JP6073040B2 - ナノスケール・イオン貯蔵材料およびその電気エネルギー貯蔵法 - Google Patents
ナノスケール・イオン貯蔵材料およびその電気エネルギー貯蔵法 Download PDFInfo
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- JP6073040B2 JP6073040B2 JP2009549177A JP2009549177A JP6073040B2 JP 6073040 B2 JP6073040 B2 JP 6073040B2 JP 2009549177 A JP2009549177 A JP 2009549177A JP 2009549177 A JP2009549177 A JP 2009549177A JP 6073040 B2 JP6073040 B2 JP 6073040B2
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- 239000011232 storage material Substances 0.000 title description 67
- 238000000034 method Methods 0.000 title description 38
- 238000004146 energy storage Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 84
- 229910052723 transition metal Inorganic materials 0.000 claims description 71
- -1 lithium phosphate transition metal Chemical class 0.000 claims description 65
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 20
- 239000010450 olivine Substances 0.000 claims description 18
- 229910052609 olivine Inorganic materials 0.000 claims description 18
- 239000000463 material Substances 0.000 description 163
- 229910052744 lithium Inorganic materials 0.000 description 111
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 100
- 239000012071 phase Substances 0.000 description 91
- 150000002500 ions Chemical class 0.000 description 82
- 239000006104 solid solution Substances 0.000 description 68
- 239000002245 particle Substances 0.000 description 61
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 37
- 239000007769 metal material Substances 0.000 description 32
- 230000006399 behavior Effects 0.000 description 31
- 238000003860 storage Methods 0.000 description 31
- 239000002086 nanomaterial Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 24
- 238000005259 measurement Methods 0.000 description 22
- 230000007547 defect Effects 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 239000013078 crystal Substances 0.000 description 19
- 238000010586 diagram Methods 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 18
- 150000003624 transition metals Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 230000008859 change Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 230000007423 decrease Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 230000002950 deficient Effects 0.000 description 13
- 230000007704 transition Effects 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000010587 phase diagram Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000012798 spherical particle Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 230000032258 transport Effects 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011362 coarse particle Substances 0.000 description 6
- 230000007812 deficiency Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000013081 microcrystal Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000005204 segregation Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- 239000002228 NASICON Substances 0.000 description 4
- 238000003991 Rietveld refinement Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 239000002707 nanocrystalline material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000009838 combustion analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241001562081 Ikeda Species 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910001246 LixFePO4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004774 atomic orbital Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004335 scaling law Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- H01M4/58—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
