-12-06 | 2016-01-26 | Johnson Matthey Plc | Nanoparticulate composition and method for its production |
US20160126545A1 (en) * | 2013-06-05 | 2016-05-05 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
US9350015B2 (en) | 2011-04-19 | 2016-05-24 | Samsung Sdi Co., Ltd. | Anode active material, anode and lithium battery including the material, and method of preparing the material |
US9428396B2 (en) | 2011-04-28 | 2016-08-30 | Ishihara Sangyo Kaisha, Ltd | Method for producing lithium titanate precursor, method for producing lithium titanate, lithium titanate, electrode active material, and electricity storage device |
US20160304355A1 (en) * | 2015-04-14 | 2016-10-20 | Korea Basic Science Institute | Synthesis method of lithium-titanium oxide using solid-state method |
CN109524632A (zh) * | 2017-09-19 | 2019-03-26 | 株式会社东芝 | 活性物质、电极、二次电池、电池组和车辆 |
US10505186B2 (en) | 2015-01-30 | 2019-12-10 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
US10511014B2 (en) | 2015-01-30 | 2019-12-17 | Kabushiki Kaisha Toshiba | Battery module and battery pack |
US10516163B2 (en) | 2015-03-13 | 2019-12-24 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
US10553868B2 (en) | 2014-12-02 | 2020-02-04 | Kabushiki Kaisha Toshiba | Negative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle |
CN111969185A (zh) * | 2020-07-07 | 2020-11-20 | 湖南大学 | 包覆TiO2的石墨双离子电池复合正极材料及其制备方法 |
US10984961B2 (en) | 2016-06-22 | 2021-04-20 | Nippon Chemi-Con Corporation | Hybrid capacitor and manufacturing method thereof |
US11152159B2 (en) | 2016-06-22 | 2021-10-19 | Nippon Chemi-Con Corporation | Hybrid capacitor and manufacturing method thereof |
US11289277B2 (en) * | 2017-05-01 | 2022-03-29 | Tayca Corporation | Lithium ion capacitor positive electrode |
Families Citing this family (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2002319587B2 (en) | 2001-07-20 | 2007-05-10 | Altair Nanomaterials Inc. | Process for making lithium titanate |
JP4496688B2 (ja) * | 2001-09-06 | 2010-07-07 | 株式会社ジーエス・ユアサコーポレーション | 二次電池 |
CA2394056A1 (fr) * | 2002-07-12 | 2004-01-12 | Hydro-Quebec | Particules comportant un noyau non conducteur ou semi conducteur recouvert d'un couche conductrice, leurs procedes d'obtention et leur utilisation dans des dispositifs electrochimiques |
US8524397B1 (en) | 2004-11-08 | 2013-09-03 | Quallion Llc | Battery having high rate and high capacity capabilities |
US7632317B2 (en) | 2002-11-04 | 2009-12-15 | Quallion Llc | Method for making a battery |
JP2005135775A (ja) * | 2003-10-30 | 2005-05-26 | Yuasa Corp | リチウムイオン二次電池 |
JP2006040557A (ja) * | 2004-07-22 | 2006-02-09 | Hitachi Maxell Ltd | 有機電解液二次電池 |
FR2873497B1 (fr) * | 2004-07-23 | 2014-03-28 | Accumulateurs Fixes | Accumulateur electrochimique au lithium fonctionnant a haute temperature |
CA2482003A1 (fr) | 2004-10-12 | 2006-04-12 | Hydro-Quebec | Melange ternaire polymere - sel fondu - solvant, procede de fabrication et utilisation dans les systemes electrochimiques |
JP2006156836A (ja) * | 2004-11-30 | 2006-06-15 | Tdk Corp | 電解液及び電気化学デバイス |
JP4213688B2 (ja) * | 2005-07-07 | 2009-01-21 | 株式会社東芝 | 非水電解質電池及び電池パック |
JP5466408B2 (ja) * | 2006-02-28 | 2014-04-09 | プリメット プレシジョン マテリアルズ, インコーポレイテッド | リチウムベースの化合物のナノ粒子組成物および該ナノ粒子組成物を形成する方法 |
JP4602306B2 (ja) | 2006-09-29 | 2010-12-22 | 株式会社東芝 | 非水電解質電池用負極活物質、非水電解質電池、電池パック及び自動車 |
CA2566906A1 (en) * | 2006-10-30 | 2008-04-30 | Nathalie Ravet | Carbon-coated lifepo4 storage and handling |
CA2708708C (en) * | 2007-12-10 | 2013-11-05 | Umicore | Negative electrode material for li-ion batteries |
CN101515640B (zh) * | 2008-02-22 | 2011-04-20 | 比亚迪股份有限公司 | 一种负极和包括该负极的锂离子二次电池 |
US20090221405A1 (en) * | 2008-03-03 | 2009-09-03 | Leao Wang | Shaking mechanism of a treadmill |
