JP6126318B2 - Method for producing positive electrode active material for olivine type lithium ion secondary battery - Google Patents
Method for producing positive electrode active material for olivine type lithium ion secondary battery Download PDFInfo
- Publication number
- JP6126318B2 JP6126318B2 JP2016555272A JP2016555272A JP6126318B2 JP 6126318 B2 JP6126318 B2 JP 6126318B2 JP 2016555272 A JP2016555272 A JP 2016555272A JP 2016555272 A JP2016555272 A JP 2016555272A JP 6126318 B2 JP6126318 B2 JP 6126318B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- compound
- positive electrode
- active material
- electrode active
- 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.)
- Active
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 51
- 239000007774 positive electrode material Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000010450 olivine Substances 0.000 title claims description 16
- 229910052609 olivine Inorganic materials 0.000 title claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000002002 slurry Substances 0.000 claims description 64
- -1 phosphate compound Chemical class 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000002642 lithium compounds Chemical class 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims description 12
- 239000003002 pH adjusting agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000006182 cathode active material Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000007524 organic acids Chemical class 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910005323 Li(Fe, Mn)PO4 Inorganic materials 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
- 229910011849 LiFe0.2Mn0.8PO4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910018611 Mn 1-a PO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical group [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000006064 precursor glass Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 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
-
- 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
-
- 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
本発明は、特殊な条件を要することのない簡便な手段によるオリビン型リチウムイオン二次電池用正極活物質の製造方法に関する。 The present invention relates to a method for producing a positive electrode active material for an olivine-type lithium ion secondary battery by a simple means that does not require special conditions.
携帯電子機器、ハイブリッド自動車、電気自動車等に用いられる二次電池の開発が行われており、特にリチウムイオン二次電池は広く知られている。こうしたなか、オリビン型構造を有するＬｉ（Ｆｅ，Ｍｎ）ＰＯ4等のリチウム遷移金属リン酸塩化合物からなる正極活物質は、資源的な制約に大きく左右されることがなく、しかも高い安全性を発揮することができるため、高出力で大容量のリチウムイオン二次電池を得るのに最適な正極材料となる。そして、これらの有用な正極活物質を得るべく、従来より種々の開発がなされている。Secondary batteries used for portable electronic devices, hybrid cars, electric cars, and the like have been developed. In particular, lithium ion secondary batteries are widely known. Under these circumstances, the positive electrode active material made of a lithium transition metal phosphate compound such as Li (Fe, Mn) PO 4 having an olivine type structure is not greatly affected by resource constraints and has high safety. Therefore, it is an optimum positive electrode material for obtaining a high-output and large-capacity lithium ion secondary battery. Various developments have been made in the past to obtain these useful positive electrode active materials.
例えば、特許文献１〜２では、リン酸リチウムや金属化合物等の原料化合物、及び導電性炭素材料から得られる混合物を焼成する、いわゆる固相反応法を用いた製造方法が開示されており、特許文献３には、酸化リチウムや所望の希土類酸化物を混合及び溶融することにより得られた前駆体ガラスを、熱処理又はレーザー照射する製造方法が開示されている。
一方、特許文献４には、原料化合物を水熱反応に付することにより得られたスラリーを造粒する、上記固相反応法に依ることのない製造方法が開示されている。For example, Patent Documents 1 and 2 disclose a manufacturing method using a so-called solid-phase reaction method in which a mixture obtained from a raw material compound such as lithium phosphate and a metal compound and a conductive carbon material is disclosed. Document 3 discloses a manufacturing method in which a precursor glass obtained by mixing and melting lithium oxide or a desired rare earth oxide is subjected to heat treatment or laser irradiation.
On the other hand, Patent Document 4 discloses a production method that does not depend on the solid phase reaction method, in which a slurry obtained by subjecting a raw material compound to a hydrothermal reaction is granulated.
しかしながら、特許文献１〜２のような固相反応法を用いるのでは、不活性ガス雰囲気下での焼成や粉砕処理のように複雑な操作が必要であり、また特許文献３の方法であっても、過度の昇温を余儀なくされ、レーザー照射のような特殊な処理を要する等、製造工程が煩雑であるとともに、得られる活物質がもたらす性能を十分に高めることが困難である。
一方、特許文献４に記載の水熱反応を用いれば、上記のような従来の製造方法の簡略化を図ることは可能であるものの、１００℃以上の加温条件下での加圧を要するため、専用の設備を整備せざるを得ず、依然として改善の余地がある。However, the use of the solid phase reaction method as in Patent Documents 1 and 2 requires complicated operations such as firing and pulverization in an inert gas atmosphere. However, an excessive temperature rise is required, and a special process such as laser irradiation is required, so that the manufacturing process is complicated and it is difficult to sufficiently enhance the performance provided by the obtained active material.
On the other hand, if the hydrothermal reaction described in Patent Document 4 is used, it is possible to simplify the conventional production method as described above, but it requires pressurization under a heating condition of 100 ° C. or higher. However, there is still room for improvement due to the necessity of developing dedicated equipment.
したがって、本発明の課題は、簡便な手段によって優れた電池物性を実現する正極材料を得ることのできる、オリビン型リチウムイオン二次電池用正極活物質の製造方法を提供することにある。 Therefore, the subject of this invention is providing the manufacturing method of the positive electrode active material for olivine type lithium ion secondary batteries which can obtain the positive electrode material which implement | achieves the outstanding battery physical property by a simple means.
そこで本発明者らは、種々検討したところ、所望の原料化合物に加え、特定のｐＨ調整剤を含有する混合物スラリーを用いることにより、必要以上の加温や加圧を要することのない簡便な方法によって、オリビン型リチウムイオン二次電池用正極活物質が得られることを見出し、本発明を完成させるに至った。 Therefore, the present inventors have made various studies, and by using a mixture slurry containing a specific pH adjuster in addition to a desired raw material compound, a simple method that does not require more heating or pressurization than necessary. Thus, it was found that a positive electrode active material for olivine type lithium ion secondary battery was obtained, and the present invention was completed.
すなわち、本発明は、（ａ）遷移金属化合物、（ｂ）リン酸化合物、（ｃ）リチウム化合物、（ｄ）水、並びに（ｅ）ＮａＯＨ及びＫＯＨから選ばれる１種又は２種のｐＨ調整剤を含有する混合物スラリーを、大気圧以下の雰囲気圧力で撹拌して反応させることを特徴とする、オリビン型リチウムイオン二次電池用正極活物質の製造方法を提供することにある。 That is, the present invention provides (a) a transition metal compound, (b) a phosphoric acid compound, (c) a lithium compound, (d) water, and (e) one or two kinds of pH adjusting agents selected from NaOH and KOH. It is another object of the present invention to provide a method for producing a positive electrode active material for an olivine-type lithium ion secondary battery, which comprises reacting a slurry containing a mixture slurry with an atmospheric pressure of atmospheric pressure or lower.
本発明の製造方法によれば、大気圧以下の雰囲気圧力で撹拌するのみで、原料化合物の反応を進行させることができるので、特別な製造設備を要することなく簡便な方法によって、オリビン型リチウムイオン二次電池用正極活物質を製造することができる。また、本発明の製造方法により得られるオリビン型リチウムイオン二次電池用正極活物質は、電池特性に優れるリチウムイオン二次電池を得ることのできる正極材料としても、極めて有用である。 According to the production method of the present invention, since the reaction of the raw material compound can proceed only by stirring at atmospheric pressure below atmospheric pressure, the olivine type lithium ion can be obtained by a simple method without requiring special production equipment. A positive electrode active material for a secondary battery can be produced. Moreover, the positive electrode active material for olivine type lithium ion secondary batteries obtained by the production method of the present invention is extremely useful as a positive electrode material from which a lithium ion secondary battery having excellent battery characteristics can be obtained.