- H01M4/36—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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
他の実施形態によると、結晶のいずれかの主軸により形成される面は、いずれも、8%または7.5%または6%を越えるような歪みをもつことはない。
全体の組成LiFePO4のリン酸リチウム鉄は、以下の割合の出発材料を用いて作成された。
Li2CO3 (Alfa-Aesar, 99.999%) 0.739g、
蓚酸鉄(II) (Alfa-Aesar, 99.999%) 3.598g、
リン酸アンモニウム (Aldrich, 99.998%) 2.301g
ナノスケール・リン酸リチウム鉄粉末 3.95g、
スーパーP炭素 0.50g、
Kynar 2801バインダー 0.55g、
γ-ブチロラクトン(溶媒) 28.5g
を持つ電極に作成される。これらは、混合されて、自由に流れる懸濁液を生成し、アルミニウム箔の上に一様な層として型に取られる。この被覆は、真空中で100−110℃で乾燥され、その後、約100マイクロメートルの厚さを持つと測定された。次に、Swagelok電池またはコイン電池に合うのに適した1〜2cmの円板にパンチされた。この電極の被覆は、微小孔の高分子セパレータと、負極としてのリチウム箔(正電極の理論的貯蔵容量より少なくとも10倍大きな全体のリチウム含有量)と、リチウム塩としてLiPF6を含む通常の非水リチウムイオン・バッテリー電解質とを用いて、Swagelok電池またはコイン形電池のハードウェアを用いるリチウム半電池に組み立てられた。高い充電レートまたは放電レートで高い容量を出すナノスケール材料の能力はめだっている。ここで、充電容量の保持は、図16に示されるように、同じ電圧範囲でC/5のレートで観察される容量に比べて、2.0−3.8Vの電圧範囲にわたって、あるCレートで測定される容量の百分率として記載するために用いられる。容量保持は、1.8Cのレートで、95.9%であり、4.4Cのレートで、92.1%であり、9Cのレートで、88.1%であり、18Cのレートで、82.6%であり、31Cのレートで、75.6%であり、44Cのレートで、69.1%であった。バッテリー分野の当業者が認識するように、これらは通常のイオン貯蔵材料に比べて異常に高い容量保持である。この試料について第1回の充電サイクルの間に測定される容量は、第1回の放電サイクルの間に測定される容量より約6.6%小さく、これは、製造された状態での材料の非化学量論性xが約6.6%であることを示した。
全体の組成Li0.99FePO4をもつナノスケール・イオン貯蔵材料は、より大きなバッチ寸法が作成され、出発物質の異なる供給源が用いられたことを除いて、例1で説明された手順に従って合成され試験された。この組成は、以下の割合の出発材料を用いて作成された。
Li2CO3 (SQM社) 7.4337g、
蓚酸鉄(II) (Elementis社) 36.2696g、
リン酸アンモニウム (Heico社) 22.5541g
LiFePO4とLio 95FePO4の全体の組成をもつナノスケール・イオン貯蔵材料が、例2において説明された手順に従って、合成され、試験された。ここで、炭酸リチウムの質量は、特定された全体の組成を達成するように調節されている。LiFePO4とLi0 95FePO4の粉末は、BET法で測定され、それぞれ、39.78m2/gと46.2m2/gの比表面積をもち、41.9nmと36.1nmの等価球状粒子径に対応する。燃焼分析は、2つの粉末がそれぞれ2.3wt%と3wt%の残留炭素濃度をもつことを示した。図7と図8は、それぞれ、これらの2つの試料のC/50のレートでの充電曲線と放電曲線を、数マイクロメートルの平均粒子寸法と著しく劣るレート性能とをもつAldrich Chemical社からの市販の炭素被覆LiFePO4に比べて、示す。これらの材料の非常に高いレート性能(図19参照)により、これらの低レートの充電/放電曲線は電池の準平衡電圧を示す。これらの曲線から分かるように、連続的な充電と放電の間に、少なくとも約15%のリチウム非化学量論性と少なくとも10%のリチウム非化学量論性yが得られた。図12〜図14は、前に説明したように、ナノスケールLi0.95FePO4試料のPITT測定を示す。開路電圧(OCV)より5mV高い単独ステップの放電の間、160mAh/のC/50のレートで測定された全放電容量の10.5%が測定され(3.8Vから2Vへ)、約4.5%より大きい非化学量論性yが動的な放電条件の間に存在することを示した。開路電圧より5mV低い単独ステップの充電の間、全充電容量の10.5%が測定され(2.9Vから3.8Vへ)、約10.5%より大きい非化学量論性xが動的な充電条件の間に存在することを示した。比較のため、Aldrich Chemical社からの比較試料について開路電圧より上と下へ5mVでの容量から測定されたy値とx値がそれぞれ0.7%と1.2%である。図16と表1、表2は、前に説明したナノスケールLi1-xFePO4試料のX線粉末回折測定を示す。この試料のリートベルト精密化処理から、約28nmの結晶寸法が決定され、これは、計算された等価球面粒子径に近く、試料の高い表面積がリン酸リチウム鉄のナノスケール微結晶によるものであり、高い表面不純物または追加の相によるものでないことを示す。図19は、例2におけるように、Swagelokハードウェアを用いて構成された3つのリチウム半電池からの試験結果を示す。
この予言的な例において、たとえば例1、例3に示されたような、ナノスケール・イオン貯蔵材料を用いる正電極(広い範囲のCレートでの電気化学的性能でよく特徴づけられる)は、巻回される円筒状リチウムイオン電池を構成するために使用される。数マイクロメートルの平均粒子径の石墨化メソ炭素微粒子(MCMB,大阪ガス社)などの高レート石墨アノードが用いられる。そのような電池の性能(種々のCレートでの充電容量とエネルギーを含む)は、この場合のように、プロトタイプ電池におけるこの電極の密度、厚さおよび性能が既知であれば、電池の構成部品の体積と質量からモデル化できる。3.8Vでの十分充電された状態から出発して、2.0Vの電圧下限すなわち100%の深さの放電へ放電して、このモデルは、そのような電池が、少なくとも約100Wh/kg(205Wh/L)の比エネルギーで少なくとも約500W/kg(1000W/L)の電力を、少なくとも約95Wh/kg(190Wh/L)の比エネルギーで少なくとも約950W/kg(2000W/L)の電力を、少なくとも約90Wh/kg(180Wh/L)の比エネルギーで少なくとも約1300W/kg(2500W/L)の電力を、少なくとも約85Wh/kg(175Wh/L)の比エネルギーで少なくとも約1600W/kg(3200W/L)の電力を提供する。理解されるように、より浅い深さの放電について、比電力と電力密度はこれらの値より大きく高くなりうる。
例3に説明されたLiFePO4の組成の、39.8m2/gの比表面積をもつナノスケール・イオン貯蔵材料が用いられた。さらに、48.8m2/gの比表面積をもつ試料が、最終の焼成が600℃で行われたことを除いて、例2に説明されたのと同じ方法により作成された。比較のため、Aldrich Chemical社からの市販の炭素被覆LiFePO4が使用され、この試料は、例3で説明された14.8m2/gの比表面積をもつ。全部で3つの試料は、電極に作成され、例1の手順を用いてSwagelok電池で試験された。開路電圧(OCV)測定は、関心のある測定温度で、50%の充電状態で、少なくとも12時間待った後で、行われた。PITT測定は、十分に放電または充電した状態から初めて、5mVまたは10mVの電圧ステップを用いて、前に説明したように行われた。
Claims (3)
- 比表面積が少なくとも15m2/gであり、
リン酸リチウム遷移金属は、Li1−xMPO4(MはFe、0<x≦0.15)の組成である、合成されたままのリン酸リチウム遷移金属粉末。 - 上記粉末の比表面積が20m2/g以上である、請求項1に記載されたリン酸リチウム遷移金属粉末。
- 上記リン酸リチウム遷移金属はかんらん石構造を持つ、請求項1に記載されたリン酸リチウム遷移金属粉末。
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