KR100931095B1 (ko) * | 2008-03-06 | 2009-12-10 | 현대자동차주식회사 | 금속산화물을 양극 및 음극에 적용한 비대칭 하이브리드커패시터 |
JP5319947B2 (ja) * | 2008-03-25 | 2013-10-16 | 株式会社東芝 | 非水電解質電池 |
JP2009238656A (ja) * | 2008-03-28 | 2009-10-15 | Gs Yuasa Corporation | 非水電解質電池用活物質及びそれを備えた非水電解質電池 |
JP5196555B2 (ja) * | 2008-08-06 | 2013-05-15 | 独立行政法人産業技術総合研究所 | 電極材料前駆体の製造方法及び得られた電極材料前駆体を用いる電極材料の製造方法 |
RU2397576C1 (ru) | 2009-03-06 | 2010-08-20 | ООО "Элионт" | Анодный материал для литий-ионных хит и способ его получения |
US20100273055A1 (en) * | 2009-04-28 | 2010-10-28 | 3M Innovative Properties Company | Lithium-ion electrochemical cell |
CN102428031B (zh) * | 2009-05-26 | 2016-08-10 | 石原产业株式会社 | 钛酸锂、生产钛酸锂的方法以及各自包含钛酸锂的电极活性材料和蓄电装置 |
US8519527B2 (en) * | 2009-09-29 | 2013-08-27 | Bae Systems Information And Electronic Systems Integration Inc. | Isostress grid array and method of fabrication thereof |
DE102009049470A1 (de) * | 2009-10-15 | 2011-04-28 | Süd-Chemie AG | Verfahren zur Herstellung von feinteiligen Lithiumtitan-Spinellen und deren Verwendung |
CA2785010A1 (en) * | 2009-12-22 | 2011-06-30 | Ishihara Sangyo Kaisha, Ltd. | Lithium titanate, manufacturing method therefor, slurry used in said manufacturing method, electrode active material containing said lithium titanate, and lithium secondary battery using said electrode active material |
JP5434632B2 (ja) * | 2010-01-28 | 2014-03-05 | 株式会社Gsユアサ | 非水電解質二次電池用活物質及び非水電解質二次電池 |
AT509504A1 (de) * | 2010-02-19 | 2011-09-15 | Rubacek Lukas | Verfahren zum herstellen von lithiumtitanat |
JP5553110B2 (ja) * | 2010-05-18 | 2014-07-16 | 株式会社村田製作所 | 電極活物質およびその製造方法、ならびにそれを備えた非水電解質二次電池 |
TWI420729B (zh) * | 2010-07-12 | 2013-12-21 | Ind Tech Res Inst | 可快速充電鋰離子電池負極材料及其製備方法 |
DE102010032207B4 (de) * | 2010-07-26 | 2014-02-13 | Süd-Chemie Ip Gmbh & Co. Kg | Verfahren zur Verminderung von magnetischen und/oder oxidischen Verunreinigungen in Lithium-Metall-Sauerstoff-Verbindungen |
JP5690521B2 (ja) * | 2010-07-28 | 2015-03-25 | テイカ株式会社 | 鉄含有チタン酸リチウムの製造方法 |
JP5602541B2 (ja) * | 2010-08-25 | 2014-10-08 | 株式会社オハラ | 全固体リチウムイオン電池 |
KR101217561B1 (ko) | 2010-11-02 | 2013-01-02 | 삼성에스디아이 주식회사 | 음극 및 이를 포함하는 리튬전지 |
TWI441779B (zh) | 2010-12-20 | 2014-06-21 | Ind Tech Res Inst | 摻雜磷之尖晶石結構鋰鈦氧化物材料及其製備方法 |
CN102569764B (zh) * | 2010-12-28 | 2015-05-20 | 清华大学 | 钛酸锂复合材料及其制备方法以及锂离子电池 |
US9065148B2 (en) * | 2011-02-15 | 2015-06-23 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material for lithium ion secondary battery and method for producing the same |
DE102011016836A1 (de) * | 2011-04-12 | 2012-10-18 | Süd-Chemie AG | Verfahren zur Herstellung von Lithiumtitan-Spinell |
US9786912B2 (en) | 2011-04-28 | 2017-10-10 | Ishihara Sangyo Kaisha, Ltd. | Titanium raw material for lithium titanate production and method for producing lithium titanate using same |
WO2012169331A1 (ja) * | 2011-06-10 | 2012-12-13 | 東邦チタニウム株式会社 | チタン酸リチウム一次粒子、チタン酸リチウム凝集体及びこれらを用いたリチウムイオン二次電池、リチウムイオンキャパシタ |
EP2595224A1 (en) * | 2011-11-18 | 2013-05-22 | Süd-Chemie IP GmbH & Co. KG | Doped lithium titanium spinel compound and electrode comprising the same |
CN102544468B (zh) * | 2012-02-10 | 2016-12-14 | 中国科学院福建物质结构研究所 | 碳包覆的介孔钛酸锂锂离子电池负极材料及其制备方法 |
CN102683663B (zh) * | 2012-05-07 | 2016-08-03 | 宁德新能源科技有限公司 | 锂离子二次电池及其负极材料及其制备方法 |
DE102012208608A1 (de) * | 2012-05-23 | 2013-11-28 | Robert Bosch Gmbh | Verfahren zum Herstellen einer Elektrode für einen elektrochemischen Energiespeicher und Elektrode |
US9825292B2 (en) | 2012-10-10 | 2017-11-21 | Hydro-Quebec | Layered and spinel lithium titanates and processes for preparing the same |
CN103050730A (zh) * | 2012-11-29 | 2013-04-17 | 东莞市翔丰华电池材料有限公司 | 含金属铌改性钛酸锂电池 |
US9157019B2 (en) * | 2013-03-26 | 2015-10-13 | Jiali Wu | Thermal conductivity improved composition with addition of nano particles used for interface materials |
JP6138554B2 (ja) * | 2013-04-03 | 2017-05-31 | 日本ケミコン株式会社 | 複合材料、この複合材料の製造方法、この複合材料を用いたリチウムイオン二次電池及び電気化学キャパシタ |
US11223042B2 (en) * | 2014-03-31 | 2022-01-11 | Tronox Llc | Lithium-intercalated titanium dioxide, lithium titanate particles made therefrom, and related methods |
CN104852035B (zh) * | 2015-04-28 | 2017-07-07 | 湖南瑞翔新材料股份有限公司 | 氧化铝包覆的钛酸锂的制备方法 |
DE102015218436A1 (de) | 2015-09-25 | 2017-03-30 | Robert Bosch Gmbh | Symmetrischer Hybridsuperkondensator |
DE102015218435A1 (de) * | 2015-09-25 | 2017-03-30 | Robert Bosch Gmbh | Symmetrischer Hybridsuperkondensator und Verwendung von Li3V2(PO4)3 als Elektrodenmaterial für einen Hybridsuperkondensator |
CN105449187A (zh) * | 2015-12-20 | 2016-03-30 | 华南理工大学 | 一种高性能共掺杂钛酸锂电极材料的制备方法 |
JP6594202B2 (ja) * | 2015-12-28 | 2019-10-23 | 株式会社オザワエナックス | 高純度・高結晶チタン酸リチウムの製造方法及びこれを用いた高純度・高結晶チタン酸リチウム |
JP6696689B2 (ja) | 2016-03-16 | 2020-05-20 | 株式会社東芝 | 活物質、電極、非水電解質電池、電池パック、及び車両 |
WO2018154595A1 (en) | 2017-02-21 | 2018-08-30 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | A method of producing high performance lithium titanate anode material for lithium ion battery applications |
JP6353114B2 (ja) * | 2017-04-25 | 2018-07-04 | 株式会社東芝 | 負極 |
US11515519B2 (en) * | 2017-10-17 | 2022-11-29 | VoltaXplore Inc | Graphene-polymer porous scaffold for stable lithium-sulfur batteries |
US11456449B2 (en) * | 2018-08-02 | 2022-09-27 | Kabushiki Kaisha Toshiba | Electrode for a secondary battery, secondary battery, battery pack and vehicle |
CN110061223B (zh) * | 2019-05-06 | 2020-10-23 | 合肥工业大学 | 一种基于近化学平衡体系制备钛酸锂包覆高镍三元正极材料的方法 |
CN111029149B (zh) * | 2019-12-27 | 2021-09-17 | 安徽航睿电子科技有限公司 | 一种智能薄膜电容器 |
CN111900375B (zh) * | 2020-06-30 | 2022-05-10 | 国网浙江省电力有限公司湖州供电公司 | 一种电力储能用长寿命负极材料的制备方法及其在锂离子电池中的应用 |
KR102318880B1 (ko) * | 2020-08-06 | 2021-11-02 | 주식회사 나래나노텍 | Sn-Ti계 세라믹체를 포함하는 이차전지용 음극 활물질과 이의 제조방법 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5415878A (en) * | 1990-08-29 | 1995-05-16 | London School Of Pharmacy Innovations Limited | Slow release compositions |
US5591546A (en) * | 1994-04-21 | 1997-01-07 | Hival Ltd. | Secondary cell |
US6083644A (en) * | 1996-11-29 | 2000-07-04 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
US6103422A (en) * | 1995-12-26 | 2000-08-15 | Kao Corporation | Cathode active material and nonaqueous secondary battery containing the same |
US6221531B1 (en) * | 1998-07-09 | 2001-04-24 | The University Of Chicago | Lithium-titanium-oxide anodes for lithium batteries |
US20010031401A1 (en) * | 1999-02-16 | 2001-10-18 | Tetsuya Yamawaki | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US20010041293A1 (en) * | 2000-03-06 | 2001-11-15 | Barsukov Igor V. | Engineered carbonaceous materials and power sources using these materials |
US6749648B1 (en) * | 2000-06-19 | 2004-06-15 | Nanagram Corporation | Lithium metal oxides |
US6855273B2 (en) * | 1999-04-30 | 2005-02-15 | Acep, Inc. | Electrode materials with high surface conductivity |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2001A (en) * | 1841-03-12 | Sawmill | ||
JPS5180317A (da) | 1975-01-07 | 1976-07-13 | Tokai Carbon Kk | |
JPS53149194A (en) | 1977-05-31 | 1978-12-26 | Sharp Corp | Coating method for graphite substrate with silicon carbide |
SU826469A1 (ru) | 1979-08-07 | 1981-04-30 | Предприятие П/Я В-8117 | Электрощеточный материал |
JPS5926928A (ja) * | 1982-07-31 | 1984-02-13 | Res Inst For Prod Dev | チタン酸アルカリ金属の製造法 |
JP3502118B2 (ja) * | 1993-03-17 | 2004-03-02 | 松下電器産業株式会社 | リチウム二次電池およびその負極の製造法 |
JP3492397B2 (ja) * | 1993-08-10 | 2004-02-03 | 川鉄鉱業株式会社 | チタン酸アルカリ粉末、その製造方法、その含有複合材料及びチタン酸アルカリ焼結体の製造方法 |
JP3197779B2 (ja) * | 1995-03-27 | 2001-08-13 | 三洋電機株式会社 | リチウム電池 |