以下、本発明について詳細に説明する。
本発明のオリビン型リチウムイオン二次電池用正極活物質の製造方法は、（ａ）遷移金属化合物、（ｂ）リン酸化合物、（ｃ）リチウム化合物、（ｄ）水、並びに（ｅ）ＮａＯＨ及びＫＯＨから選ばれる１種又は２種のｐＨ調整剤を含有する混合物スラリーを、大気圧以下の雰囲気圧力で撹拌して反応させることを特徴とする。これにより、目的物であるオリビン型リチウムイオン二次電池用正極活物質として、リチウム遷移金属リン酸塩化合物が得られる。Hereinafter, the present invention will be described in detail.
The method for producing a positive electrode active material for an olivine-type lithium ion secondary battery of the present invention comprises (a) a transition metal compound, (b) a phosphoric acid compound, (c) a lithium compound, (d) water, and (e) NaOH and A mixture slurry containing one or two kinds of pH adjusting agents selected from KOH is stirred and reacted at an atmospheric pressure equal to or lower than atmospheric pressure. Thereby, a lithium transition metal phosphate compound is obtained as a positive electrode active material for an olivine-type lithium ion secondary battery, which is a target product.
成分（ａ）の遷移金属化合物を構成する遷移金属（Ｍ）としては、例えば、Ｆｅ、Ｎｉ、Ｃｏ、Ｚｎ、Ｍｎ、Ｖ、Ｚｒ、Ｙ、Ｍｏ、Ｌａ、Ｃｅ及びＮｄ等が挙げられ、これらを含む遷移金属化合物を１種単独で用いてもよく、２種以上組み合わせて用いてもよい。かかる遷移金属化合物（Ｍ）としては、例えばフッ化物、塩化物、ヨウ化物等のハロゲン化遷移金属塩、硫酸遷移金属塩の他、有機酸遷移金属塩、並びにこれらの水和物等が挙げられる。このうち、有機酸遷移金属塩を構成する有機酸としては、炭素数１〜２０の有機酸、さらに炭素数２〜１２の有機酸が好ましい。さらに好ましくは、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。 Examples of the transition metal (M) constituting the transition metal compound of component (a) include Fe, Ni, Co, Zn, Mn, V, Zr, Y, Mo, La, Ce, and Nd. One kind of transition metal compound containing may be used alone, or two or more kinds may be used in combination. Examples of the transition metal compound (M) include halogenated transition metal salts such as fluoride, chloride and iodide, transition metal salts of sulfuric acid, organic acid transition metal salts, and hydrates thereof. . Among these, the organic acid constituting the organic acid transition metal salt is preferably an organic acid having 1 to 20 carbon atoms, and more preferably an organic acid having 2 to 12 carbon atoms. More preferred are dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
さらに必要に応じて、（ｆ）遷移金属（Ｍ）以外の金属（Ｒ）化合物を用いてもよい。成分（ｆ）の金属（Ｒ）化合物を構成する金属（Ｒ）としては、例えば、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、及びＢｉ等が挙げられ、これらを含む金属化合物を１種単独で用いてもよく、２種以上組み合わせて用いてもよい。かかる金属化合物（Ｒ）としては、例えばフッ化物、塩化物、ヨウ化物等のハロゲン化金属塩、硫酸金属塩の他、有機酸金属塩、並びにこれらの水和物等が挙げられる。このうち、有機酸金属塩を構成する有機酸としては、炭素数１〜２０の有機酸、さらに炭素数２〜１２の有機酸が好ましい。さらに好ましくは、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。 Furthermore, you may use metal (R) compounds other than (f) transition metal (M) as needed. Examples of the metal (R) constituting the metal (R) compound of the component (f) include Al, Mg, Ca, Sr, Ba, Pb, Bi, and the like. Or may be used in combination of two or more. Examples of the metal compound (R) include metal halides such as fluorides, chlorides and iodides, sulfate metal salts, organic acid metal salts, and hydrates thereof. Among these, the organic acid constituting the organic acid metal salt is preferably an organic acid having 1 to 20 carbon atoms, and more preferably an organic acid having 2 to 12 carbon atoms. More preferred are dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid.
成分（ｂ）のリン酸化合物としては、オルトリン酸、メタリン酸、ピロリン酸、三リン酸、四リン酸、リン酸アンモニウム、リン酸水素アンモニウム等が用いられる。なかでも、オルトリン酸が好ましい。 As the phosphoric acid compound of component (b), orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, ammonium hydrogenphosphate, and the like are used. Of these, orthophosphoric acid is preferable.
成分（ｃ）のリチウム化合物としては、フッ化リチウム、塩化リチウム、臭化リチウム、ヨウ化リチウム等のリチウム金属塩、水酸化リチウム、炭酸リチウム等が挙げられ、得られるリチウム遷移金属リン酸塩化合物粒子における比表面積を低減させる観点、及びコスト面等の観点から、炭酸リチウムを使用するのが好ましい。 Examples of the lithium compound of component (c) include lithium metal salts such as lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium carbonate, etc., and lithium transition metal phosphate compounds obtained It is preferable to use lithium carbonate from the viewpoint of reducing the specific surface area of the particles and the cost.
混合物スラリー中における（ａ）遷移金属化合物、（ｂ）リン酸化合物、（ｃ）リチウム化合物、及び必要に応じて用いる（ｆ）遷移金属以外の金属化合物の含有量は、目的物によって異なる。例えば、目的物がリチウム遷移金属リン酸塩化合物であるリン酸鉄リチウム（ＬｉＦｅＰＯ4）の場合には、（ａ）遷移金属（鉄）化合物の含有量と（ｃ）リチウム化合物の含有量とのモル比は、鉄イオンとリチウムイオンとの換算比（鉄イオン：リチウムイオン）で１：２．５〜１：３．５が好ましい。また、（ｃ）リチウム化合物の含有量と（ｂ）リン酸化合物の含有量とのモル比は、リチウムイオンとリン酸イオンとの換算比（リチウムイオン：リン酸イオン）で２．５：１〜３．５：１であるのが好ましい。また、目的物がリチウム遷移金属リン酸塩化合物であるリン酸マンガン鉄リチウム（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ4）の場合には、（ａ）遷移金属（鉄、マンガン）化合物の合計含有量と（ｃ）リチウム化合物の含有量とのモル比は、遷移金属イオン（鉄イオン）及びマンガンイオンの合計とリチウムイオンとの換算比（遷移金属イオン：リチウムイオン）で１：１〜１：３．５が好ましい。また、（ｃ）リチウム化合物の含有量と（ｂ）リン酸化合物の含有量とのモル比は、リチウムイオンとリン酸イオンとの換算比（リチウムイオン：リン酸イオン）で１：１〜３．５：１であるのが好ましい。The contents of (a) a transition metal compound, (b) a phosphoric acid compound, (c) a lithium compound, and (f) a metal compound other than the transition metal used as necessary in the mixture slurry vary depending on the target product. For example, when the target product is lithium iron phosphate (LiFePO 4 ), which is a lithium transition metal phosphate compound, the content of (a) the content of the transition metal (iron) compound and (c) the content of the lithium compound The molar ratio is preferably 1: 2.5 to 1: 3.5 in terms of conversion ratio of iron ions to lithium ions (iron ions: lithium ions). The molar ratio of the content of the (c) lithium compound and the content of the (b) phosphate compound is 2.5: 1 in terms of a conversion ratio of lithium ions to phosphate ions (lithium ions: phosphate ions). It is preferably ˜3.5: 1. When the target product is lithium manganese iron phosphate (LiFe 0.2 Mn 0.8 PO 4 ), which is a lithium transition metal phosphate compound, (a) the total content of transition metal (iron, manganese) compounds and (c ) The molar ratio with the lithium compound content is 1: 1 to 1: 3.5 in terms of the conversion ratio of transition metal ions (iron ions) and manganese ions to lithium ions (transition metal ions: lithium ions). preferable. The molar ratio of the content of the (c) lithium compound and the content of the (b) phosphate compound is 1: 1 to 3 in terms of the conversion ratio of lithium ions to phosphate ions (lithium ions: phosphate ions). .5: 1 is preferred.
混合物スラリー中における成分（ｄ）の水の含有量は、原料化合物の溶解性、撹拌の容易性、合成の効率等の点から、成分（ｂ）のリン酸化合物のリンイオン１モルに対し、１０〜５０モルが好ましく、さらに１３〜３０モルが好ましい。 The water content of component (d) in the mixture slurry is 10 with respect to 1 mol of phosphorus ions of the phosphate compound of component (b) from the viewpoints of solubility of raw material compounds, ease of stirring, synthesis efficiency, and the like. -50 mol is preferable, and 13-30 mol is more preferable.
成分（ｅ）のＮａＯＨ及びＫＯＨから選ばれる１種又は２種のｐＨ調整剤は、混合物スラリー中において成分（ｄ）の水が介在するなか、必要以上の加温や加圧を要することなく、上記成分（ａ）〜（ｃ）の反応を良好に促進する作用をもたらすものと考えられる。成分（ｅ）のなかでも、得られる電池特性をより高める観点から、ＮａＯＨであるのが好ましい。 One or two kinds of pH adjusting agents selected from NaOH and KOH of the component (e) do not require heating or pressurization more than necessary while the water of the component (d) is present in the mixture slurry. It is thought that it brings about the effect | action which accelerates | stimulates reaction of said component (a)-(c) favorably. Among the components (e), NaOH is preferable from the viewpoint of further improving the obtained battery characteristics.
混合物スラリー中における成分（ｃ）のリチウム化合物の含有量と成分（ｅ）のＮａＯＨ及びＫＯＨから選ばれる１種又は２種のｐＨ調整剤の含有量とのモル比は、リチウムイオンと水酸化物イオンとの換算比（リチウムイオン：水酸化物イオン）で２．５：０．５〜１：２であるのが好ましく、２：１〜１：１．５であるのがより好ましい。 The molar ratio of the content of the lithium compound of component (c) and the content of one or two pH adjusters selected from NaOH and KOH of component (e) in the mixture slurry is lithium ion and hydroxide. It is preferably 2.5: 0.5 to 1: 2 in terms of conversion ratio (lithium ion: hydroxide ion), more preferably 2: 1 to 1: 1.5.
混合物スラリーを得るにあたり、これら成分（ａ）〜（ｅ）、及び必要に応じて用いる成分（ｆ）の添加順序は特に限定されないが、リチウム遷移金属リン酸塩化合物を目的物とする場合には、副反応を防止し、反応を容易に進行させる観点から、少なくとも予め（ｂ）リン酸化合物、（ｃ）リチウム化合物、（ｄ）水、及び（ｅ）ｐＨ調整剤を混合して前駆体スラリーを調製した後、（ａ）遷移金属化合物、及び必要に応じて用いる（ｆ）遷移金属以外の金属化合物を添加して、混合物スラリーを得るのが好ましい。すなわち、このような順序で原料を添加すると、過度に粘性が上昇することなく、撹拌も容易となり、必要以上の加温や加圧を要することなく反応を良好に進行させることができる。 In order to obtain a mixture slurry, the order of addition of these components (a) to (e) and component (f) used as necessary is not particularly limited. From the viewpoint of preventing side reactions and facilitating the reaction, at least (b) a phosphate compound, (c) a lithium compound, (d) water, and (e) a pH adjuster are mixed in advance to form a precursor slurry. After preparing (a), it is preferable to add (a) a transition metal compound and (f) a metal compound other than the transition metal used as necessary to obtain a mixture slurry. That is, when the raw materials are added in this order, the viscosity does not increase excessively, stirring is facilitated, and the reaction can proceed favorably without requiring unnecessary heating or pressurization.
（ｃ）リチウム化合物、（ｂ）リン酸化合物、（ｄ）水、及び（ｅ）ｐＨ調整剤の添加順序は特に限定されないが、得られる混合物スラリーの分散性等を高める観点、及び反応を良好に進行させる観点から、予め（ｃ）リチウム化合物、（ｅ）ｐＨ調整剤、及び（ｄ）水を混合し、スラリー水を得るのが好ましい。かかるスラリー水は、（ｄ）水１００質量部に対し、２０〜５０質量部の（ｃ）リチウム化合物を含有するのが好ましく、２５〜４５質量部の（ｃ）リチウム化合物を含有するのがより好ましく、３０〜４０質量部の（ｃ）リチウム化合物を含有するのがさらに好ましい。次いで、得られたスラリー水に（ｂ）リン酸化合物を滴下しながら撹拌して、上記前駆体スラリーを得るのが好ましい。（ｂ）リン酸化合物を滴下して少量ずつ加えながら撹拌することで、得られる前駆体スラリー中における反応が良好に進行して、生成する前駆体粒子が均一に分散しつつ生成され、かかる粒子が不要に凝集するのを効果的に抑制することができる。
なお、（ｂ）リン酸化合物としてオルトリン酸（Ｈ3ＰＯ4）を用いる場合、７０〜９０質量％濃度の水溶液として用いるのが好ましい。（ｂ）リン酸化合物の上記スラリー水への滴下速度は、好ましくは１５〜５０ｍＬ／分であり、より好ましくは２０〜４５ｍＬ／分であり、さらに好ましくは２８〜４０ｍＬ／分である。また、スラリー水の撹拌時間は、好ましくは１〜２４時間であり、より好ましくは５〜１５時間である。The order of addition of (c) lithium compound, (b) phosphoric acid compound, (d) water, and (e) pH adjuster is not particularly limited, but the viewpoint of improving the dispersibility of the resulting mixture slurry and the like are favorable. From the viewpoint of proceeding to (1), it is preferable to previously mix (c) a lithium compound, (e) a pH adjuster, and (d) water to obtain slurry water. Such slurry water preferably contains 20 to 50 parts by mass of (c) lithium compound, and more preferably contains 25 to 45 parts by mass of (c) lithium compound with respect to (d) 100 parts by mass of water. Preferably, 30 to 40 parts by mass of (c) a lithium compound is contained. Next, it is preferable to stir while dropping the phosphoric acid compound (b) into the obtained slurry water to obtain the precursor slurry. (B) By adding dropwise the phosphoric acid compound and stirring while adding little by little, the reaction in the resulting precursor slurry proceeds well, and the resulting precursor particles are produced while being uniformly dispersed. Can be effectively prevented from aggregating.
Incidentally, (b) the case of using orthophosphoric acid (H 3 PO 4) as a phosphate compound, preferably used as an aqueous solution of 70 to 90% strength by weight. (B) The dropping rate of the phosphoric acid compound into the slurry water is preferably 15 to 50 mL / min, more preferably 20 to 45 mL / min, and further preferably 28 to 40 mL / min. The stirring time of the slurry water is preferably 1 to 24 hours, more preferably 5 to 15 hours.
スラリー水を撹拌する際における、スラリー水の温度は、好ましくは２０〜６０℃であり、より好ましくは２０〜５０℃である。
なお、スラリー水を撹拌する際、さらにスラリー水の沸点温度以下に冷却するのが好ましい。具体的には、７０℃以下に冷却するのが好ましく、２０〜６０℃に冷却するのがより好ましい。The temperature of the slurry water when stirring the slurry water is preferably 20 to 60 ° C, more preferably 20 to 50 ° C.
In addition, when stirring slurry water, it is preferable to cool to below the boiling point temperature of slurry water. Specifically, cooling to 70 ° C. or lower is preferable, and cooling to 20 to 60 ° C. is more preferable.
上記前駆体スラリーは、リン１モルに対し、リチウムを２．７〜３．３モル含有するのが好ましく、２．７９〜２．９７モル含有するのがより好ましい。リチウムのモル量が上記下限値に満たない場合は、未反応のリン酸の増大によって必要以上のｐＨ低下を招き、続く工程中に不要な金属水和物が生成して混合物の粘度が増大してしまい、反応を良好に進行させることができなくなるおそれがある。一方、リチウムのモル量が上記上限値を超えると、良好な性能をもたらすリチウム遷移金属リン酸塩化合物が得られないおそれがある。 The precursor slurry preferably contains 2.7 to 3.3 moles of lithium, more preferably 2.79 to 2.97 moles per mole of phosphorus. When the molar amount of lithium is less than the above lower limit, an increase in unreacted phosphoric acid causes a pH drop more than necessary, and unnecessary metal hydrates are generated during the subsequent process, increasing the viscosity of the mixture. Therefore, there is a possibility that the reaction cannot proceed well. On the other hand, when the molar amount of lithium exceeds the upper limit, a lithium transition metal phosphate compound that provides good performance may not be obtained.
上記調製した前駆体スラリーに、（ａ）遷移金属化合物、及び必要に応じて用いる（ｆ）遷移金属以外の金属化合物を添加すればよい。これら（ａ）遷移金属化合物や（ｆ）遷移金属以外の金属化合物の添加順序は特に制限されない。また、これらの化合物を添加するとともに、必要に応じて酸化防止剤を添加してもよい。かかる酸化防止剤としては、亜硫酸ナトリウム（Ｎａ2ＳＯ3）、ハイドロサルファイトナトリウム（Ｎａ2Ｓ2Ｏ4）、アンモニア水等を使用することができる。酸化防止剤の添加量は、過剰に添加されることでリチウム遷移金属リン酸塩化合物の生成が抑制されるのを防止する観点から、（ａ）遷移金属化合物及び（ｆ）遷移金属以外の金属化合物合計１モルに対し、好ましくは０．０１〜１モルであり、より好ましくは０．０３〜０．５モルである。What is necessary is just to add metal compounds other than (a) transition metal compound and (f) transition metal used as needed to the prepared precursor slurry. The order of addition of these (a) transition metal compounds and (f) metal compounds other than transition metals is not particularly limited. Moreover, while adding these compounds, you may add antioxidant as needed. As such an antioxidant, sodium sulfite (Na 2 SO 3 ), hydrosulfite sodium (Na 2 S 2 O 4 ), aqueous ammonia and the like can be used. The addition amount of the antioxidant is (a) a transition metal compound and (f) a metal other than the transition metal from the viewpoint of preventing the formation of a lithium transition metal phosphate compound by being added in excess. Preferably it is 0.01-1 mol with respect to 1 mol of total compounds, More preferably, it is 0.03-0.5 mol.
上記成分（ａ）〜（ｅ）、及び必要に応じて成分（ｆ）を含有する混合物スラリーの２５℃におけるｐＨは、副反応を防止する観点、及び反応を良好に進行させる観点から、好ましくは３．５〜９．０であり、より好ましくは４．０〜８．０であり、さらに好ましくは４．５〜７．５である。 The pH at 25 ° C. of the mixture slurry containing the components (a) to (e) and, if necessary, the component (f) is preferably from the viewpoint of preventing side reactions and allowing the reaction to proceed well. It is 3.5-9.0, More preferably, it is 4.0-8.0, More preferably, it is 4.5-7.5.
得られた混合物スラリーは、大気圧以下の雰囲気圧力で撹拌して、目的物を生成させるための反応を進行させる。大気圧以下とは、具体的には０．１ＭＰａ以下であればよい。すなわち、本発明の製造方法は、特段加圧する必要なく、また大がかりな装置を要することなく、反応を良好に進行させることができる。撹拌する時間は、好ましくは６〜４８時間であり、より好ましくは１２〜２４時間である。
また、反応させる際の温度は、好ましくは１００℃未満であり、より好ましくは６５〜９５℃であり、さらに好ましくは７０〜９０℃である。したがって、過度の加熱を要することがないため、例えば、少なくとも１００℃以上の加熱を要する水熱反応よりも簡便な手段によって、反応を良好に進行させることができる。
なお、混合物スラリー撹拌する際に用いる装置としては、特に制限されず、バッチ式、連続式のいずれであってもよく、加熱方式（間接又は直接）のものも使用することができる。The obtained mixture slurry is stirred at an atmospheric pressure equal to or lower than atmospheric pressure, and a reaction for generating a target product proceeds. Specifically, the atmospheric pressure or lower may be 0.1 MPa or lower. That is, the production method of the present invention allows the reaction to proceed satisfactorily without the need for special pressurization and without requiring a large-scale apparatus. The stirring time is preferably 6 to 48 hours, and more preferably 12 to 24 hours.
Moreover, the temperature at the time of making it react becomes like this. Preferably it is less than 100 degreeC, More preferably, it is 65-95 degreeC, More preferably, it is 70-90 degreeC. Therefore, since excessive heating is not required, for example, the reaction can be favorably progressed by a simpler means than a hydrothermal reaction that requires heating of at least 100 ° C. or more.
In addition, it does not restrict | limit especially as an apparatus used when stirring a mixture slurry, Any of a batch type and a continuous type may be sufficient, and the thing of a heating system (indirect or direct) can also be used.
上記混合物スラリーを撹拌して反応させ、次いでろ過することにより、オリビン型リチウムイオン二次電池用正極活物質の粒子が高収率で得られ、その結晶度も高い。かかる粒子の平均粒径は、リチウムイオン電池の電池特性を高める観点から、好ましくは１０〜５００ｎｍであり、より好ましくは１０〜１００ｎｍである。 By stirring and reacting the mixture slurry and then filtering, particles of the positive electrode active material for olivine type lithium ion secondary battery can be obtained in high yield, and the crystallinity thereof is also high. The average particle diameter of such particles is preferably 10 to 500 nm, more preferably 10 to 100 nm, from the viewpoint of improving the battery characteristics of the lithium ion battery.
得られたオリビン型リチウムイオン二次電池用正極活物質は、洗浄後にろ過し、次いで乾燥することにより、単離することができる。洗浄する際における水の使用量は、オリビン型リチウムイオン二次電池用正極活物質１質量部に対し、好ましくは５〜１００質量部であり、より好ましくは５〜５０質量部である。乾燥手段としては、真空乾燥、噴霧乾燥、箱型乾燥、流動床乾燥、外熱式乾燥、凍結乾燥が挙げられる。なかでも、真空乾燥が好ましい。また、乾燥する際、予めオリビン型リチウムイオン二次電池用正極活物質を用いて調製したスラリーを用いるのがよい。かかるスラリーにおけるオリビン型リチウムイオン二次電池用正極活物質の含有量（固形分濃度）は、電池特性を高める観点から、好ましくは２０〜６０質量％であり、より好ましくは３０〜５０質量％であり、さらに好ましくは３５〜４５質量％である。 The obtained positive electrode active material for olivine type lithium ion secondary battery can be isolated by filtering after washing and then drying. The amount of water used for washing is preferably 5 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to 1 part by mass of the positive electrode active material for olivine type lithium ion secondary battery. Examples of the drying means include vacuum drying, spray drying, box drying, fluidized bed drying, external heat drying, and freeze drying. Of these, vacuum drying is preferred. Moreover, when drying, it is good to use the slurry previously prepared using the positive electrode active material for olivine type lithium ion secondary batteries. The content (solid content concentration) of the positive electrode active material for the olivine type lithium ion secondary battery in the slurry is preferably 20 to 60% by mass, more preferably 30 to 50% by mass, from the viewpoint of improving battery characteristics. Yes, and more preferably 35 to 45% by mass.
この際、分散剤や増粘剤をスラリーに少量添加しても良く、分散剤としては、例えば、ポリカルボン酸系、ポリエーテル系、ポリアクリル酸系などを用いることができる。
増粘剤としては、例えば、酢酸、クエン酸などの有機酸を用いることができる。At this time, a small amount of a dispersant or a thickener may be added to the slurry, and as the dispersant, for example, a polycarboxylic acid type, a polyether type, a polyacrylic acid type, or the like can be used.
As the thickener, for example, organic acids such as acetic acid and citric acid can be used.
こうして得られる乾燥物については、乾燥時又は乾燥後にセパレータ、サイクロン、篩等で分級してもよく、また乳鉢ピンミル、ロールミル、クラッシャー等を用いて粉砕してもよい。また、より優れた電池特性を発揮させる観点から、得られた粒子の表面に炭素を担持させるべく、炭素源としてグルコース、ポリビニルアルコール、カルボキシメチルセルロース、カーボンブラック等の導電性炭素材料を用い、得られたオリビン型リチウムイオン二次電池用正極活物質及び導電性炭素材料を含有するスラリーを調製し、造粒後に焼成する処理を施してもよい。かかるスラリーには、適宜、有機バインダー、無機バインダーを含有させてもよい。
なお、かかる焼成する処理を施す場合、不活性ガス雰囲気下又は還元条件下で、好ましくは５００〜８００℃で１０分〜２４時間、より好ましくは６００〜７５０℃で０．５〜３時間焼成するのが好ましい。焼成に用いる装置としては、焼成雰囲気及び温度の調整が可能なものであれば特に制限されず、バッチ式、連続式、加熱方式（間接又は直接）のいずれの方式のものも使用することができる。かかる装置としては、例えば、外熱キルンやローラーハース等の管状電気炉が挙げられる。The dried product thus obtained may be classified with a separator, cyclone, sieve or the like during or after drying, or may be pulverized with a mortar pin mill, roll mill, crusher or the like. In addition, from the viewpoint of exhibiting more excellent battery characteristics, in order to carry carbon on the surface of the obtained particles, a conductive carbon material such as glucose, polyvinyl alcohol, carboxymethyl cellulose, carbon black or the like is used as a carbon source. In addition, a slurry containing a positive electrode active material for an olivine type lithium ion secondary battery and a conductive carbon material may be prepared and subjected to a firing process after granulation. Such a slurry may appropriately contain an organic binder and an inorganic binder.
In addition, when performing the process which carries out such baking, it bakes by an inert gas atmosphere or reducing conditions, Preferably it is 500-800 degreeC for 10 minutes-24 hours, More preferably, it is 0.5-3 hours at 600-750 degreeC. Is preferred. The apparatus used for firing is not particularly limited as long as the firing atmosphere and temperature can be adjusted, and any of a batch system, a continuous system, and a heating system (indirect or direct) can be used. . Examples of such an apparatus include tubular electric furnaces such as an external heat kiln and a roller hearth.
得られたオリビン型リチウムイオン二次電池用正極活物質の平均粒径は、電池特性を高める観点から、好ましくは３〜１５０μｍであり、より好ましくは３〜１００μｍであり、さらに好ましくは５〜５０μｍである。 The average particle diameter of the obtained positive electrode active material for the olivine type lithium ion secondary battery is preferably 3 to 150 μm, more preferably 3 to 100 μm, and further preferably 5 to 50 μm, from the viewpoint of improving battery characteristics. It is.
本発明の製造方法により得られるオリビン型リチウムイオン二次電池用正極活物質としては、具体的には、例えば以下のような態様が含まれる。
ＬｉＦｅaＭｎ1-aＰＯ4 ・・・（Ｉ）
（式中、ａは０≦ａ＜０．５を満たす数を示す。）
ＬｉＦｅa1Ｍｎb1Ｍ1 cＰＯ4 ・・・（II）
（式中、Ｍ1はＮｉ、Ｃｏ、Ｚｎ、Ｖ、Ｚｒ、Ｙ、Ｍｏ、Ｌａ、Ｃｅ及びＮｄから選ばれる１種又は２種以上を示す。ａ1、ｂ1及びｃは、０＜ａ1＜０．５、０．５＜ｂ1＜１、及び０＜ｃ≦０．２を満たし、かつ２ａ1＋２ｂ1＋（Ｍ1の価数）×ｃ＝２を満たす数を示す。）
ＬｉＦｅa2Ｍｎb2ＲdＰＯ4 ・・・（III）
（式中、ＲはＡｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ、及びＧｄから選ばれる１種又は２種以上を示す。ａ2、ｂ2及びｄは、０＜ａ2＜０．５、０．５＜ｂ2＜１、及び０＜ｄ≦０．２を満たし、かつ２ａ2＋２ｂ2＋（Ｒの価数）×ｄ＝２を満たす数を示す。）
ＬｉＦｅa3Ｍｎb3Ｍ1 c1Ｒd1ＰＯ4 ・・・（IV）
（式中、Ｍ1はＮｉ、Ｃｏ、Ｚｎ、Ｖ、Ｚｒ、Ｙ、Ｍｏ、Ｌａ、Ｃｅ及びＮｄから選ばれる１種又は２種以上を、ＲはＡｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｐｂ、及びＢｉから選ばれる１種又は２種以上を示す。ａ3、ｂ3、ｃ1及びｄ1は、０＜ａ3＜０．５、０．５＜ｂ3＜１、及び０＜（ｃ1＋ｄ1）≦０．２を満たし、かつ２ａ3＋２ｂ3＋（Ｍ1の価数）×ｃ1＋（Ｒの価数）×ｄ1＝２を満たす数を示す。）Specific examples of the positive electrode active material for an olivine type lithium ion secondary battery obtained by the production method of the present invention include the following embodiments.
LiFe a Mn 1-a PO 4 (I)
(In the formula, a represents a number satisfying 0 ≦ a <0.5.)
LiFe a1 Mn b1 M 1 c PO 4 (II)
(In the formula, M 1 represents one or more selected from Ni, Co, Zn, V, Zr, Y, Mo, La, Ce and Nd. A1, b1 and c are 0 <a1 <0. .5,0.5 <b1 <1, and meet 0 <c ≦ 0.2, and shows a number satisfying 2a1 + 2b1 + (valence of M 1) × c = 2. )
LiFe a2 Mn b2 R d PO 4 (III)
(In the formula, R represents one or more selected from Al, Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, and Gd. A2, b2, and d represents a number satisfying 0 <a2 <0.5, 0.5 <b2 <1, and 0 <d ≦ 0.2, and satisfying 2a2 + 2b2 + (R valence) × d = 2.)
LiFe a3 Mn b3 M 1 c1 R d1 PO 4 (IV)
(In the formula, M 1 represents one or more selected from Ni, Co, Zn, V, Zr, Y, Mo, La, Ce and Nd, and R represents Al, Mg, Ca, Sr, Ba, Pb. 1 or 2 or more selected from Bi, a3, b3, c1 and d1 are 0 <a3 <0.5, 0.5 <b3 <1, and 0 <(c1 + d1) ≦ 0.2 the filled, and shows a number satisfying 2a3 + 2b3 + (valence of M 1) × c1 + (valence of R) × d1 = 2.)
本発明のオリビン型リチウムイオン二次電池用正極活物質を含むリチウムイオン電池用正極を適用できるリチウムイオン電池としては、正極と負極と電解液とセパレータを必須構成とするものであれば特に限定されない。 The lithium ion battery to which the positive electrode for a lithium ion battery including the positive electrode active material for an olivine type lithium ion secondary battery of the present invention can be applied is not particularly limited as long as it has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components. .
ここで、負極については、リチウムイオンを充電時には吸蔵し、かつ放電時には放出することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。たとえば、リチウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムを電気化学的に吸蔵・放出し得るインターカレート材料で形成された電極、特に炭素材料を用いることが好ましい。 Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.
電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常リチウムイオン二次電池の電解液の用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。 The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a lithium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones An oxolane compound or the like can be used.
支持塩は、その種類が特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2及びＬｉＮ（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2及びＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 and LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and organic salt derivatives It is preferable that it is at least 1 type of these.
セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。 The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
［実施例１］
ＬｉＯＨ・Ｈ2Ｏ ２．５６９ｇ（６０ｍｍｏｌ）、ＮａＯＨ ４．４ｇ（１１０ｍｍｏｌ）、水 ３０ｍＬを混合してスラリー水を得た。次いで、得られたスラリー水を、２５℃の温度に保持しながら１０分間撹拌しつつ８５％のリン酸水溶液 ６．９１８ｇを３５ｍＬ／分で滴下し、続いて１２時間撹拌することにより前駆体スラリーを得た。かかる前駆体スラリーは、リン１モルに対し、１モルのリチウムを含有していた。[Example 1]
The slurry water was obtained by mixing 2.569 g (60 mmol) of LiOH.H 2 O, 4.4 g (110 mmol) of NaOH, and 30 mL of water. Next, the slurry water obtained was stirred for 10 minutes while maintaining the temperature at 25 ° C., and 6.918 g of 85% phosphoric acid aqueous solution was added dropwise at 35 mL / min, and then the precursor slurry was stirred for 12 hours. Got. Such precursor slurry contained 1 mole of lithium per mole of phosphorus.
次に、得られた前駆体スラリー全量に対し、ＭｎＳＯ4・５Ｈ2Ｏ １１．５７２ｇ、ＦｅＳＯ4・７Ｈ2Ｏ ３．３３６ｇを添加して、ｐＨ４．３の混合物スラリーを得た。このとき、添加したＭｎＳＯ4とＦｅＳＯ4のモル比（マンガン化合物：鉄化合物）は、４：１であった。また、混合物スラリー中におけるリチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）は０．５４５：１であった。
続いて、得られた混合物スラリーを０．１ＭＰａの雰囲気圧力下、９０℃で１２時間撹拌し、反応を進行させた。生成した結晶をろ過し、次いで結晶１質量部に対し、１２質量部の水により洗浄した。洗浄した結晶を６０℃１Ｔｏｒｒの条件で真空乾燥して、正極活物質であるリン酸マンガン鉄リチウム化合物（ＬｉＭｎ0.8Ｆｅ0.2ＰＯ4）を得た。Next, 11.572 g of MnSO 4 .5H 2 O and 3.336 g of FeSO 4 .7H 2 O were added to the total amount of the obtained precursor slurry to obtain a mixture slurry having a pH of 4.3. At this time, the molar ratio of MnSO 4 and FeSO 4 added (manganese compound: iron compound) was 4: 1. Moreover, the molar ratio (lithium ion: hydroxide ion) of the lithium compound content and the NaOH content in the mixture slurry was 0.545: 1.
Subsequently, the resulting mixture slurry was stirred at 90 ° C. for 12 hours under an atmospheric pressure of 0.1 MPa to allow the reaction to proceed. The produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was vacuum-dried at 60 ° C. and 1 Torr to obtain a lithium iron manganese phosphate compound (LiMn 0.8 Fe 0.2 PO 4 ) as a positive electrode active material.
［実施例２］
ＮａＯＨを４．８ｇ（１２０ｍｍｏｌ）とし、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．５：１、ｐＨ＝６．０）を得た以外、実施例１と同様にして正極活物質を得た。[Example 2]
4.8 g (120 mmol) of NaOH, and the mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ion: hydroxide ion) = 0.5: 1, pH = 6.0) A positive electrode active material was obtained in the same manner as in Example 1 except that it was obtained.
［実施例３］
ＮａＯＨを５．６ｇ（１４０ｍｍｏｌ）とし、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．４２９：１、ｐＨ＝８．０）を得た以外、実施例１と同様にして正極活物質を得た。[Example 3]
5.6 g (140 mmol) of NaOH, and the mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ions: hydroxide ions) = 0.429: 1, pH = 8.0) A positive electrode active material was obtained in the same manner as in Example 1 except that it was obtained.
［実施例４］
ＮａＯＨの代わりにＫＯＨを６．７２７ｇ（１２０ｍｍｏｌ）を用い、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．５：１、ｐＨ＝５．３）を得た以外、実施例１と同様にして正極活物質を得た。[Example 4]
6.727 g (120 mmol) of KOH was used instead of NaOH, and the mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ion: hydroxide ion) = 0.5: 1, pH = A positive electrode active material was obtained in the same manner as in Example 1 except that 5.3) was obtained.
［実施例５］
ＬｉＯＨ・Ｈ2Ｏを５．１３８ｇ（１２０ｍｍｏｌ）、ＮａＯＨを２．４ｇ（６０ｍｍｏｌ）とし、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝２．０：１、ｐＨ＝５．６、リン１モルに対して２モルのリチウムを含有）を得た以外、実施例１と同様にして正極活物質を得た。[Example 5]
5.138 g (120 mmol) of LiOH.H 2 O and 2.4 g (60 mmol) of NaOH, and mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ions: hydroxide ions) = A positive electrode active material was obtained in the same manner as in Example 1, except that 2.0: 1, pH = 5.6, and 2 mol of lithium per mol of phosphorus were obtained.
［実施例６］
ＬｉＯＨ・Ｈ2Ｏを６．２９５ｇ（１５０ｍｍｏｌ）、ＮａＯＨを１．２ｇ（３０ｍｍｏｌ）とし、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝５．０：１、ｐＨ＝６．５、リン１モルに対して２．５モルのリチウムを含有）を得た以外、実施例１と同様にして正極活物質を得た。[Example 6]
6.295 g (150 mmol) of LiOH.H 2 O and 1.2 g (30 mmol) of NaOH, mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ions: hydroxide ions) = A positive electrode active material was obtained in the same manner as in Example 1, except that 5.0: 1, pH = 6.5, and 2.5 mol of lithium per mol of phosphorus were obtained.
［実施例７］
ＭｎＳＯ4・５Ｈ2Ｏを１０．８４９ｇ（４５ｍｍｏｌ）、ＦｅＳＯ4・７Ｈ2Ｏを２．５０２ｇ（９ｍｍｏｌ）とし、ＭｇＳＯ4・７Ｈ2Ｏを１．４８６ｇ（６ｍｍｏｌ）を添加し、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．５４５：１、ｐＨ＝５．８、リン１モルに対して１モルのリチウムを含有）を得た以外、実施例１と同様にして正極活物質を得た。[Example 7]
10.4849 g (45 mmol) of MnSO 4 .5H 2 O, 2.502 g (9 mmol) of FeSO 4 .7H 2 O, 1.486 g (6 mmol) of MgSO 4 .7H 2 O were added, and the mixture slurry (lithium The molar ratio of the compound content to the NaOH content (lithium ions: hydroxide ions) = 0.545: 1, pH = 5.8, containing 1 mol of lithium per mol of phosphorus) A positive electrode active material was obtained in the same manner as in Example 1 except that.
［実施例８］
ＭｎＳＯ4・５Ｈ2Ｏを１０．８４９ｇ（４５ｍｍｏｌ）、ＦｅＳＯ4・７Ｈ2Ｏを３．１６９ｇ（１１．４ｍｍｏｌ）とし、Ｚｒ（ＳＯ4）2・４Ｈ2Ｏを０．６４０ｇ（１．８ｍｍｏｌ）を添加し、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．５４５：１、ｐＨ＝５．９、リン１モルに対して１モルのリチウムを含有）を得た以外、実施例１と同様にして正極活物質を得た。[Example 8]
10.4849 g (45 mmol) of MnSO 4 .5H 2 O, 3.169 g (11.4 mmol) of FeSO 4 .7H 2 O, and 0.640 g (1.8 mmol) of Zr (SO 4 ) 2 .4H 2 O The mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ion: hydroxide ion) = 0.545: 1, pH = 5.9, 1 for 1 mole of phosphorus A positive electrode active material was obtained in the same manner as in Example 1 except that a molar amount of lithium was obtained.
［実施例９］
反応温度を８０℃とした以外、実施例１と同様にして正極活物質を得た。[Example 9]
A positive electrode active material was obtained in the same manner as in Example 1 except that the reaction temperature was 80 ° C.
［実施例１０］
反応温度を７０℃とした以外、実施例１と同様にして正極活物質を得た。[Example 10]
A positive electrode active material was obtained in the same manner as in Example 1 except that the reaction temperature was 70 ° C.
［比較例１］
ＬｉＯＨ・Ｈ2Ｏ ７．７０７ｇ（１８０ｍｍｏｌ）と水 ３０ｍＬを混合してスラリー水を得た。次いで、得られたスラリー水を、２５℃の温度に保持しながら１０分間撹拌しつつ８５％のリン酸水溶液 ６．９１８ｇを３５ｍＬ／分で滴下し、続いて１２時間撹拌することにより前駆体スラリーを得た。かかるスラリーは、リン１モルに対し、３．０モルのリチウムを含有していた。[Comparative Example 1]
7.707 g (180 mmol) of LiOH.H 2 O and 30 mL of water were mixed to obtain slurry water. Next, the slurry water obtained was stirred for 10 minutes while maintaining the temperature at 25 ° C., and 6.918 g of 85% phosphoric acid aqueous solution was added dropwise at 35 mL / min, and then the precursor slurry was stirred for 12 hours. Got. Such a slurry contained 3.0 moles of lithium per mole of phosphorus.
次に、得られた前駆体スラリー全量に対し、ＭｎＳＯ4・５Ｈ2Ｏ １１．５７２ｇ、ＦｅＳＯ4・７Ｈ2Ｏ ３．３３６ｇを添加して、ｐＨ５．３の混合物スラリーを得た。このとき、添加したＭｎＳＯ4とＦｅＳＯ4のモル比（マンガン化合物：鉄化合物）は、４：１であった。
次いで、得られた混合物スラリーをオートクレーブに投入し、１７０℃で０．５時間水熱反応を行った。オートクレーブ内の雰囲気圧力は、０．８ＭＰａであった。生成した結晶をろ過し、次いで結晶１質量部に対し、１２質量部の水により洗浄した。洗浄した結晶を６０℃１Ｔｏｒｒの条件で真空乾燥して、正極活物質であるリン酸マンガン鉄リチウム化合物（ＬｉＭｎ0.8Ｆｅ0.2ＰＯ4）を得た。Next, 11.572 g of MnSO 4 .5H 2 O and 3.336 g of FeSO 4 .7H 2 O were added to the total amount of the obtained precursor slurry to obtain a mixture slurry having a pH of 5.3. At this time, the molar ratio of MnSO 4 and FeSO 4 added (manganese compound: iron compound) was 4: 1.
Subsequently, the obtained mixture slurry was put into an autoclave and subjected to a hydrothermal reaction at 170 ° C. for 0.5 hour. The atmospheric pressure in the autoclave was 0.8 MPa. The produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was vacuum-dried at 60 ° C. and 1 Torr to obtain a lithium iron manganese phosphate compound (LiMn 0.8 Fe 0.2 PO 4 ) as a positive electrode active material.
［比較例２］
オートクレーブ内の雰囲気圧力を０．１ＭＰａの雰囲気圧力とした以外、比較例１と同様にして正極活物質を得た。[Comparative Example 2]
A positive electrode active material was obtained in the same manner as in Comparative Example 1 except that the atmospheric pressure in the autoclave was changed to an atmospheric pressure of 0.1 MPa.
［比較例３］
ＮａＯＨの代わりにＮＨ4ＯＨを７．２９９ｇ（１２０ｍｍｏｌ）を用い、混合物スラリー（リチウム化合物の含有量とＮａＯＨの含有量とのモル比（リチウムイオン：水酸化物イオン）＝０．５：１、ｐＨ＝４．４）を得た以外、実施例１と同様にして正極活物質を得た。
実施例１〜１０、比較例１〜３の上記諸条件等を表１に示す。[Comparative Example 3]
7. 299 g (120 mmol) of NH 4 OH was used instead of NaOH, and a mixture slurry (molar ratio of lithium compound content to NaOH content (lithium ion: hydroxide ion) = 0.5: 1, A positive electrode active material was obtained in the same manner as in Example 1 except that pH = 4.4) was obtained.
The above conditions and the like of Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Table 1.
《試験例１：生成相の観察》
実施例１〜１０及び比較例１〜３で得られた正極活物質を用い、ＸＲＤ分析により生成相を観察し、評価した。
結果を表２に示す。<< Test Example 1: Observation of Formation Phase >>
Using the positive electrode active materials obtained in Examples 1 to 10 and Comparative Examples 1 to 3, the generated phase was observed and evaluated by XRD analysis.
The results are shown in Table 2.
《試験例２：充放電特性の評価》
実施例１〜１０及び比較例１〜３で得られた正極活物質を用い、リチウムイオン二次電池の正極を作製した。具体的には、得られた正極活物質、ケッチェンブラック、ポリフッ化ビニリデンを重量比７５：１５：１０の配合割合で混合し、これにＮ−メチル−２−ピロリドンを加えて充分混練し、正極スラリーを調製した。正極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、正極とした。
次いで、上記の正極を用いてコイン型リチウムイオン二次電池を構築した。負極には、φ１５ｍｍに打ち抜いたリチウム箔を用いた。電解液には、エチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒に、ＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で溶解したものを用いた。セパレータには、ポリプロピレンなどの高分子多孔フィルムなど、公知のものを用いた。これらの電池部品を露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。<< Test Example 2: Evaluation of charge / discharge characteristics >>
The positive electrode of the lithium ion secondary battery was produced using the positive electrode active material obtained in Examples 1-10 and Comparative Examples 1-3. Specifically, the obtained positive electrode active material, ketjen black, and polyvinylidene fluoride were mixed at a mixing ratio of 75:15:10 by weight, and N-methyl-2-pyrrolidone was added thereto and kneaded sufficiently. A positive electrode slurry was prepared. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.
Next, a coin-type lithium ion secondary battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / L in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).
製造したリチウム二次電池を用い、放電容量測定装置（ＨＪ−１００１ＳＤ８、北斗電工製）にて充放電を１サイクル行った。充電条件は、電流０．１ＣＡ（１７ｍＡｈ／ｇ）、電圧４．５Ｖの定電流電圧充電とし、放電条件は電流３ＣＡ（５１０ｍＡｈ／ｇ）、電圧２．０Ｖの定電流電圧放電とした。
結果を表３に示す。Using the manufactured lithium secondary battery, one cycle of charge and discharge was performed with a discharge capacity measuring device (HJ-1001SD8, manufactured by Hokuto Denko). The charging conditions were constant current voltage charging with a current of 0.1 CA (17 mAh / g) and a voltage of 4.5 V, and the discharging conditions were constant current voltage discharging with a current of 3 CA (510 mAh / g) and a voltage of 2.0 V.
The results are shown in Table 3.
表１〜３の結果より、ｐＨ調整剤を用いることなく、１００℃未満の温度、大気圧雰囲気下で水熱合成を行った比較例２、及びｐＨ調整剤としてＮＨ4ＯＨを用いた比較例３は、不純物相が確認された上、十分な電池特性を発揮することができなかったことがわかる。
これに比して、実施例１〜１０は、単相の活物質が得られ、水熱反応を経ることにより得られる従来の正極活物質（比較例１）と同等の電池特性を発揮できることがわかる。From the results of Tables 1 to 3, Comparative Example 2 in which hydrothermal synthesis was performed at a temperature below 100 ° C. and atmospheric pressure without using a pH adjusting agent, and Comparative Example using NH 4 OH as a pH adjusting agent 3 shows that the impurity phase was confirmed and sufficient battery characteristics could not be exhibited.
On the other hand, Examples 1 to 10 can obtain a battery characteristic equivalent to that of a conventional positive electrode active material (Comparative Example 1) obtained by obtaining a single-phase active material and undergoing a hydrothermal reaction. Recognize.
Claims (3)
得られた前駆体スラリーに（ａ）遷移金属化合物を添加して混合物スラリーを得る請求項１又は２に記載のオリビン型リチウムイオン二次電池用正極活物質の製造方法。 In advance, (c) a lithium compound, (d) water, and (e) one or two kinds of pH adjusting agents selected from NaOH and KOH are mixed, and then (b) a phosphoric acid compound is added to form a precursor slurry. Prepared,
The manufacturing method of the positive electrode active material for olivine type lithium ion secondary batteries of Claim 1 or 2 which adds a transition metal compound to the obtained precursor slurry, and obtains a mixture slurry.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014216802 | 2014-10-24 | ||
| JP2014216802 | 2014-10-24 | ||
| PCT/JP2015/079775 WO2016063932A1 (en) | 2014-10-24 | 2015-10-22 | Manufacturing method for positive electrode active material for olivine-type lithium-ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2016063932A1 JPWO2016063932A1 (en) | 2017-04-27 |
| JP6126318B2 true JP6126318B2 (en) | 2017-05-10 |
Family
ID=55760963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016555272A Active JP6126318B2 (en) | 2014-10-24 | 2015-10-22 | Method for producing positive electrode active material for olivine type lithium ion secondary battery |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6126318B2 (en) |
| WO (1) | WO2016063932A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021033706A1 (en) | 2019-08-19 | 2021-02-25 | Ａｐｂ株式会社 | Lithium ion battery module and battery pack |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4737607B2 (en) * | 2005-07-22 | 2011-08-03 | テイカ株式会社 | Method for producing carbon-olivine type lithium iron phosphate composite particles, and positive electrode material for lithium ion battery |
| JP5463561B2 (en) * | 2006-08-09 | 2014-04-09 | 関東電化工業株式会社 | COMPOUND HAVING ORIBIN STRUCTURE, PROCESS FOR PRODUCING THE SAME, POSITIVE ACTIVE MATERIAL USING COMPOUND HAVING ORIBIN STRUCTURE AND NON-AQUEOUS ELECTROLYTE BATTERY |
| JP5272756B2 (en) * | 2008-02-12 | 2013-08-28 | 株式会社Ｇｓユアサ | Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery, and production method thereof |
| JP5429980B2 (en) * | 2009-11-05 | 2014-02-26 | テイカ株式会社 | Method for producing carbon-olivine-type manganese iron phosphate lithium composite and positive electrode material for lithium ion battery |
| JP2012221855A (en) * | 2011-04-12 | 2012-11-12 | Sony Corp | Positive electrode active material for nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery, and battery pack, electronic device, electric vehicle, power storage device, and electric power system comprising nonaqueous electrolyte battery |
| TW201311547A (en) * | 2011-08-03 | 2013-03-16 | Murata Manufacturing Co | Iron lithium phosphate preparation method, electrode active material, and secondary battery |
| JP2013077456A (en) * | 2011-09-30 | 2013-04-25 | Fdk Twicell Co Ltd | Alkaline secondary battery |
| DE102011056812A1 (en) * | 2011-12-21 | 2013-06-27 | Chemische Fabrik Budenheim Kg | Metal phosphates and process for their preparation |
-
2015
- 2015-10-22 WO PCT/JP2015/079775 patent/WO2016063932A1/en active Application Filing
- 2015-10-22 JP JP2016555272A patent/JP6126318B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016063932A1 (en) | 2016-04-28 |
| JPWO2016063932A1 (en) | 2017-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5281765B2 (en) | Method for producing lithium iron phosphorus-based composite oxide carbon composite and method for producing coprecipitate containing lithium, iron and phosphorus | |
| EP2407426A1 (en) | Process for producing lithium borate compound | |
| US10205168B2 (en) | Sodium transition metal silicates | |
| JP2017004927A (en) | Manufacturing method of olivine type lithium phosphate positive electrode material | |
| JP5842792B2 (en) | Method for producing secondary battery positive electrode active material precursor | |
| JP5725456B2 (en) | Method for producing positive electrode active material for lithium ion secondary battery | |
| JP5505868B2 (en) | Precursor of positive electrode active material for lithium secondary battery and method for producing the same | |
| JP2010232091A (en) | Method for manufacturing positive active material for lithium ion battery, positive active material for lithium ion battery, electrode for lithium ion battery, and lithium ion battery | |
| JP5765811B2 (en) | Method for producing lithium iron phosphate positive electrode active material | |
| JP6315858B1 (en) | Method for producing lithium manganese phosphate positive electrode active material | |
| JP6126318B2 (en) | Method for producing positive electrode active material for olivine type lithium ion secondary battery | |
| JP6307127B2 (en) | Method for producing lithium phosphate positive electrode active material | |
| JP5765810B2 (en) | Cathode active material for lithium ion battery and method for producing the same | |
| JP6180070B2 (en) | Method for producing lithium iron phosphate | |
| JP5649068B2 (en) | Cathode active material for lithium ion battery and method for producing the same | |
| JP5820522B1 (en) | Positive electrode active material for lithium secondary battery and method for producing the same | |
| JP5769140B2 (en) | Method for producing positive electrode active material for lithium secondary battery | |
| JP5649067B2 (en) | Cathode active material for lithium ion battery and method for producing the same | |
| JP5876558B1 (en) | Positive electrode active material for olivine type lithium ion secondary battery and method for producing the same | |
| JP5886923B1 (en) | Method for producing lithium silicate compound having amorphous structure | |
| JP5825573B2 (en) | Cathode active material for lithium ion battery and method for producing the same | |
| JP5649069B2 (en) | Cathode active material for lithium ion battery and method for producing the same | |
| JP2018041683A (en) | Method for manufacturing olivine type lithium phosphate-based positive electrode material | |
| JP6126033B2 (en) | Method for producing olivine-type silicate compound | |
| JP2022135548A (en) | Production method for olivine-type lithium phosphate-based positive electrode active material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161026 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20161026 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20170104 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170117 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170206 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170310 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20170321 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170404 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170406 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6126318 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |