JP5479096B2 - リチウム金属リン酸化物の製造方法 - Google Patents
リチウム金属リン酸化物の製造方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 13
- 239000010452 phosphate Substances 0.000 title claims description 11
- 229910019142 PO4 Inorganic materials 0.000 title claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007858 starting material Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims 1
- 230000026731 phosphorylation Effects 0.000 claims 1
- 238000006366 phosphorylation reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 104
- 238000000034 method Methods 0.000 description 26
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 239000002131 composite material Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003746 solid phase reaction Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical compound [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- 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
-
- 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
Description
(Mは、3族〜11族の遷移金属、Mg、Al、Ga及びBから選ばれ、0.05≦x≦1.2、0.8≦y≦1.2)
a)前記金属、前記金属を含有した金属酸化物、リチウム塩及びリン酸塩を混合する第1の段階;
b)選択的に、以前段階の混合物に炭素物質をさらに添加して混合する第2の段階;
c)以前段階(第1の段階又は第2の段階)の混合物を熱処理して焼成する第3の段階を含むことができる。
本発明に記載された物質を電極活物質として含む電極は、公知の方法により製造できる。例えば、前記電極は、本発明により前述した物質を活物質として用いる以外にも、電気伝導性を与えるための導電剤と、材料及び集電体を接着させる結合剤とがさらに用いられる。
実施例1の方法により製造されたLiFePO4及び炭素の複合体に対してX線回折分析を行った結果、結晶性に優れるLiFePO4が得られることを確認した(図1参照)。
また、SEM分析及び粒度分析により粒子の形態及び粒度分布を確認した(図2及び図3参照)。SEM写真から分かるように、サブミクロンサイズの一次粒子が集まって二次粒子を形成し、3μmのD50値を示す。このような粒子の形状及びサイズは、粒子内でのリチウム拡散速度が低いLiFePO4において、性能向上のための重要な役割をする。
Claims (11)
- 下記化学式1で表されるリチウム金属リン酸化物を製造する方法であって、
LixMyPO4 〔化学式1〕
(上記式中、
Mは、3族〜11族の遷移金属、Al、Ga及びBから選ばれるものであり、
0.05≦x≦1.2であり、
0.8≦y≦1.2である)
a1)還元状態の金属(M)と、前記金属(M)を含有した金属酸化物とを機械的にミーリングして、2価の酸化数のみを有する金属酸化物を生成する段階と、
a2)前記2価の酸化数のみを有する金属酸化物と、リチウム塩及びリン酸塩とを混合する段階と、及び、
b)得られた混合物に熱処理し焼成する段階とを含んでなり、
前記還元状態の金属(M)と機械的にミーリングされる金属酸化物における金属の酸化数が+3価であり、又は+3価及び+2価が混合されているものである、製造方法。 - 前記b)段階の以前に、炭素物質を添加して混合する段階をさらに含んでなる、請求項1に記載の製造方法。
- 前記リチウム塩が、塩化リチウム(LiCl)、炭酸リチウム(Li2CO3)、水酸化リチウム(LiOH)、リン酸リチウム(Li3PO4)及び硝酸リチウム(LiNO3)からなる群より選ばれることを特徴とする、請求項1又は2に記載の製造方法。
- 前記リン酸塩が、(NH4)H2PO4、(NH4)2HPO4、(NH4)3PO4、H3PO4、P2O5、P4O10、Li3PO4及びFePO4・nH2Oからなる群より選ばれることを特徴とする、請求項1〜3の何れか一項に記載の製造方法。
- 前記炭素物質が、カーボンブラック、スクロース、ピッチ、セルロースアセテート、有機酸、レジン、レゾルシン−ホルムアルデヒドからなる群より選ばれることを特徴とする、請求項2に記載の製造方法。
- 前記熱処理温度が、450℃〜850℃範囲であることを特徴とする、請求項1〜5の何れか一項に記載の製造方法。
- 前記熱処理が、不活性雰囲気で行われることを特徴とする、請求項1〜6の何れか一項に記載の製造方法。
- 前記金属Mが、Fe又はMnであることを特徴とする、請求項1〜7の何れか一項に記載の製造方法。
- 金属(M)及び前記金属を含有した金属酸化物の混合物を出発原料とする、請求項1〜8の何れか一項に記載の製造方法により製造されたことを特徴とする、リチウム金属リン酸化物。
- 請求項9に記載のリチウム金属リン酸化物を電極活物質として含むことを特徴とする、電極。
- 請求項10に記載の電極を備えることを特徴とする、二次電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20060078702 | 2006-08-21 | ||
KR10-2006-0078702 | 2006-08-21 | ||
PCT/KR2007/003962 WO2008023908A1 (en) | 2006-08-21 | 2007-08-20 | Method for preparing lithium metal phosphate |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7988879B2 (en) | 2006-08-21 | 2011-08-02 | Lg Chem, Ltd. | Method for preparing lithium metal phosphate |
TWI466370B (zh) * | 2008-01-17 | 2014-12-21 | A123 Systems Inc | 鋰離子電池的混合式金屬橄欖石電極材料 |
CN101980956A (zh) * | 2008-03-31 | 2011-02-23 | 户田工业株式会社 | 磷酸铁锂颗粒粉末的制造方法、橄榄石型结构的磷酸铁锂颗粒粉末、使用该磷酸铁锂颗粒粉末的正极材料片和非水溶剂类二次电池 |
WO2009131095A1 (ja) * | 2008-04-25 | 2009-10-29 | 住友大阪セメント株式会社 | リチウムイオン電池用正極活物質の製造方法、該製造方法で得られたリチウムイオン電池用正極活物質、リチウムイオン電池用電極、及びリチウムイオン電池 |
US20110110838A1 (en) * | 2009-07-10 | 2011-05-12 | Intematix Corporation | METHOD OF SOLID-LIQUID MIXING GEL PROCESS FOR LiFePO4 SYNTHESIS |
KR101865419B1 (ko) | 2009-08-25 | 2018-06-07 | 에이일이삼 시스템즈, 엘엘씨 | 개선된 비용량 및 에너지 밀도를 갖는 리튬 이온 배터리를 위한 혼합된 금속 감람석 전극 물질 |
US9660267B2 (en) | 2009-09-18 | 2017-05-23 | A123 Systems, LLC | High power electrode materials |
TWI496737B (zh) * | 2009-09-18 | 2015-08-21 | A123 Systems Llc | 磷酸鐵及其製備方法 |
KR101392816B1 (ko) | 2010-04-21 | 2014-05-08 | 주식회사 엘지화학 | 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 |
KR101219395B1 (ko) * | 2010-07-15 | 2013-01-11 | 전자부품연구원 | 리튬이차전지용 양극재료 및 그의 제조방법 |
KR101174394B1 (ko) | 2010-12-10 | 2012-08-21 | 한국세라믹기술원 | 메조포어를 갖는 올리빈 구조의 리튬 금속 인산화물의 제조 방법, 이에 의하여 제조된 메조포어를 갖는 올리빈 구조의 리튬 금속 인산화물 및 이를 포함하는 전기 화학 소자 |
JP5736865B2 (ja) * | 2011-03-16 | 2015-06-17 | 東洋インキScホールディングス株式会社 | リチウム二次電池用正極活物質材料の製造方法、及びそれを用いたリチウム二次電池 |
JP2013069456A (ja) * | 2011-09-21 | 2013-04-18 | Fuji Heavy Ind Ltd | 正極活物質の製造方法、正極、および蓄電デバイス |
KR101973052B1 (ko) * | 2012-08-10 | 2019-04-26 | 삼성에스디아이 주식회사 | 리튬 금속인산화물의 제조방법 |
US9660266B2 (en) | 2012-11-21 | 2017-05-23 | Lg Chem, Ltd. | Lithium secondary battery |
CN104718657B (zh) * | 2012-11-21 | 2018-01-12 | 株式会社Lg 化学 | 锂二次电池 |
US10128540B2 (en) | 2012-11-22 | 2018-11-13 | Lg Chem, Ltd. | Lithium secondary battery |
KR101570977B1 (ko) * | 2012-11-22 | 2015-11-23 | 주식회사 엘지화학 | 리튬 이차전지 |
KR101580842B1 (ko) * | 2014-01-07 | 2015-12-29 | 동국대학교 산학협력단 | 리튬 망간계 산화물의 표면처리 방법 및 그를 이용하여 제조된 리튬망간계 산화물 |
CA2977349C (en) * | 2015-03-31 | 2020-10-06 | Toray Industries, Inc. | Lithium manganese phosphate nanoparticles and method for manufacturing same, carbon-coated lithium manganese phosphate nanoparticles, carbon-coated lithium manganese phosphate nanoparticle granulated body, and lithium ion cell |
WO2018029745A1 (ja) * | 2016-08-08 | 2018-02-15 | 東レ株式会社 | リン酸マンガンリチウムナノ粒子およびその製造方法、炭素被覆リン酸マンガンリチウムナノ粒子、炭素被覆リン酸マンガンリチウムナノ粒子造粒体、リチウムイオン電池 |
TWI821195B (zh) * | 2017-07-19 | 2023-11-11 | 加拿大商納諾萬麥帝瑞爾公司 | 合成橄欖石型磷酸鋰金屬陰極材料的方法 |
TWI739098B (zh) * | 2018-06-25 | 2021-09-11 | 國立清華大學 | 用於鋰離子電池之二價金屬磷酸鹽粉末和鋰金屬磷酸鹽粉末及其製備方法 |
CN110371940A (zh) * | 2019-09-04 | 2019-10-25 | 井冈山大学 | 一种LiMnPO4前驱体模板Li3PO4空心微球及其制备方法和应用 |
CN113582148A (zh) * | 2021-07-28 | 2021-11-02 | 澳门大学 | 磷酸盐掺杂的金属磷化物及其制备方法和应用、金属磷化物复合材料及其制备方法和应用 |
WO2023192443A1 (en) | 2022-04-01 | 2023-10-05 | Aspen Aerogels, Inc. | Carbon powder containing lithium iron phosphate cathode materials |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100211179B1 (ko) * | 1997-04-25 | 1999-07-15 | 손욱 | 리튬 이차전지용 양극 활물질 LixMn2O4 분말 및 그 제조방법 |
US6136472A (en) * | 1998-06-26 | 2000-10-24 | Valence Technology, Inc. | Lithium-containing silicon/phosphates, method of preparation, and uses thereof including as electrodes for a battery |
KR20010025116A (ko) * | 1999-04-06 | 2001-03-26 | 이데이 노부유끼 | 양극 활물질의 제조 방법 및 비수 전해질 이차 전지의제조 방법 |
US6528033B1 (en) * | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
TW525313B (en) * | 2000-04-25 | 2003-03-21 | Sony Corp | Positive electrode active material and non-aqueous electrolyte cell |
KR100364659B1 (ko) * | 2000-08-25 | 2002-12-16 | 유광수 | 리튬이차전지용 양극활물질인 Li(Mn1-δCoδ)2O4 조성물 및 그 제조방법 |
CA2320661A1 (fr) | 2000-09-26 | 2002-03-26 | Hydro-Quebec | Nouveau procede de synthese de materiaux limpo4 a structure olivine |
US6645452B1 (en) * | 2000-11-28 | 2003-11-11 | Valence Technology, Inc. | Methods of making lithium metal cathode active materials |
DE10117904B4 (de) * | 2001-04-10 | 2012-11-15 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | Binäre, ternäre und quaternäre Lithiumeisenphosphate, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP4187523B2 (ja) * | 2002-01-31 | 2008-11-26 | 日本化学工業株式会社 | リチウム鉄リン系複合酸化物炭素複合体、その製造方法、リチウム二次電池正極活物質及びリチウム二次電池 |
EP2583939A3 (en) | 2002-05-17 | 2015-03-11 | Valence Technology (Nevada), Inc. | Synthesis of metal compounds useful as cathode active materials |
US7390472B1 (en) * | 2002-10-29 | 2008-06-24 | Nei Corp. | Method of making nanostructured lithium iron phosphate—based powders with an olivine type structure |
JP4343618B2 (ja) * | 2003-08-21 | 2009-10-14 | セントラル硝子株式会社 | ポリアニオン型リチウム鉄複合酸化物の製造方法及びそれを用いた電池 |
JP4483253B2 (ja) * | 2003-09-30 | 2010-06-16 | 三菱化学株式会社 | リチウム二次電池用正極材料、リチウム二次電池用正極及びリチウム二次電池 |
JP4522682B2 (ja) * | 2003-10-09 | 2010-08-11 | 住友大阪セメント株式会社 | 電極材料粉体の製造方法と電極材料粉体及び電極並びにリチウム電池 |
JP4707950B2 (ja) * | 2003-12-26 | 2011-06-22 | 住友大阪セメント株式会社 | リチウム電池用正極活物質の製造方法とリチウム電池用正極活物質及びリチウム電池用電極並びにリチウム電池 |
TWI279020B (en) * | 2004-11-03 | 2007-04-11 | Tatung Co Ltd | Preparation of olivine LiFePO4 cathode materials for lithium batteries via a solution method |
KR100701244B1 (ko) | 2004-11-16 | 2007-04-06 | 한국전기연구원 | 카본이 도포된 리튬이차전지용 리튬 전이금속 인산화물 양극활물질의 제조방법 |
JP4951879B2 (ja) * | 2005-06-08 | 2012-06-13 | 日本電気株式会社 | リチウム二次電池及びリチウム二次電池用正極活物質 |
US7988879B2 (en) | 2006-08-21 | 2011-08-02 | Lg Chem, Ltd. | Method for preparing lithium metal phosphate |
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