JP6328888B2 - アモルファスおよび部分的にアモルファスからなるナノスケールイオン貯蔵材料 - Google Patents
アモルファスおよび部分的にアモルファスからなるナノスケールイオン貯蔵材料 Download PDFInfo
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- JP6328888B2 JP6328888B2 JP2013097415A JP2013097415A JP6328888B2 JP 6328888 B2 JP6328888 B2 JP 6328888B2 JP 2013097415 A JP2013097415 A JP 2013097415A JP 2013097415 A JP2013097415 A JP 2013097415A JP 6328888 B2 JP6328888 B2 JP 6328888B2
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- lithium
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- crystalline
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- 239000011232 storage material Substances 0.000 title description 26
- 239000000463 material Substances 0.000 claims description 112
- 229910052744 lithium Inorganic materials 0.000 claims description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 69
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 229910052723 transition metal Inorganic materials 0.000 claims description 25
- 150000003624 transition metals Chemical class 0.000 claims description 25
- 239000002086 nanomaterial Substances 0.000 claims description 20
- 239000010450 olivine Substances 0.000 claims description 19
- 229910052609 olivine Inorganic materials 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 description 48
- 238000000034 method Methods 0.000 description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 150000002500 ions Chemical class 0.000 description 33
- 238000002441 X-ray diffraction Methods 0.000 description 31
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 27
- 239000000843 powder Substances 0.000 description 26
- 238000003860 storage Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- 239000002245 particle Substances 0.000 description 20
- 208000028659 discharge Diseases 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- 230000007704 transition Effects 0.000 description 18
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000006104 solid solution Substances 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 238000007600 charging Methods 0.000 description 10
- 239000002178 crystalline material Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000011863 silicon-based powder Substances 0.000 description 9
- 239000012798 spherical particle Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000003991 Rietveld refinement Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910052732 germanium Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006138 lithiation reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 Co and Ni Chemical class 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910021398 atomic carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
-
- 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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/02—Amorphous compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
当該技術分野には、バッテリ等の装置において有用なイオン貯蔵材料、特にナノスケールのイオン貯蔵材料が含まれる。
イオン貯蔵材料は、蓄電池および他の電気化学的デバイスにおいて幅広く用いられている。アルカリ遷移金属リン酸塩を含む様々なイオン貯蔵材料が知られているが、この種の結晶化された化合物には、数多くのタイプの構造が存在する。具体例として、かんらん石(AXMXO4)、ナシコン(NASICON)(AX(M’,M”)2(XO4)3)、VOPO4、LiVPO4F、LiFe(P2O7)若しくはFe4(P2O7)3などの構造タイプの秩序的な若しくは部分的無秩序な構造が含まれる。ここで、Aはアルカリイオンであり、M、M’、M”は金属である。脱リチオ化状態で調製されたアモルファスFePO4材料もリチウム貯蔵材料として使用されている(岡田等の日本特許出願第06-283207号の抄録)。また、リチウムコバルトリン酸塩を含むアモルファスマテリアルも記載されている(米国特許第5,705,296号)。
アンドープのLi0.90FePO4、Li1.0FePO4、Li0.95FePO4の混合物を出発材料Li2CO3、FeC2O4・2H2O及び(NH4)H2PO4から調製した。出発原料は、ポリプロピレンのジャー(jar)において鋼鉄の破砕ボールを使用して、アセトン溶媒を用いて、72時間ボールミルしその後乾燥させた。その後窒素ガスを流しながら乾燥したマテリアルを最初350℃で10時間その後600℃で20時間焼成した。結果として得られるサンプルは、A(Li0.90FePO4)、B(Li1.0FePO4)、及びC(Li0.95FePO4)とラベルした。これらのサンプルは、ナノスケールであり、BET比表面積がそれぞれ38.43、39.48及び33.60m2/gであることが分かった。これらのサンプルはそれぞれ5.43%、4.90%、4.63%の炭素含有量を有していた。これらの粉末を、スウェージロック(登録商標)タイプのリチウム半電池に組み込み、低いレート及び高いレートでテストした。図1は、様々なCレートにおける放電キャパシティのプロットである。それぞれの曲線は、3つのセルの平均である。これらの結果は、当該マテリアルが高いレートにおいて高いキャパシティを有することを示している。図2A、B及びCは、それぞれサンプルA(0.0900モルLi2O3)、サンプルB(0.1000モルLi2CO3)、及びサンプルC(0.0950モルLi2O3)について、C/50レートで1サイクル充電若しくは放電した場合のキャパシティを示している。低いレートにおけるこれらの結果により、延長された低い電圧放電”テイル”が固溶液挙動を示すことが示されている。
Li0.5FePO4(サンプルF)、LiFePO4(サンプルG)の2つの混合物を実施例1に記載されたサンプルと同じ出発原料及び手順を用いて調製した。BET比表面積及び炭素含有量はそれぞれ42.86m2/g及び22.96m2/g、4.00%及び4.68%であった。Siとそれぞれのサンプル(図16−17)についての、質量で50:50の混合物のXRDによれば、Li0.5FePO4サンプルが、より高いLi含有量の前述のサンプルより、Siに対する強度においてより減少した、幅広のかんらん石ピークを有することが示された。FePO4サンプルはなお異なる。すなわち、容易に識別することができるかんらん石のピークはなく、ただ幅広いピークが存在する。これは、またヘキサゴナルFePO4相と適合しなかった。前述のXRDパターンのいずれもが(Liを欠く組成物についてのものでさえ)、ヘキサゴナルのFePO4相であることを示さないことは注目に値する。これにより、当該結果は、リチウムの存在がサンプルの完全な結晶化を促進するのではなく、かんらん石相の結晶化を促進し、Liが存在しない状態において、異なるアモルファス若しくは非結晶の相が形成されることが示された。
アンドープの主に結晶性のナノスケールLiFePO4粉末を、実施例1の方法を用いて調製して、最終焼成を700℃で5時間実行した。当該粉末は、39.8m2/gのBET比表面積を有することが分かった。これは、42nmの等価球状粒子サイズに相当する。透過型電子顕微鏡(”TEM”)は、粉末粒子が等軸であることを示しており、そしてTEMイメージおよびX線回折のリートベルト解析により、BET測定により推定されるものと非常に近似する結晶サイズが示された。
アンドープの主に結晶性のナノスケールLiFePO4粉末を実施例1の方法を用いて調製して、最終焼成を600℃で20時間実行した。当該粉末は、BET比表面積48.8m2/gを有することが分かった。これは、等価球状粒子サイズ34nmに相当する。TEMは、粉末粒子が等軸であることを示しており、TEMイメージ及びX線回折データのリートベルト解析により、BET測定から推定されるものと非常に近い結晶サイズが示された。
組成がLi0.99Nb0.01Mn0.70Fe0.30PO4の主に結晶性のナノスケール粉末を実施例1の方法を用いて調製した。Nbシュウ酸塩及びMnカルボン酸塩を出発物質として添加した。当該粉末は、BET比表面積40.2m2/g、炭素含有量2.44質量%を有することが分かった。X線回折データのリートベルト解析により、BET測定から推定されるものと非常に近い結晶サイズが示された。
Claims (13)
- LiaMcNdXeOf(ここで、Mは、1以上の第1列遷移金属、Nは、周期律表のIIA族、IIIA族、IVA族、VA族、VIA族、IIB族、IIIB族、若しくはVIIB族の元素、Xは、P、0≦a≦1、0.8≦c≦1.2、0≦d≦0.10、0.9≦e≦2.2、および3.6≦f≦8.8)で示される金属リン酸塩又はリチウム金属リン酸塩であって、さらに炭素を少なくとも4.00質量%含み、少なくとも10m 2 /gの比表面積を有し、調製された状態において、前記金属リン酸塩はアモルファス相であり、前記リチウム金属リン酸塩はアモルファス相及びかんらん石相を有する、ナノスケールマテリアル。
- 上記Mが、Ti、V、Cr、Mn、Fe、CoおよびNiからなる群から選択された第1列遷移金属の少なくとも1つを含むことを特徴とする請求項1記載のナノスケールマテリアル。
- 上記Mが、Feであることを特徴とする請求項1記載のナノスケールマテリアル。
- 上記Mが、Mn及びFeを含むことを特徴とする請求項1記載のナノスケールマテリアル。
- 上記NがNbであることを特徴とする請求項1記載のナノスケールマテリアル。
- 上記調製された状態で、上記1以上の第1列遷移金属の濃度に比して、少なくとも5モル%の濃度でリチウムを含有することを特徴とする請求項1記載のナノスケールマテリアル。
- 上記調製された状態で、上記1以上の第1列遷移金属の濃度に比して、少なくとも10モル%の濃度でリチウムを含有することを特徴とする請求項1記載のナノスケールマテリアル。
- 上記調製された状態で、上記1以上の第1列遷移金属の濃度に比して、95モル%以下の濃度でリチウムを含有することを特徴とする請求項1記載のナノスケールマテリアル。
- 上記調製された状態で、上記1以上の第1列遷移金属の濃度に比して、85モル%以下の濃度でリチウムを含有することを特徴とする請求項1記載のナノスケールマテリアル。
- 少なくとも25m2/gの比表面積を有することを特徴とする、請求項1記載のナノスケールマテリアル。
- 少なくとも50m2/gの比表面積を有することを特徴とする、請求項1記載のナノスケールマテリアル。
- 請求項1記載のナノスケールマテリアルを含むカソード。
- 請求項12記載のカソードを含む電気化学セル。
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