JPH09309427A (ja) * | 1996-03-19 | 1997-12-02 | Denso Corp | 車両用ブレーキ装置 |
JP4052695B2 (ja) * | 1996-06-14 | 2008-02-27 | 日立マクセル株式会社 | リチウム二次電池 |
US6686094B2 (en) * | 1996-07-30 | 2004-02-03 | Sony Corporation | Non-acqueous electrolyte secondary cell |
JPH10139429A (ja) * | 1996-11-13 | 1998-05-26 | Murata Mfg Co Ltd | リチウムチタン複合酸化物の製造方法 |
JPH10162828A (ja) * | 1996-11-29 | 1998-06-19 | Seiko Instr Inc | 非水電解質電池およびその製造方法 |
JPH10251020A (ja) * | 1997-03-11 | 1998-09-22 | Ishihara Sangyo Kaisha Ltd | 金属置換チタン酸リチウムおよびその製造方法ならびにそれを用いてなるリチウム電池 |
JPH10334917A (ja) * | 1997-06-04 | 1998-12-18 | Toshiba Battery Co Ltd | 非水溶媒二次電池 |
JPH1111948A (ja) * | 1997-06-16 | 1999-01-19 | Tohkem Prod:Kk | 安定なアナターゼ型二酸化チタン |
KR100518706B1 (ko) * | 1997-07-15 | 2005-10-05 | 소니 가부시끼 가이샤 | 비수성 전해액 2차 전지 |
JPH11111293A (ja) * | 1997-10-07 | 1999-04-23 | Hitachi Maxell Ltd | 有機電解液二次電池 |
FR2781184A1 (fr) * | 1998-07-20 | 2000-01-21 | Michelin Rech Tech | Roue avec jante ayant des sieges inclines vers l'exterieur |
JP2000251894A (ja) * | 1998-12-29 | 2000-09-14 | Hitachi Maxell Ltd | 非水二次電池およびその使用方法 |
JP4540167B2 (ja) * | 1999-02-16 | 2010-09-08 | 東邦チタニウム株式会社 | チタン酸リチウムの製造方法 |
JP3625680B2 (ja) * | 1999-03-25 | 2005-03-02 | 三洋電機株式会社 | リチウム二次電池 |
KR20010025116A (ko) * | 1999-04-06 | 2001-03-26 | 이데이 노부유끼 | 양극 활물질의 제조 방법 및 비수 전해질 이차 전지의제조 방법 |
US6252762B1 (en) * | 1999-04-21 | 2001-06-26 | Telcordia Technologies, Inc. | Rechargeable hybrid battery/supercapacitor system |
CA2658748A1 (fr) | 1999-04-30 | 2000-10-30 | Hydro-Quebec | Nouveaux materiaux d`electrode presentant une conductivite de surface elevee |
JP4177529B2 (ja) | 1999-08-30 | 2008-11-05 | 松下電器産業株式会社 | 非水電解質二次電池用負極、および非水電解質二次電池 |
JP4729774B2 (ja) * | 2000-02-28 | 2011-07-20 | 株式会社豊田中央研究所 | リチウム二次電池用負極材料の製造方法 |
JP2003272630A (ja) | 2002-03-19 | 2003-09-26 | Denso Corp | 負極活物質の製造方法 |
-
2000
- 2000-12-05 CA CA002327370A patent/CA2327370A1/fr not_active Abandoned
-
2001
- 2001-12-03 ES ES01999531T patent/ES2337026T3/es not_active Expired - Lifetime
- 2001-12-03 DE DE60140564T patent/DE60140564D1/de not_active Expired - Lifetime
- 2001-12-03 PT PT01999531T patent/PT1339642E/pt unknown
- 2001-12-03 CA CA2428090A patent/CA2428090C/fr not_active Expired - Lifetime
- 2001-12-03 DK DK01999531.5T patent/DK1339642T3/da active
- 2001-12-03 AU AU2002221410A patent/AU2002221410A1/en not_active Abandoned
- 2001-12-03 WO PCT/CA2001/001714 patent/WO2002046101A2/en active Search and Examination
- 2001-12-03 JP JP2002547845A patent/JP4790204B2/ja not_active Expired - Lifetime
- 2001-12-03 EP EP01999531A patent/EP1339642B1/fr not_active Expired - Lifetime
- 2001-12-03 AT AT01999531T patent/ATE449035T1/de active
-
2004
- 2004-04-23 US US10/830,240 patent/US20040202934A1/en not_active Abandoned
-
2007
- 2007-06-08 US US11/808,353 patent/US20070243467A1/en not_active Abandoned
-
2008
- 2008-05-02 US US12/149,535 patent/US8114469B2/en not_active Expired - Fee Related
-
2010
- 2010-06-07 JP JP2010129824A patent/JP5089732B2/ja not_active Expired - Lifetime
-
2012
- 2012-01-27 US US13/360,173 patent/US9077031B2/en not_active Expired - Fee Related
-
2014
- 2014-08-18 US US14/461,786 patent/US9559356B2/en not_active Expired - Lifetime
-
2016
- 2016-08-31 US US15/252,944 patent/US10734647B2/en not_active Expired - Lifetime
-
2020
- 2020-06-24 US US16/910,396 patent/US20200373570A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5415878A (en) * | 1990-08-29 | 1995-05-16 | London School Of Pharmacy Innovations Limited | Slow release compositions |
US5591546A (en) * | 1994-04-21 | 1997-01-07 | Hival Ltd. | Secondary cell |
US6103422A (en) * | 1995-12-26 | 2000-08-15 | Kao Corporation | Cathode active material and nonaqueous secondary battery containing the same |
US6083644A (en) * | 1996-11-29 | 2000-07-04 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
US6221531B1 (en) * | 1998-07-09 | 2001-04-24 | The University Of Chicago | Lithium-titanium-oxide anodes for lithium batteries |
US20010031401A1 (en) * | 1999-02-16 | 2001-10-18 | Tetsuya Yamawaki | Process for producing lithium titanate and lithium ion battery and negative electrode therein |
US6855273B2 (en) * | 1999-04-30 | 2005-02-15 | Acep, Inc. | Electrode materials with high surface conductivity |
US20010041293A1 (en) * | 2000-03-06 | 2001-11-15 | Barsukov Igor V. | Engineered carbonaceous materials and power sources using these materials |
US6749648B1 (en) * | 2000-06-19 | 2004-06-15 | Nanagram Corporation | Lithium metal oxides |
Cited By (79)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040175622A9 (en) * | 2002-04-29 | 2004-09-09 | Zhendong Hu | Method of preparing electrode composition having a carbon-containing-coated metal oxide, electrode composition and electrochemical cell |
US20030207178A1 (en) * | 2002-04-29 | 2003-11-06 | Zhendong Hu | Method of preparing electrode composition having a carbon-containing-coated metal oxide, electrode composition and electrochemical cell |
US20080318127A1 (en) * | 2002-12-19 | 2008-12-25 | Uchicago Argonne, Llc | Anode material for lithium batteries |
US7919207B2 (en) * | 2002-12-19 | 2011-04-05 | U Chicago Argonne Llc | Anode material for lithium batteries |
US20070259259A1 (en) * | 2004-02-12 | 2007-11-08 | Commissariat A L'energie Antomique | Lithium Battery Which is Protected in Case of Inappropriate Use |
US20090253036A1 (en) * | 2004-04-13 | 2009-10-08 | Nanotecture Ltd. | Electrochemical Cell |
US20080315161A1 (en) * | 2004-07-28 | 2008-12-25 | Gs Yuasa Corporation | Electrochemical Device-Oriented Electrode Material and Production Method Thereof , as Well as Electrochemical Device-Oriented Electrode and Electochemical Device |
US20060234123A1 (en) * | 2005-04-15 | 2006-10-19 | Avestor Limited Partnership | Lithium Rechargeable Battery |
WO2007006123A1 (en) * | 2005-04-15 | 2007-01-18 | Avestor Limited Partnership | Lithium ion rocking chair rechargeable battery |
US20060234125A1 (en) * | 2005-04-15 | 2006-10-19 | Avestor Limited Partnership | Lithium Ion Rocking Chair Rechargeable Battery |
KR100686805B1 (ko) | 2005-04-25 | 2007-02-26 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
US20070148545A1 (en) * | 2005-12-23 | 2007-06-28 | The University Of Chicago | Electrode materials and lithium battery systems |
US7968231B2 (en) | 2005-12-23 | 2011-06-28 | U Chicago Argonne, Llc | Electrode materials and lithium battery systems |
US20120100426A1 (en) * | 2006-05-01 | 2012-04-26 | Jim Kim | Lithium secondary battery of improved low-temperature power property |
US20080261113A1 (en) * | 2006-11-15 | 2008-10-23 | Haitao Huang | Secondary electrochemical cell with high rate capability |
EP2084765A4 (en) * | 2006-11-15 | 2013-10-02 | Valence Technology Inc | SECONDARY ELECTROCHEMICAL CELL WITH HIGH SPEED CAPACITY |
EP2084765A2 (en) * | 2006-11-15 | 2009-08-05 | Valence Technology, INC. | Secondary electrochemical cell with high rate capability |
CN101636861B (zh) * | 2006-12-07 | 2015-07-01 | 克拉瑞特(加拿大)有限公司 | 颗粒阴极材料的制备方法及通过该方法制备的材料 |
CN105633347A (zh) * | 2006-12-07 | 2016-06-01 | 庄信万丰股份有限公司 | 颗粒性阴极材料的制备方法及通过该方法制备的材料 |
EP2095451A4 (en) * | 2006-12-07 | 2010-09-29 | Phostech Lithium Inc | PROCESS FOR PREPARING PARTICULATE CATHODE MATERIAL AND MATERIAL OBTAINED BY SAID METHOD |
WO2008067677A1 (en) * | 2006-12-07 | 2008-06-12 | Phostech Lithium Inc. | A method for preparing a particulate cathode material, and the material obtained by said method |
US20100323245A1 (en) * | 2006-12-07 | 2010-12-23 | Guoxian Liang | A method for preparing a particulate cathode material, and the material obtained by said method |
EP2458666A1 (en) * | 2006-12-07 | 2012-05-30 | Phostech Lithium Inc. | A particle compositon for a particulate cathode material |
US10329154B2 (en) | 2006-12-07 | 2019-06-25 | Johnson Matthey Public Limited Company | Method for preparing a particulate cathode material |
US20090004563A1 (en) * | 2007-06-28 | 2009-01-01 | Zhimin Zhong | Substituted lithium titanate spinel compound with improved electron conductivity and methods of making the same |
US9242871B2 (en) | 2007-12-06 | 2016-01-26 | Johnson Matthey Plc | Nanoparticulate composition and method for its production |
CN101960655A (zh) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | 锂离电池阳极及其制造方法 |
US20110008676A1 (en) * | 2008-03-04 | 2011-01-13 | Golovin M Neal | Anode for lithium-ion cell and method of making the same |
WO2009126377A3 (en) * | 2008-03-04 | 2009-12-23 | Enerdel. Inc. | Anode for lithium-ion cell and method of making the same |
US20110012067A1 (en) * | 2008-04-14 | 2011-01-20 | Dow Global Technologies Inc. | Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
US8784694B2 (en) * | 2008-04-14 | 2014-07-22 | Dow Global Technologies Llc | Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
US9413006B2 (en) | 2008-04-14 | 2016-08-09 | Dow Global Technologies Llc | Lithium manganese phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
US20090297947A1 (en) * | 2008-05-30 | 2009-12-03 | Haixia Deng | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
US8277683B2 (en) | 2008-05-30 | 2012-10-02 | Uchicago Argonne, Llc | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
US20110189545A1 (en) * | 2008-06-03 | 2011-08-04 | Süd-Chemie AG | Process for the preparation of lithium titanium spinel and its use |
US9187336B2 (en) | 2008-06-03 | 2015-11-17 | Sued-Chemie Ip Gmbh & Co. Kg | Process for the preparation of lithium titanium spinel and its use |
US20110123858A1 (en) * | 2008-07-28 | 2011-05-26 | Hydro-Quebec | Composite electrode material |
US9240596B2 (en) | 2008-07-28 | 2016-01-19 | Hydro-Quebec | Composite electrode material |
WO2010012076A1 (en) * | 2008-07-28 | 2010-02-04 | Hydro - Quebec | Composite electrode material |
US9085491B2 (en) | 2008-10-07 | 2015-07-21 | Sued-Chemie Ip Gmbh & Co. Kg | Carbon-coated lithium titanium spinel |
TWI461366B (zh) * | 2008-10-07 | 2014-11-21 | Sued Chemie Ip Gmbh & Co Kg | 經碳塗覆之鋰鈦尖晶石 |
CN102186775B (zh) * | 2008-10-07 | 2015-11-25 | Sc知识产权有限两合公司 | 涂覆碳的锂钛尖晶石 |
US8426061B2 (en) | 2009-03-12 | 2013-04-23 | Belenos Clean Power Holding Ag | Nitride and carbide anode materials |
US20100233538A1 (en) * | 2009-03-12 | 2010-09-16 | Belenos Clean Power Holding Ag | Open porous electrically conductive nanocomposite material |
US9761867B2 (en) | 2009-03-12 | 2017-09-12 | Belenos Clean Power Holding Ag | Open porous electrically conductive nanocomposite material |
US20100233546A1 (en) * | 2009-03-12 | 2010-09-16 | Belenos Clean Power Holding Ag | Nitride and Carbide Anode Materials |
US20100308277A1 (en) * | 2009-04-01 | 2010-12-09 | The Swatch Group Research And Development Ltd | Electrically conductive nanocomposite material comprising sacrificial nanoparticles and open porous nanocomposites produced thereof |
US8507135B2 (en) * | 2009-04-01 | 2013-08-13 | The Swatch Group Research And Development Ltd | Electrically conductive nanocomposite material comprising sacrificial nanoparticles and open porous nanocomposites produced thereof |
US20120208066A1 (en) * | 2009-08-17 | 2012-08-16 | Li-Tec Battery Gmbh | Method for the production of an electrode stack |
US20130244114A1 (en) * | 2010-08-31 | 2013-09-19 | Toda Kogyo Corporation | Lithium titanate particles and process for producing the lithium titante particles, MG-Containing lithium titanate particles and process for producing the MG-Containing lithium particles, negative electrode active substance particles for non-aqueous electrolyte secondary batteries, and non-aqeous electrolyte secondary battery |
US9847526B2 (en) | 2010-08-31 | 2017-12-19 | Toda Kogyo Corporation | Lithium titanate particles and process for producing the lithium titanate particles, Mg-containing lithium titanate particles and process for producing the Mg-containing lithium titanate particles, negative electrode active substance particles for non-aqueous electrolyte secondary batteries, and non-aqueous electrolyte secondary battery |
US9293235B2 (en) * | 2010-08-31 | 2016-03-22 | Toda Kogyo Corporation | Lithium titanate particles and process for producing the lithium titanate particles, Mg-containing lithium titanate particles and process for producing the Mg-containing lithium titanate particles, negative electrode active substance particles for non-aqueous electrolyte secondary batteries, and non-aqueous electrolyte secondary battery |
US9350015B2 (en) | 2011-04-19 | 2016-05-24 | Samsung Sdi Co., Ltd. | Anode active material, anode and lithium battery including the material, and method of preparing the material |
US9428396B2 (en) | 2011-04-28 | 2016-08-30 | Ishihara Sangyo Kaisha, Ltd | Method for producing lithium titanate precursor, method for producing lithium titanate, lithium titanate, electrode active material, and electricity storage device |
US20140325807A1 (en) * | 2011-06-09 | 2014-11-06 | Meriem Anouti | Method for assembling a hybrid lithium supercapacitor |
US9136066B2 (en) * | 2011-06-09 | 2015-09-15 | Blue Solutions | Method for assembling a hybrid lithium supercapacitor |
CN104039708A (zh) * | 2011-11-28 | 2014-09-10 | 雷诺股份公司 | 在碳的存在下通过碾磨来生产基于Li4Ti5O12的材料 |
US20140322609A1 (en) * | 2011-11-30 | 2014-10-30 | Posco Es Materials Co., Ltd. | Preparation method of lithium titanium composite oxide doped with dissimilar metal, and lithium titanium composite oxide doped with dissimilar metal prepared thereby |
US20130161558A1 (en) * | 2011-12-26 | 2013-06-27 | Taiyo Yuden Co., Ltd. | Lithium-titanium complex oxide, and battery electrode and lithium ion secondary battery containing same |
CN103579600A (zh) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种过渡金属改性钛酸锂材料的制备方法 |
US20160126545A1 (en) * | 2013-06-05 | 2016-05-05 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
US10749173B2 (en) * | 2013-06-05 | 2020-08-18 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
US10170758B2 (en) * | 2013-06-05 | 2019-01-01 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
US20150140433A1 (en) * | 2013-11-20 | 2015-05-21 | Kabushiki Kaisha Toshiba | Battery active material, nonaqueous electrolyte battery and battery pack |
CN103682298A (zh) * | 2013-11-27 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种掺镧钛酸锂复合材料及制备方法和应用 |
CN103594694A (zh) * | 2013-11-28 | 2014-02-19 | 扬州大学 | 一种球形钛酸锂离子电池负极材料的制备方法 |
US11495789B2 (en) * | 2014-05-13 | 2022-11-08 | Kabushiki Kaisha Toshiba | Composite active material |
US20150333322A1 (en) * | 2014-05-13 | 2015-11-19 | Kabushiki Kaisha Toshiba | Composite |
US10553868B2 (en) | 2014-12-02 | 2020-02-04 | Kabushiki Kaisha Toshiba | Negative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle |
US10505186B2 (en) | 2015-01-30 | 2019-12-10 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
US10511014B2 (en) | 2015-01-30 | 2019-12-17 | Kabushiki Kaisha Toshiba | Battery module and battery pack |
US10516163B2 (en) | 2015-03-13 | 2019-12-24 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack and battery module |
US9896346B2 (en) * | 2015-04-14 | 2018-02-20 | Korea Basic Science Institute | Synthesis method of lithium-titanium oxide using solid-state method |
US20160304355A1 (en) * | 2015-04-14 | 2016-10-20 | Korea Basic Science Institute | Synthesis method of lithium-titanium oxide using solid-state method |
US10984961B2 (en) | 2016-06-22 | 2021-04-20 | Nippon Chemi-Con Corporation | Hybrid capacitor and manufacturing method thereof |
US11152159B2 (en) | 2016-06-22 | 2021-10-19 | Nippon Chemi-Con Corporation | Hybrid capacitor and manufacturing method thereof |
US11289277B2 (en) * | 2017-05-01 | 2022-03-29 | Tayca Corporation | Lithium ion capacitor positive electrode |
CN109524632A (zh) * | 2017-09-19 | 2019-03-26 | 株式会社东芝 | 活性物质、电极、二次电池、电池组和车辆 |
CN111969185A (zh) * | 2020-07-07 | 2020-11-20 | 湖南大学 | 包覆TiO2的石墨双离子电池复合正极材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1339642B1 (fr) | 2009-11-18 |
AU2002221410A1 (en) | 2002-06-18 |
WO2002046101A2 (en) | 2002-06-13 |
JP4790204B2 (ja) | 2011-10-12 |
WO2002046101A3 (en) | 2002-09-19 |
CA2327370A1 (fr) | 2002-06-05 |
DE60140564D1 (de) | 2009-12-31 |
JP5089732B2 (ja) | 2012-12-05 |
US20070243467A1 (en) | 2007-10-18 |
US20140356725A1 (en) | 2014-12-04 |
US20120135311A1 (en) | 2012-05-31 |
JP2005504693A (ja) | 2005-02-17 |
DK1339642T3 (da) | 2010-03-15 |
CA2428090C (fr) | 2010-04-20 |
US10734647B2 (en) | 2020-08-04 |
US9559356B2 (en) | 2017-01-31 |
US9077031B2 (en) | 2015-07-07 |
PT1339642E (pt) | 2010-02-03 |
US20160372746A1 (en) | 2016-12-22 |
JP2010280560A (ja) | 2010-12-16 |
ES2337026T3 (es) | 2010-04-20 |
CA2428090A1 (fr) | 2002-06-13 |
US20080285211A1 (en) | 2008-11-20 |
US20200373570A1 (en) | 2020-11-26 |
ATE449035T1 (de) | 2009-12-15 |
US8114469B2 (en) | 2012-02-14 |
EP1339642A2 (en) | 2003-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20200373570A1 (en) | Li4Ti5O12, Li(4-a)ZaTi5O12 OR Li4ZßTi(5-ß)O12, PARTICLES, PROCESSES FOR OBTAINING SAME AND USE AS ELECTROCHEMICAL GENERATORS | |
KR101604081B1 (ko) | 복합체 음극활물질, 이를 포함하는 음극, 이를 채용한 리튬전지 및 이의 제조 방법 | |
KR101378125B1 (ko) | 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 | |
US20070292760A1 (en) | Lithium-ion storage battery comprising TiO2-B as negative electrode active material | |
KR20120010211A (ko) | 다공성 실리콘계 화합물 또는 다공성 실리콘, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지용 음극 활물질 및 리튬 이차 전지 | |
JP2011001256A (ja) | 窒化リチウム−遷移金属複合酸化物の製造方法、窒化リチウム−遷移金属複合酸化物およびリチウム電池 | |
WO2017022464A1 (ja) | α-リチウム固体電解質 | |
KR20140048456A (ko) | 양극 활물질, 그 제조방법, 및 이를 포함하는 리튬 전지 | |
JP5197008B2 (ja) | 陰極複合材料及びその製造方法、陰極及びリチウムイオン電池 | |
US20150171426A1 (en) | POROUS AMORPHOUS GeOx AND ITS APPLICATION AS AN ANODE MATERIAL IN LI-ION BATTERIES | |
WO2022044720A1 (ja) | リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池 | |
US20190267615A1 (en) | Oxyfluoride cathodes and a method of producing the same | |
US20200403224A1 (en) | Lithium molybdate anode material | |
KR101713259B1 (ko) | 이차전지용 리튬 티탄 산화물-TiO₂ 복합체, 이의 제조 방법, 및 이를 포함하는 이차전지 | |
JP2020123581A (ja) | α−リチウム固体電解質 | |
KR100788257B1 (ko) | 고전압 전극 조성을 구비한 리튬 이차 전지 | |
KR101044577B1 (ko) | 고전압 리튬 이차 전지 | |
JP2023526984A (ja) | 新規の固体硫化物電解質 | |
KR100836515B1 (ko) | 고전압 전해액을 구비한 리튬 이차 전지 | |
CN114944493B (zh) | 一种锂离子锂氧气混合电池及其制备方法 | |
Zaghib et al. | Li 4 Ti 5 O 12, Li (4-α) Z α Ti 5 O 12 or Li 4 Z β Ti (5-β) O 12 particles, processes for obtaining same and their use in electrochemical generators | |
JP7465672B2 (ja) | 蓄電デバイス用負極材料 | |
WO2023135970A1 (ja) | 負極活物質及び負極 | |
CN117976832A (zh) | 一种包覆型硅负极材料及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HYDRO QUEBEC, CANADA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZAGHIB, KARIM;GAUTHIER, MICHEL;BROCHU, FERNAND;AND OTHERS;REEL/FRAME:016913/0588;SIGNING DATES FROM 20011206 TO 20011219 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |