JP6042515B2 - Positive electrode active material for secondary battery and method for producing the same - Google Patents
Positive electrode active material for secondary battery and method for producing the same Download PDFInfo
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- JP6042515B2 JP6042515B2 JP2015178163A JP2015178163A JP6042515B2 JP 6042515 B2 JP6042515 B2 JP 6042515B2 JP 2015178163 A JP2015178163 A JP 2015178163A JP 2015178163 A JP2015178163 A JP 2015178163A JP 6042515 B2 JP6042515 B2 JP 6042515B2
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- secondary battery
- metal
- positive electrode
- ion secondary
- active material
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- 239000007774 positive electrode material Substances 0.000 title claims description 97
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- 239000003575 carbonaceous material Substances 0.000 claims description 54
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 51
- 229910001416 lithium ion Inorganic materials 0.000 claims description 51
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910021292 NaFe0.15Mn0.7Co0.15PO4 Inorganic materials 0.000 description 1
- 229910021294 NaFe0.15Mn0.7Mg0.15 PO4 Inorganic materials 0.000 description 1
- 229910021291 NaFe0.19Mn0.75Mo0.03PO4 Inorganic materials 0.000 description 1
- 229910021288 NaFe0.9Mn0.1PO4 Inorganic materials 0.000 description 1
- 229910018908 NaN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002009 diols Chemical class 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
- 150000002016 disaccharides Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、酸化物に水溶性炭素材料由来の炭素と金属フッ化物とが、ともに担持してなる二次電池用正極活物質に関する。 The present invention relates to a positive electrode active material for a secondary battery in which carbon derived from a water-soluble carbon material and a metal fluoride are both supported on an oxide.
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、室温付近で動作する最も優れた二次電池として広く知られている。こうしたなか、Ｌｉ（Ｆｅ，Ｍｎ）ＰＯ4やＬｉ2（Ｆｅ，Ｍｎ）ＳｉＯ4等のリチウム含有オリビン型リン酸金属塩は、ＬｉＣｏＯ２等のリチウム遷移金属酸化物に比べて、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は最適な正極材料となる。しかしながら、これらの化合物は、結晶構造に由来して導電性を十分に高めるのが困難な性質を有しており、またリチウムイオンの拡散性にも改善の余地があるため、従来より種々の開発がなされている。 Secondary batteries used in portable electronic devices, hybrid cars, electric cars, and the like have been developed. In particular, lithium ion secondary batteries are widely known as the most excellent secondary batteries that operate near room temperature. Under these circumstances, lithium-containing olivine-type phosphate metal salts such as Li (Fe, Mn) PO 4 and Li 2 (Fe, Mn) SiO 4 are more resource-constrained than lithium transition metal oxides such as LiCoO 2. Therefore, it is possible to exhibit high safety, and therefore, it is an optimum positive electrode material for obtaining a high-output and large-capacity lithium ion secondary battery. However, these compounds have the property that it is difficult to sufficiently increase the conductivity due to the crystal structure, and there is room for improvement in the diffusibility of lithium ions. Has been made.
さらに、普及が進んでいるリチウムイオン二次電池では、充電後長時間放置すると内部抵抗が徐々に上昇し、電池性能の劣化が生じる現象が知られている。これは、製造時に電池材料が含有していた水分が、電池の充放電が繰り返される中で材料から脱離し、かかる水分と電池に充満している非水電解液ＬｉＰＦ6との化学反応によって、フッ化水素が発生するためである。こうした電池性能の劣化を有効に抑制するには、二次電池に用いる正極活物質の水分含有量を低減することが有効であることも知られている（特許文献１参照）。 Furthermore, in lithium ion secondary batteries, which are spreading, it is known that the internal resistance gradually increases when the battery is left for a long time after charging, and the battery performance is deteriorated. This is because the moisture contained in the battery material at the time of manufacture is desorbed from the material during repeated charging and discharging of the battery, and by the chemical reaction between the moisture and the nonaqueous electrolyte LiPF 6 filling the battery, This is because hydrogen fluoride is generated. It is also known that reducing the water content of the positive electrode active material used in the secondary battery is effective for effectively suppressing such deterioration in battery performance (see Patent Document 1).
こうしたなか、例えば、特許文献２には、炭素質物質前駆体を含む原料混合物の焼成処理後、粉砕処理や分級処理を乾燥雰囲気下で行うことにより、かかる水分含有量を一定値以下に低減する技術が開示されている。また、特許文献３には、所定のリン酸リチウム化合物やケイ酸リチウム化合物等と導電性炭素材料を湿式ボールミルにより混合した後、メカノケミカル処理を行うことにより、表面に均一に導電性炭素材料が沈着されてなる複合酸化物を得る技術が開示されている。 Under these circumstances, for example, Patent Document 2 discloses that after the firing treatment of the raw material mixture containing the carbonaceous material precursor, the water content is reduced to a certain value or less by performing pulverization treatment and classification treatment in a dry atmosphere. Technology is disclosed. In Patent Document 3, a predetermined lithium phosphate compound, lithium silicate compound, and the like and a conductive carbon material are mixed by a wet ball mill, and then a mechanochemical treatment is performed so that the conductive carbon material is uniformly applied to the surface. A technique for obtaining a composite oxide deposited is disclosed.
一方、リチウムは希少有価物質であることから、リチウムイオン二次電池に代えてナトリウムを用いたナトリウムイオン二次電池等も種々検討されはじめている。
例えば、特許文献４には、マリサイト型ＮａＭｎＰＯ4を用いたナトリウムイオン二次電池用活物質が開示されており、また特許文献５には、オリビン型構造を有するリン酸遷移金属ナトリウムを含む正極活物質が開示されており、いずれの文献においても高性能なナトリウムイオン二次電池が得られることを示している。
On the other hand, since lithium is a rare valuable material, various studies have been made on sodium ion secondary batteries using sodium instead of lithium ion secondary batteries.
For example, Patent Document 4 discloses a sodium ion secondary battery active material using marisite-type NaMnPO 4 , and Patent Document 5 discloses a positive electrode containing sodium phosphate transition metal having an olivine structure. An active material is disclosed, and any literature indicates that a high-performance sodium ion secondary battery can be obtained.
しかしながら、上記いずれの文献に記載の技術においても、リン酸リチウム化合物等の表面が、炭素源によって充分に被覆されずに一部の表面が露出しているため、水分の吸着を抑制できずに水分含有量が高まり、サイクル特性等の電池物性が充分に高い二次電池用正極活物質を得るのは困難であることが判明した。 However, in any of the techniques described in any of the above documents, the surface of the lithium phosphate compound or the like is not sufficiently covered with the carbon source, and a part of the surface is exposed. It has been found that it is difficult to obtain a positive electrode active material for a secondary battery in which the moisture content is increased and the battery properties such as cycle characteristics are sufficiently high.
したがって、本発明の課題は、高性能なリチウムイオン二次電池又はナトリウムイオン二次電池を得るべく、水分の吸着を効果的に抑制することのできる二次電池用正極活物質及びその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a positive electrode active material for a secondary battery that can effectively suppress moisture adsorption and a method for manufacturing the same, in order to obtain a high-performance lithium ion secondary battery or a sodium ion secondary battery. It is to provide.
そこで本発明者らは、種々検討したところ、特定の酸化物に、水溶性炭素材料由来の炭素と、特定量の金属フッ化物とが担持してなる二次電池用正極活物質であれば、水溶性炭素材料由来の炭素と金属フッ化物が共に酸化物表面を効率的に被覆して水分の吸着を有効に抑制できるため、リチウムイオン又はナトリウムイオンが有効に電気伝導を担うことのできる二次電池用正極活物質として、極めて有用であることを見出し、本発明を完成させるに至った。 Therefore, the present inventors have made various studies, as long as it is a positive electrode active material for a secondary battery in which carbon derived from a water-soluble carbon material and a specific amount of metal fluoride are supported on a specific oxide, Since carbon and metal fluoride derived from water-soluble carbon materials can effectively coat the oxide surface and effectively suppress moisture adsorption, lithium ions or sodium ions can effectively carry electrical conduction. It has been found that it is extremely useful as a positive electrode active material for batteries, and the present invention has been completed.
すなわち、本発明は、少なくとも鉄又はマンガンを含む下記式（Ａ）、（Ｂ）又は（Ｃ）：
ＬｉＦｅaＭｎbＭcＰＯ4・・・（Ａ）
（式（Ａ）中、ＭはＭｇ、Ｃａ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ａ、ｂ及びｃは、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦０．２、及び２ａ＋２ｂ＋（Ｍの価数）×ｃ＝２を満たし、かつａ＋ｂ≠０を満たす数を示す。）
Ｌｉ2ＦｅｄＭｎｅＮｆＳｉＯ4・・・（Ｂ）
（式（Ｂ）中、ＮはＮｉ、Ｃｏ、Ａｌ、Ｚｎ、Ｖ又はＺｒを示す。ｄ、ｅ及びｆは、０≦ｄ≦１、０≦ｅ≦１、及び０≦ｆ＜１、２ｄ＋２ｅ＋（Ｎの価数）×ｆ＝２を満たし、かつｄ＋ｅ≠０を満たす数を示す。）
ＮａＦｅｇＭｎｈＱｉＰＯ4・・・（Ｃ）
（式（Ｃ）中、ＱはＭｇ、Ｃａ、Ｃｏ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ｇ、ｈ及びｉは、０≦ｇ≦１、０≦ｈ≦１、０≦ｉ＜１、及び２ｇ＋２ｈ＋（Ｑの価数）×ｉ＝２を満たし、かつｇ＋ｈ≠０を満たす数を示す。）
で表される酸化物に、水溶性炭素材料由来の炭素と、０．１〜５質量％の金属フッ化物が担持されてなる二次電池用正極活物質を提供するものである。
That is, the present invention includes at least the following formula (A), (B) or (C) containing iron or manganese:
LiFe a Mn b M c PO 4 (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 0.2, and 2a + 2b + (M valence) × c = 2 and a number satisfying a + b ≠ 0 are shown.)
Li 2 Fe d Mn e N f SiO 4 ··· (B)
(In the formula (B), N represents Ni, Co, Al, Zn, V, or Zr. D, e, and f are 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, and 0 ≦ f <1, 2d + 2e +. (The valence of N) × f = 2 is satisfied, and d + e ≠ 0 is satisfied.)
NaFe g Mn h Q i PO 4 (C)
(In the formula (C), Q represents Mg, Ca, Co, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. G, h, and i are 0 ≦ g ≦. 1, 0 ≦ h ≦ 1, 0 ≦ i <1, and 2g + 2h + (valence of Q) × i = 2 and a number satisfying g + h ≠ 0 are shown.)
The positive electrode active material for secondary batteries by which carbon derived from water-soluble carbon material and 0.1-5 mass% metal fluoride are carry | supported by the oxide represented by these are provided.
また、本発明は、リチウム化合物又はナトリウム化合物、リン酸化合物又はケイ酸化合物、並びに少なくとも鉄化合物又はマンガン化合物を含む金属塩を含有し、かつ水溶性炭素材料を含有するスラリー水を水熱反応に付して複合体Ｙを得る工程（Ｉ）、並びに、
得られた複合体Ｙに、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体を添加して湿式混合し、焼成する工程（II）
を備える、上記二次電池用正極活物質の製造方法を提供するものである。
Further, the present invention provides a hydrothermal reaction to slurry water containing a lithium compound or sodium compound, a phosphoric acid compound or a silicic acid compound, and a metal salt containing at least an iron compound or a manganese compound and containing a water-soluble carbon material. Step (I) to obtain complex Y by attaching, and
Step (II) in which 0.1 to 40 parts by mass of a metal fluoride precursor is added to 100 parts by mass of the complex Y and the resulting composite Y is wet-mixed and fired.
The manufacturing method of the said positive electrode active material for secondary batteries provided with these is provided.
本発明によれば、所定の酸化物に、水溶性炭素材料由来の炭素と特定量の金属フッ化物が補い合いながら有効に担持されてなることにより、酸化物表面の一部において、炭素と金属フッ化物のいずれも存在することなく酸化物が露出してしまうのを有効に抑制するので、酸化物表面における露出部が効果的に低減された二次電池用正極活物質を得ることができる。そのため、かかる正極活物質は水分の吸着を効果的に抑制できるため、これを用いたリチウムイオン二次電池又はナトリウムイオン二次電池において、リチウムイオン又はナトリウムイオンが有効に電気伝導を担いつつ、様々な使用環境下でもサイクル特性等の優れた電池特性を安定して発現することができる。 According to the present invention, carbon and metal fluoride are partially supported on a part of the oxide surface by effectively supporting a predetermined oxide with carbon derived from a water-soluble carbon material and a specific amount of metal fluoride. Since it is possible to effectively prevent the oxide from being exposed without the presence of any compound, a positive electrode active material for a secondary battery in which the exposed portion on the oxide surface is effectively reduced can be obtained. Therefore, since such a positive electrode active material can effectively suppress the adsorption of moisture, in a lithium ion secondary battery or a sodium ion secondary battery using the positive electrode active material, lithium ions or sodium ions effectively carry electric conduction, and various Excellent battery characteristics such as cycle characteristics can be stably exhibited even in a different use environment.
以下、本発明について詳細に説明する。
本発明で用いる酸化物は、少なくとも鉄又はマンガンを含み、かつ下記式（Ａ）、（Ｂ）又は（Ｃ）：
ＬｉＦｅaＭｎbＭcＰＯ4・・・（Ａ）
（式（Ａ）中、ＭはＭｇ、Ｃａ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ａ、ｂ及びｃは、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦０．２、及び２ａ＋２ｂ＋（Ｍの価数）×ｃ＝２を満たし、かつａ＋ｂ≠０を満たす数を示す。）
Ｌｉ2ＦｅｄＭｎｅＮｆＳｉＯ4・・・（Ｂ）
（式（Ｂ）中、ＮはＮｉ、Ｃｏ、Ａｌ、Ｚｎ、Ｖ又はＺｒを示す。ｄ、ｅ及びｆは、０≦ｄ≦１、０≦ｅ≦１、０≦ｆ＜１、及び２ｄ＋２ｅ＋（Ｎの価数）×ｆ＝２を満たし、かつｄ＋ｅ≠０を満たす数を示す。）
ＮａＦｅｇＭｎｈＱｉＰＯ4・・・（Ｃ）
（式（Ｃ）中、ＱはＭｇ、Ｃａ、Ｃｏ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ｇ、ｈ及びｉは、０≦ｇ≦１、０≦ｈ≦１、０≦ｉ＜１、及び２ｇ＋２ｈ＋（Ｑの価数）×ｉ＝２を満たし、かつｇ＋ｈ≠０を満たす数を示す。）
のいずれかの式で表される。
これらの酸化物は、いずれもオリビン型構造を有しており、少なくとも鉄又はマンガンを含む。上記式（Ａ）又は式（Ｂ）で表される酸化物を用いた場合には、リチウムイオン電池用正極活物質が得られ、上記式（Ｃ）で表される酸化物を用いた場合には、ナトリウムイオン電池用正極活物質が得られる。
Hereinafter, the present invention will be described in detail.
The oxide used in the present invention contains at least iron or manganese and has the following formula (A), (B) or (C):
LiFe a Mn b M c PO 4 (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 0.2, and 2a + 2b + (M valence) × c = 2 and a number satisfying a + b ≠ 0 are shown.)
Li 2 Fe d Mn e N f SiO 4 ··· (B)
(In the formula (B), N represents Ni, Co, Al, Zn, V, or Zr. D, e, and f are 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, 0 ≦ f <1, and 2d + 2e +. (The valence of N) × f = 2 is satisfied, and d + e ≠ 0 is satisfied.)
NaFe g Mn h Q i PO 4 (C)
(In the formula (C), Q represents Mg, Ca, Co, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. G, h, and i are 0 ≦ g ≦. 1, 0 ≦ h ≦ 1, 0 ≦ i <1, and 2g + 2h + (valence of Q) × i = 2 and a number satisfying g + h ≠ 0 are shown.)
It is expressed by one of the following formulas.
These oxides all have an olivine structure and contain at least iron or manganese. When the oxide represented by the above formula (A) or (B) is used, a positive electrode active material for a lithium ion battery is obtained, and when the oxide represented by the above formula (C) is used. Provides a positive electrode active material for a sodium ion battery.
上記式（Ａ）で表される酸化物は、いわゆる少なくとも遷移金属として鉄（Ｆｅ）及びマンガン（Ｍｎ）を含むオリビン型リン酸遷移金属リチウム化合物である。式（Ａ）中、Ｍは、Ｍｇ、Ｃａ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示し、好ましくはＭｇ、Ｚｒ、Ｍｏ又はＣｏである。ａは、０≦ａ≦１であって、好ましくは０．０１≦ａ≦０．９９であり、より好ましくは０．１≦ａ≦０．９である。ｂは、０≦ｂ≦１であって、好ましくは０．０１≦ｂ≦０．９９であり、より好ましくは０．１≦ｂ≦０．９である。ｃは、０≦ｃ≦０．２をであって、好ましくは０≦ｃ≦０．１である。そして、これらａ、ｂ及びｃは、２ａ＋２ｂ＋（Ｍの価数）×ｃ＝２を満たし、かつａ＋ｂ≠０を満たす数である。上記式（Ａ）で表されるオリビン型リン酸遷移金属リチウム化合物としては、具体的には、例えばＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、ＬｉＦｅ0.9Ｍｎ0.1ＰＯ４、ＬｉＦｅ0.15Ｍｎ0.75Ｍｇ0.1ＰＯ４、ＬｉＦｅ0.19Ｍｎ0.75Ｚｒ0.03ＰＯ４等が挙げられ、なかでもＬｉＦｅ0.2Ｍｎ0.8ＰＯ４が好ましい。 The oxide represented by the above formula (A) is an olivine-type transition metal lithium compound containing at least iron (Fe) and manganese (Mn) as so-called transition metals. In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd, and is preferably Mg, Zr, Mo, or Co. a is 0 ≦ a ≦ 1, preferably 0.01 ≦ a ≦ 0.99, and more preferably 0.1 ≦ a ≦ 0.9. b is 0 ≦ b ≦ 1, preferably 0.01 ≦ b ≦ 0.99, and more preferably 0.1 ≦ b ≦ 0.9. c satisfies 0 ≦ c ≦ 0.2, and preferably 0 ≦ c ≦ 0.1. These a, b and c are numbers satisfying 2a + 2b + (valence of M) × c = 2 and satisfying a + b ≠ 0. Specific examples of the olivine-type transition metal lithium compound represented by the above formula (A) include LiFe 0.2 Mn 0.8 PO 4 , LiFe 0.9 Mn 0.1 PO 4 , LiFe 0.15 Mn 0.75 Mg 0.1 PO 4 , and LiFe. Examples include 0.19 Mn 0.75 Zr 0.03 PO 4 , and LiFe 0.2 Mn 0.8 PO 4 is particularly preferable.
上記式（Ｂ）で表される酸化物は、いわゆる少なくとも遷移金属として鉄（Ｆｅ）及びマンガン（Ｍｎ）を含むオリビン型ケイ酸遷移金属リチウム化合物である。式（Ｂ）中、Ｎは、Ｎｉ、Ｃｏ、Ａｌ、Ｚｎ、Ｖ又はＺｒを示し、好ましくはＣｏ、Ａｌ、Ｚｎ、Ｖ又はＺｒである。ｄは、０≦ｄ≦１であって、好ましくは０≦ｄ＜１であり、より好ましくは０．１≦ｄ≦０．６である。ｅは、０≦ｄ≦１であって、好ましくは０≦ｅ＜１であり、より好ましくは０．１≦ｅ≦０．６である。ｆは、０≦ｆ＜１であって、好ましくは０＜ｆ＜１であり、より好ましくは０．０５≦ｆ≦０．４である。そして、これらｄ、ｅ及びｆは、２ｄ＋２ｅ＋（Ｎの価数）×ｆ＝２を満たし、かつｄ＋ｅ≠０を満たす数である。上記式（Ｂ）で表されるオリビン型ケイ酸遷移金属リチウム化合物としては、具体的には、例えばＬｉ２Ｆｅ0.45Ｍｎ0.45Ｃｏ0.1ＳｉＯ4、Ｌｉ２Ｆｅ0.36Ｍｎ0.54Ａｌ0.066ＳｉＯ4、Ｌｉ２Ｆｅ0.45Ｍｎ0.45Ｚｎ0.1ＳｉＯ4、Ｌｉ２Ｆｅ0.36Ｍｎ0.54Ｖ0.066ＳｉＯ4、Ｌｉ２Ｆｅ0.282Ｍｎ0.658Ｚｒ0.02ＳｉＯ4等が挙げられ、なかでもＬｉ２Ｆｅ0.282Ｍｎ0.658Ｚｒ0.02ＳｉＯ4が好ましい。 The oxide represented by the above formula (B) is a so-called olivine-type transition metal lithium compound containing at least iron (Fe) and manganese (Mn) as transition metals. In the formula (B), N represents Ni, Co, Al, Zn, V, or Zr, and is preferably Co, Al, Zn, V, or Zr. d is 0 ≦ d ≦ 1, preferably 0 ≦ d <1, and more preferably 0.1 ≦ d ≦ 0.6. e is 0 ≦ d ≦ 1, preferably 0 ≦ e <1, and more preferably 0.1 ≦ e ≦ 0.6. f is 0 ≦ f <1, preferably 0 <f <1, and more preferably 0.05 ≦ f ≦ 0.4. These d, e, and f are numbers satisfying 2d + 2e + (N valence) × f = 2 and d + e ≠ 0. Specific examples of the olivine-type transition metal lithium compound represented by the above formula (B) include Li 2 Fe 0.45 Mn 0.45 Co 0.1 SiO 4 , Li 2 Fe 0.36 Mn 0.54 Al 0.066 SiO 4 , Li 2 Fe 0.45 Mn 0.45 Zn 0.1 SiO 4 , Li 2 Fe 0.36 Mn 0.54 V 0.066 SiO 4 , Li 2 Fe 0.282 Mn 0.658 Zr 0.02 SiO 4 and the like can be mentioned, among which Li 2 Fe 0.282 Mn 0.658 Zr 0.02 SiO 4 is preferable.
上記式（Ｃ）で表される酸化物は、いわゆる少なくとも遷移金属として鉄（Ｆｅ）及びマンガン（Ｍｎ）を含むオリビン型リン酸遷移金属ナトリウム化合物である。式（Ｃ）中、ＱはＭｇ、Ｃａ、Ｃｏ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示し、好ましくはＭｇ、Ｚｒ、Ｍｏ又はＣｏである。ｇは、０≦ｇ≦１であって、好ましくは０＜ｇ≦１である。ｈは、０≦ｈ≦１であって、好ましくは０．５≦ｈ＜１である。ｉは、０≦ｉ＜１であって、好ましくは０≦ｉ≦０．５であり、より好ましくは０≦ｉ≦０．３である。そして、これらｇ、ｈ及びｉは、０≦ｇ≦１、０≦ｈ≦１、及び０≦ｉ＜１、２ｇ＋２ｈ＋（Ｑの価数）×ｉ＝２を満たし、かつｇ＋ｈ≠０を満たす数である。上記式（Ｃ）で表されるオリビン型リン酸遷移金属ナトリウム化合物としては、具体的には、例えばＮａＦｅ0.2Ｍｎ0.8ＰＯ４、ＮａＦｅ0.9Ｍｎ0.1ＰＯ４、ＮａＦｅ0.15Ｍｎ0.7Ｍｇ0.15ＰＯ4、ＮａＦｅ0.19Ｍｎ0.75Ｚｒ0.03ＰＯ4、ＮａＦｅ0.19Ｍｎ0.75Ｍｏ0.03ＰＯ4、ＮａＦｅ0.15Ｍｎ0.7Ｃｏ0.15ＰＯ4等が挙げられ、なかでもＮａＦｅ0.2Ｍｎ0.8ＰＯ4が好ましい。 The oxide represented by the formula (C) is an olivine-type transition metal sodium phosphate compound containing iron (Fe) and manganese (Mn) as at least transition metals. In the formula (C), Q represents Mg, Ca, Co, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd, and is preferably Mg, Zr, Mo, or Co. g is 0 ≦ g ≦ 1, and preferably 0 <g ≦ 1. h is 0 ≦ h ≦ 1, and preferably 0.5 ≦ h <1. i is 0 ≦ i <1, preferably 0 ≦ i ≦ 0.5, and more preferably 0 ≦ i ≦ 0.3. These g, h, and i are numbers satisfying 0 ≦ g ≦ 1, 0 ≦ h ≦ 1, and 0 ≦ i <1, 2 + g + 2h + (Q valence) × i = 2 and satisfying g + h ≠ 0. It is. Specific examples of the olivine-type transition metal sodium phosphate compound represented by the formula (C) include, for example, NaFe 0.2 Mn 0.8 PO 4 , NaFe 0.9 Mn 0.1 PO 4 , NaFe 0.15 Mn 0.7 Mg 0.15 PO 4 , NaFe Examples include 0.19 Mn 0.75 Zr 0.03 PO 4 , NaFe 0.19 Mn 0.75 Mo 0.03 PO 4 , NaFe 0.15 Mn 0.7 Co 0.15 PO 4 , and NaFe 0.2 Mn 0.8 PO 4 is preferred.
本発明の二次電池用正極活物質は、上記式（Ａ）、（Ｂ）又は（Ｃ）で表される酸化物に、水溶性炭素材料由来の炭素と０．１〜５質量％の金属フッ化物とが担持してなるものである。すなわち、上記酸化物に炭素と特定量の金属フッ化物との双方を担持させてなるものであって、酸化物表面を炭素又は金属フッ化物の一方が被覆しつつも、その一方が存在することなく酸化物表面が露出した部位に、炭素又は金属フッ化物の他方が有効に担持されてなる。したがって、これら水溶性炭素材料由来の炭素と特定量の金属フッ化物とが相まって上記酸化物表面の露出を効果的に抑制しながら、酸化物の全表面にわたり堅固に担持されてなるため、本発明の二次電池用正極活物質における水分吸着を有効に防止することができる。 The positive electrode active material for a secondary battery of the present invention includes a carbon derived from a water-soluble carbon material and 0.1 to 5% by mass of a metal in the oxide represented by the above formula (A), (B) or (C). It is formed by supporting fluoride. That is, the oxide is formed by supporting both carbon and a specific amount of metal fluoride, and either one of carbon or metal fluoride is coated on the oxide surface, but one of them exists. The other of carbon or metal fluoride is effectively supported on the portion where the oxide surface is exposed. Therefore, since the carbon derived from the water-soluble carbon material and a specific amount of metal fluoride are combined and effectively suppressed the exposure of the oxide surface, it is firmly supported over the entire surface of the oxide. Thus, moisture adsorption in the positive electrode active material for secondary batteries can be effectively prevented.
上記式（Ａ）、（Ｂ）又は（Ｃ）で表される酸化物に炭化された炭素として担持される水溶性炭素材料とは、２５℃の水１００ｇに、水溶性炭素材料の炭素原子換算量で０．４ｇ以上、好ましくは１．０ｇ以上溶解する炭素材料を意味し、上記式（Ａ）〜（Ｃ）で表される酸化物表面を被覆する炭素源として機能する。かかる水溶性炭素材料としては、例えば、糖類、ポリオール、ポリエーテル、及び有機酸から選ばれる１種又は２種以上が挙げられる。より具体的には、例えば、グルコース、フルクトース、ガラクトース、マンノース等の単糖類；マルトース、スクロース、セロビオース等の二糖類；デンプン、デキストリン等の多糖類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール、ブタンジオール、プロパンジオール、ポリビニルアルコール、グリセリン等のポリオールやポリエーテル；クエン酸、酒石酸、アスコルビン酸等の有機酸が挙げられる。なかでも、溶媒への溶解性及び分散性を高めて炭素材料として効果的に機能させる観点から、グルコース、フルクトース、スクロース、デキストリンが好ましく、グルコースがより好ましい。 The water-soluble carbon material supported as carbon carbonized by the oxide represented by the above formula (A), (B) or (C) is equivalent to carbon atom of the water-soluble carbon material in 100 g of water at 25 ° C. This means a carbon material that dissolves in an amount of 0.4 g or more, preferably 1.0 g or more, and functions as a carbon source for coating the oxide surface represented by the above formulas (A) to (C). Examples of the water-soluble carbon material include one or more selected from saccharides, polyols, polyethers, and organic acids. More specifically, for example, monosaccharides such as glucose, fructose, galactose and mannose; disaccharides such as maltose, sucrose and cellobiose; polysaccharides such as starch and dextrin; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and butane Examples include polyols and polyethers such as diol, propanediol, polyvinyl alcohol, and glycerin; and organic acids such as citric acid, tartaric acid, and ascorbic acid. Among these, glucose, fructose, sucrose, and dextrin are preferable, and glucose is more preferable from the viewpoint of improving the solubility and dispersibility in a solvent and effectively functioning as a carbon material.
水溶性炭素材料の炭素原子換算分は、水溶性炭素材料が炭化されることにより、上記酸化物に担持された炭素として本発明の二次電池用正極活物質中に存在することとなる。かかる水溶性炭素材料の炭素原子換算量は、本発明の二次電池用正極活物質中に、好ましくは０．１〜４質量％であり、より好ましくは０．２〜３．５質量％であり、さらに好ましくは０．３〜３質量％である。二次電池用正極活物質中に存在する水溶性炭素材料の炭素原子換算量は、炭素・硫黄分析装置を用いて測定した炭素量により、確認することができる。 The carbon atom equivalent of the water-soluble carbon material is present in the positive electrode active material for a secondary battery of the present invention as carbon supported by the oxide by carbonization of the water-soluble carbon material. The carbon atom equivalent amount of the water-soluble carbon material is preferably 0.1 to 4% by mass, more preferably 0.2 to 3.5% by mass in the positive electrode active material for a secondary battery of the present invention. Yes, and more preferably 0.3 to 3% by mass. The amount in terms of carbon atoms of the water-soluble carbon material present in the positive electrode active material for secondary battery can be confirmed by the amount of carbon measured using a carbon / sulfur analyzer.
上記酸化物に担持させる上記金属フッ化物の金属としては、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、マグネシウム（Ｍｇ）、カルシウム(Ｃａ)、アルミニウム（Ａｌ）、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）、タンタル（Ｔａ）、錫（Ｓｎ）、タングステン（Ｗ）、カリウム（Ｋ）、バリウム(Ｂａ)、ストロンチウム（Ｓｒ）が挙げられる。なかでも、金属フッ化物の疎水性を向上させ、且つイオン伝導性を向上させる観点から、リチウム、ナトリウム、マグネシウム、カルシウム、及びジルコニウムから選ばれる金属であることが好ましく、リチウム、及びマグネシウムから選ばれる金属であることがより好ましい。 Examples of the metal fluoride metal supported on the oxide include lithium (Li), sodium (Na), magnesium (Mg), calcium (Ca), aluminum (Al), titanium (Ti), vanadium (V), Chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), Examples include tantalum (Ta), tin (Sn), tungsten (W), potassium (K), barium (Ba), and strontium (Sr). Among these, from the viewpoint of improving the hydrophobicity of the metal fluoride and improving the ionic conductivity, a metal selected from lithium, sodium, magnesium, calcium, and zirconium is preferable, and selected from lithium and magnesium. More preferably, it is a metal.
上記金属フッ化物の担持量は、水溶性炭素材料が炭化されてなる炭素が存在しない酸化物の表面に金属フッ化物を有効に担持させる観点から、本発明の二次電池用正極活物質中に、０．１〜５質量％であり、好ましくは０．２〜４．５質量％であり、より好ましくは０．３〜４質量％である。上記金属フッ化物の担持量が０．１質量％未満であると、吸着水分量を充分に抑制できず、上記金属フッ化物の担持量が５質量％を超えると、詳細は不明であるが、吸着水分量が抑制されていても二次電池のサイクル特性が低下してしまうおそれがある。二次電池用正極活物質中に存在するフッ素量は、二次電池用正極活物質を酸溶解させた溶解液を用いてイオン分析計により、確認することができる。 From the viewpoint of effectively supporting the metal fluoride on the surface of the oxide containing no carbon formed by carbonizing the water-soluble carbon material, the amount of the metal fluoride supported is in the positive electrode active material for the secondary battery of the present invention. 0.1 to 5% by mass, preferably 0.2 to 4.5% by mass, and more preferably 0.3 to 4% by mass. If the supported amount of the metal fluoride is less than 0.1% by mass, the amount of adsorbed water cannot be sufficiently suppressed, and if the supported amount of the metal fluoride exceeds 5% by mass, details are unknown, Even if the amount of adsorbed moisture is suppressed, the cycle characteristics of the secondary battery may be deteriorated. The amount of fluorine present in the positive electrode active material for secondary batteries can be confirmed by an ion analyzer using a solution obtained by acid-dissolving the positive electrode active material for secondary batteries.
本発明の二次電池用正極活物質は、炭素と金属フッ化物とを互いに補い合いながら効率的に上記（Ａ）、（Ｂ）又は（Ｃ）で表される酸化物に担持させる観点から、かかる酸化物に水溶性炭素材料由来の炭素を担持させたのち、０．１〜５質量％の金属フッ化物を担持させてなるものであるのが好ましく、具体的には、酸化物と水溶性炭素材料由来の炭素とを含む複合体に、０．１〜５質量％の金属フッ化物が担持してなるものであるのが好ましい。
また、金属フッ化物は、上記複合体において、水溶性炭素材料が存在することなく酸化物表面が露出した部位に有効に担持させる観点から、上記複合体に、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体を添加して湿式混合されて複合体に担持されてなるのが好ましい。すなわち、本発明の二次電池用正極活物質は、酸化物と水溶性炭素材料由来の炭素とを含む複合体と、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体との湿式混合物の焼成物であるのが好ましい。具体的には、かかる金属フッ化物の前駆体は、その後焼成されて、金属フッ化物として担持され、本発明の二次電池用正極活物質に存在することとなる。
The positive electrode active material for a secondary battery of the present invention is required from the viewpoint of efficiently supporting carbon and metal fluoride on the oxide represented by the above (A), (B) or (C) while complementing each other. It is preferable that 0.1 to 5% by mass of a metal fluoride is supported on the oxide after supporting the carbon derived from the water-soluble carbon material, specifically, the oxide and the water-soluble carbon. It is preferable that 0.1 to 5% by mass of a metal fluoride is supported on a composite containing carbon derived from the material.
Further, from the viewpoint of effectively supporting the metal fluoride in a portion where the surface of the oxide is exposed without the presence of the water-soluble carbon material in the composite, the metal fluoride is 0% with respect to 100 parts by mass of the composite. It is preferable that 1 to 40 parts by mass of a metal fluoride precursor is added and wet mixed to be supported on the composite. That is, the positive electrode active material for a secondary battery of the present invention includes a composite containing an oxide and carbon derived from a water-soluble carbon material, and 0.1 to 40 parts by mass of a metal fluoride with respect to 100 parts by mass of the composite. A fired product of a wet mixture with a precursor of Specifically, the precursor of the metal fluoride is then fired and supported as a metal fluoride, and is present in the positive electrode active material for a secondary battery of the present invention.
上記酸化物と水溶性炭素材料由来の炭素とを含む複合体は、具体的には、リチウム化合物又はナトリウム化合物、リン酸化合物又はケイ酸化合物、並びに少なくとも鉄化合物又はマンガン化合物を含み、かつ水溶性炭素材料を含むスラリー水を水熱反応に付すことにより得られるものであるのが好ましい。すなわち、上記酸化物と水溶性炭素材料由来の炭素とを含む複合体は、リチウム化合物又はナトリウム化合物、リン酸化合物又はケイ酸化合物、並びに少なくとも鉄化合物又はマンガン化合物を含み、かつ水溶性炭素材料を含むスラリー水の、水熱反応物であるのが好ましい。 The composite containing the oxide and the carbon derived from the water-soluble carbon material specifically includes a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and at least an iron compound or a manganese compound, and is water-soluble. It is preferable that it is obtained by subjecting slurry water containing a carbon material to a hydrothermal reaction. That is, the composite containing the oxide and the carbon derived from the water-soluble carbon material includes a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and at least an iron compound or a manganese compound, and includes a water-soluble carbon material. The slurry water is preferably a hydrothermal reactant.
本発明の二次電池用正極活物質は、より具体的には、リチウム化合物又はナトリウム化合物、リン酸化合物又はケイ酸化合物、並びに少なくとも鉄化合物又はマンガン化合物を含む金属塩を含有し、かつ水溶性炭素材料を含有するスラリー水を水熱反応に付して複合体Ｙを得る工程（Ｉ）、並びに
得られた複合体Ｙに、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体を添加して湿式混合し、焼成する工程（II）
を備える製造方法により得られるものであるのが好ましい。
More specifically, the positive electrode active material for a secondary battery according to the present invention contains a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and a metal salt containing at least an iron compound or a manganese compound, and is water-soluble. The step (I) of obtaining slurry Y by subjecting slurry water containing a carbon material to a hydrothermal reaction, and the resulting complex Y are 0.1 to 40 parts by mass with respect to 100 parts by mass of the complex. Step of adding metal fluoride precursor, wet mixing and firing (II)
It is preferable that it is obtained by a manufacturing method provided with.
工程（Ｉ）は、リチウム化合物又はナトリウム化合物、リン酸化合物又はケイ酸化合物、並びに少なくとも鉄化合物又はマンガン化合物を含む金属塩を含有し、かつ水溶性炭素材料を含有するスラリー水を水熱反応に付して複合体Ｙを得る工程である。
用い得るリチウム化合物又はナトリウム化合物としては、水酸化物（例えばＬｉＯＨ・Ｈ2Ｏ、ＮａＯＨ）、炭酸化物、硫酸化物、酢酸化物が挙げられる。なかでも、水酸化物が好ましい。
スラリー水におけるリチウム化合物又はケイ酸化合物の含有量は、水１００質量部に対し、好ましくは５〜５０質量部であり、より好ましくは７〜４５質量部である。より具体的には、工程（Ｉ）においてリン酸化合物を用いた場合、スラリー水におけるリチウム化合物又はナトリウム化合物の含有量は、水１００質量部に対し、好ましくは５〜５０質量部であり、より好ましくは１０〜４５質量部である。また、ケイ酸化合物を用いた場合、スラリー水におけるケイ酸化合物の含有量は、水１００質量部に対し、好ましくは５〜４０質量部であり、より好ましくは７〜３５質量部である。
Step (I) is a hydrothermal reaction of slurry water containing a lithium compound or sodium compound, a phosphoric acid compound or a silicic acid compound, and a metal salt containing at least an iron compound or a manganese compound and containing a water-soluble carbon material. It is the process of attaching | subjecting and obtaining the composite Y.
Examples of the lithium compound or sodium compound that can be used include hydroxides (for example, LiOH.H 2 O, NaOH), carbonates, sulfates, and acetates. Of these, hydroxide is preferable.
The content of the lithium compound or silicate compound in the slurry water is preferably 5 to 50 parts by mass and more preferably 7 to 45 parts by mass with respect to 100 parts by mass of water. More specifically, when a phosphoric acid compound is used in step (I), the content of the lithium compound or sodium compound in the slurry water is preferably 5 to 50 parts by mass with respect to 100 parts by mass of water, and more Preferably it is 10-45 mass parts. Moreover, when using a silicate compound, content of the silicate compound in slurry water becomes like this. Preferably it is 5-40 mass parts with respect to 100 mass parts of water, More preferably, it is 7-35 mass parts.
スラリー水における水溶性炭素材料の含有量は、上記のとおり、炭化されてなる炭素としての水溶性炭素材料の担持量が炭素原子換算量で上記範囲内になるような量であればよく、例えば、酸化物の表面に水溶性炭素材料由来の炭素を０．１〜４質量％の量で有効に担持させる観点から、スラリー水中の水１００質量部に対し、好ましくは０．０３〜３．５質量部であり、より好ましくは０．０３〜２．５質量部である。 The content of the water-soluble carbon material in the slurry water may be an amount such that the supported amount of the water-soluble carbon material as carbon obtained by carbonization falls within the above range in terms of carbon atoms, as described above. From the viewpoint of effectively carrying carbon derived from a water-soluble carbon material in an amount of 0.1 to 4% by mass on the surface of the oxide, preferably 0.03 to 3.5 with respect to 100 parts by mass of water in the slurry water. It is a mass part, More preferably, it is 0.03-2.5 mass part.
工程（Ｉ）は、スラリー水に含有される各成分の分散性を高めつつ、得られる正極活物質の粒子を微細化し、電池物性の向上を図る観点から、リチウム化合物又はナトリウム化合物を含む混合物Ｘに、リン酸化合物又はケイ酸化合物を混合して複合体Ｘを得る工程（Ｉａ）、並びに得られた複合体Ｘに、少なくとも鉄化合物又はマンガン化合物を含む金属塩と水溶性炭素材料を添加し、得られるスラリー水Ｙを水熱反応に付して複合体Ｙを得る工程（Ｉｂ）を備えるのが好ましい。
この際、水溶性炭素材料は、最終的に水熱反応に付されるスラリー水Ｙ中に含まれていればよく、工程（Ｉａ）において、リン酸化合物又はケイ酸化合物を混合する前又は混合時に添加してもよく、或いは工程（Ｉｂ）において少なくとも鉄化合物又はマンガン化合物を含む金属塩とともに添加することによりスラリー水Ｙとしてもよい。なかでも、上記酸化物に水溶性炭素材料が炭化されてなる炭素を効率的に担持させる観点から、工程（Ｉｂ）において鉄化合物又はマンガン化合物を含む金属塩とともに水溶性炭素材料を添加するのが好ましい。
Step (I) is a mixture X containing a lithium compound or a sodium compound, from the viewpoint of improving the physical properties of the battery by increasing the dispersibility of each component contained in the slurry water and making the resulting positive electrode active material particles finer. Step (Ia) of mixing the phosphoric acid compound or silicic acid compound to obtain the complex X, and adding to the obtained complex X a metal salt containing at least an iron compound or a manganese compound and a water-soluble carbon material. It is preferable to include the step (Ib) of obtaining the composite Y by subjecting the obtained slurry water Y to a hydrothermal reaction.
At this time, the water-soluble carbon material only needs to be contained in the slurry water Y that is finally subjected to a hydrothermal reaction, and before mixing the phosphoric acid compound or the silicate compound in the step (Ia) or mixing. The slurry water Y may be added by adding together with a metal salt containing at least an iron compound or a manganese compound in the step (Ib). Among these, from the viewpoint of efficiently supporting carbon obtained by carbonizing a water-soluble carbon material on the oxide, the water-soluble carbon material is added together with a metal salt containing an iron compound or a manganese compound in the step (Ib). preferable.
工程（Ｉ）又は（Ｉａ）において、混合物Ｘにリン酸化合物又はケイ酸化合物を混合する前に、予め混合物Ｘを撹拌しておくのが好ましい。かかる混合物Ｘの撹拌時間は、好ましくは１〜１５分であり、より好ましくは３〜１０分である。また、混合物Ｘの温度は、好ましくは２０〜９０℃であり、より好ましくは２０〜７０℃である。 In the step (I) or (Ia), it is preferable to stir the mixture X in advance before mixing the phosphoric acid compound or the silicic acid compound with the mixture X. The stirring time of the mixture X is preferably 1 to 15 minutes, more preferably 3 to 10 minutes. Moreover, the temperature of the mixture X becomes like this. Preferably it is 20-90 degreeC, More preferably, it is 20-70 degreeC.
工程（Ｉ）又は（Ｉａ）で用いるリン酸化合物としては、オルトリン酸（Ｈ3ＰＯ4、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挙げられる。なかでもリン酸を用いるのが好ましく、７０〜９０質量％濃度の水溶液として用いるのが好ましい。かかる工程（Ｉ）又は（Ｉａ）では、混合物Ｘにリン酸を混合するにあたり、混合物を撹拌しながらリン酸を滴下するのが好ましい。混合物Ｘにリン酸を滴下して少量ずつ加えることで、混合物Ｘ中において良好に反応が進行して、上記（Ａ）〜（Ｃ）で表される酸化物の前駆体がスラリー中で均一に分散しつつ生成され、かかる酸化物の前駆体が不要に凝集するのをも効果的に抑制することができる。 Examples of the phosphoric acid compound used in the step (I) or (Ia) include orthophosphoric acid (H 3 PO 4 , phosphoric acid), metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. Etc. Of these, phosphoric acid is preferably used, and is preferably used as an aqueous solution having a concentration of 70 to 90% by mass. In the step (I) or (Ia), when mixing the phosphoric acid into the mixture X, it is preferable to add the phosphoric acid dropwise while stirring the mixture. By adding phosphoric acid dropwise to the mixture X and adding it little by little, the reaction proceeds well in the mixture X, and the precursors of the oxides represented by the above (A) to (C) are uniformly in the slurry. It is possible to effectively suppress the generation of the oxide precursor while being dispersed, and the unnecessary aggregation of the oxide precursor.
リン酸の上記混合物Ｘ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、リン酸を滴下しながらの混合物Ｘの撹拌時間は、好ましくは０．５〜２４時間であり、より好ましくは３〜１２時間である。さらに、リン酸を滴下しながらの混合物Ｘの撹拌速度は、好ましくは２００〜７００ｒｐｍであり、より好ましくは２５０〜６００ｒｐｍであり、さらに好ましくは３００〜５００ｒｐｍである。
なお、混合物Ｘを撹拌する際、さらに混合物Ｘの沸点温度以下に冷却するのが好ましい。具体的には、８０℃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 dropping rate of phosphoric acid into the mixture X is preferably 15 to 50 mL / min, more preferably 20 to 45 mL / min, and further preferably 28 to 40 mL / min. Moreover, the stirring time of the mixture X while dropping phosphoric acid is preferably 0.5 to 24 hours, and more preferably 3 to 12 hours. Furthermore, the stirring speed of the mixture X while dropping phosphoric acid is preferably 200 to 700 rpm, more preferably 250 to 600 rpm, and further preferably 300 to 500 rpm.
In addition, when stirring the mixture X, it is preferable to further cool below the boiling point temperature of the mixture X. Specifically, cooling to 80 ° C. or lower is preferable, and cooling to 20 to 60 ° C. is more preferable.
工程（Ｉ）又は（Ｉａ）で用いるケイ酸化合物としては、反応性のあるシリカ化合物であれば特に限定されず、非晶質シリカ、Ｎａ4ＳｉＯ4（例えばＮａ4ＳｉＯ4・Ｈ2Ｏ）等が挙げられる。 The silicic acid compound used in the step (I) or (Ia) is not particularly limited as long as it is a reactive silica compound. Amorphous silica, Na 4 SiO 4 (for example, Na 4 SiO 4 .H 2 O) Etc.
リン酸化合物又はケイ酸化合物を混合した後の混合物Ｘは、リン酸又はケイ酸１モルに対し、リチウム又はナトリウムを２．０〜４．０モル含有するのが好ましく、２．０〜３．１モル含有するのがより好ましく、このような量となるよう、上記リチウム化合物又はナトリウム化合物と、リン酸化合物又はケイ酸化合物を用いればよい。より具体的には、工程（Ｉ）又は（Ｉａ）においてリン酸化合物を用いた場合を用いた場合、リン酸化合物を混合した後の混合物Ｘは、リン酸１モルに対し、リチウム又はナトリウムを２．７〜３．３モル含有するのが好ましく、２．８〜３．１モル含有するのがより好ましく、工程（Ｉ）又は（Ｉａ）においてケイ酸化合物を用いた場合、ケイ酸化合物を混合した後の混合物Ｘは、ケイ酸１モルに対し、リチウムを２．０〜４．０モル含有するのが好ましく、２．０〜３．０含有するのがより好ましい。
このような量となるよう、上記リチウム化合物又はナトリウム化合物と、リン酸化合物又はケイ酸化合物を用いればよい。
It is preferable that the mixture X after mixing a phosphoric acid compound or a silicic acid compound contains 2.0-4.0 mol of lithium or sodium with respect to 1 mol of phosphoric acid or silicic acid, and is 2.0-3. It is more preferable to contain 1 mol, and the lithium compound or sodium compound and the phosphoric acid compound or silicic acid compound may be used so as to obtain such an amount. More specifically, when the case where a phosphoric acid compound is used in the step (I) or (Ia) is used, the mixture X after mixing the phosphoric acid compound contains lithium or sodium with respect to 1 mol of phosphoric acid. It is preferable to contain 2.7 to 3.3 mol, more preferably 2.8 to 3.1 mol, and when the silicate compound is used in step (I) or (Ia), the silicate compound is added. It is preferable that the mixture X after mixing contains 2.0-4.0 mol of lithium with respect to 1 mol of silicic acid, and it is more preferable to contain 2.0-3.0.
What is necessary is just to use the said lithium compound or sodium compound, and a phosphoric acid compound or a silicic acid compound so that it may become such quantity.
リン酸化合物又はケイ酸化合物を混合した後の混合物Ｘに対して窒素をパージすることにより、かかる混合物Ｘ中での反応を完了させて、上記（Ａ）〜（Ｃ）で表される酸化物の前駆体である複合体Ｘを混合物中に生成させる。窒素がパージされると、混合物Ｘ中の溶存酸素濃度が低減された状態で反応を進行させることができ、また得られる複合体Ｘを含有する混合物Ｘ中の溶存酸素濃度も効果的に低減されるため、次の工程で添加する鉄化合物やマンガン化合物等の酸化を抑制することができる。かかる混合物Ｘ中において、上記（Ａ）〜（Ｃ）で表される酸化物の前駆体は、微細な分散粒子として存在する。かかる複合体Ｘの前駆体は、例えば上記式（Ａ）で表される酸化物の場合、リン酸三リチウム（Ｌｉ3ＰＯ4）として得られる。 By purging the mixture X after mixing the phosphoric acid compound or the silicic acid compound with nitrogen, the reaction in the mixture X is completed, and the oxides represented by the above (A) to (C) A complex X which is a precursor of is formed in the mixture. When nitrogen is purged, the reaction can proceed in a state where the dissolved oxygen concentration in the mixture X is reduced, and the dissolved oxygen concentration in the mixture X containing the resulting complex X is also effectively reduced. Therefore, oxidation of the iron compound or manganese compound added in the next step can be suppressed. In the mixture X, the oxide precursors represented by the above (A) to (C) are present as fine dispersed particles. For example, in the case of the oxide represented by the above formula (A), the precursor of the composite X is obtained as trilithium phosphate (Li 3 PO 4 ).
窒素をパージする際における圧力は、好ましくは０．１〜０．２ＭＰａであり、より好ましくは０．１〜０．１５ＭＰａである。また、リン酸化合物又はケイ酸化合物を混合した後の混合物Ｘの温度は、好ましくは２０〜８０℃であり、より好ましくは２０〜６０℃である。例えば上記式（Ａ）で表される酸化物の場合、反応時間は、好ましくは５〜６０分であり、より好ましくは１５〜４５分である。
また、窒素をパージする際、反応を良好に進行させる観点から、リン酸化合物又はケイ酸化合物を混合した後の混合物Ｘを撹拌するのが好ましい。このときの撹拌速度は、好ましくは２００〜７００ｒｐｍであり、より好ましくは２５０〜６００ｒｐｍである。
The pressure for purging nitrogen is preferably 0.1 to 0.2 MPa, more preferably 0.1 to 0.15 MPa. Moreover, the temperature of the mixture X after mixing a phosphoric acid compound or a silicic acid compound becomes like this. Preferably it is 20-80 degreeC, More preferably, it is 20-60 degreeC. For example, in the case of the oxide represented by the above formula (A), the reaction time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
Moreover, when purging nitrogen, it is preferable to stir the mixture X after mixing a phosphoric acid compound or a silicic acid compound from a viewpoint of making reaction progress favorable. The stirring speed at this time is preferably 200 to 700 rpm, more preferably 250 to 600 rpm.
また、より効果的に複合体Ｘの分散粒子表面における酸化を抑制し、分散粒子の微細化を図る観点から、リン酸化合物又はケイ酸化合物を混合した後の混合物Ｘ中における溶存酸素濃度を０．５ｍｇ／Ｌ以下とするのが好ましく、０．２ｍｇ／Ｌ以下とするのがより好ましい。 Further, from the viewpoint of more effectively suppressing the oxidation on the surface of the dispersed particles of the complex X and miniaturizing the dispersed particles, the dissolved oxygen concentration in the mixture X after mixing the phosphoric acid compound or the silicate compound is reduced to 0. 0.5 mg / L or less is preferable, and 0.2 mg / L or less is more preferable.
工程（Ｉ）又は（Ｉｂ）では、得られた複合体Ｘと、少なくとも鉄化合物又はマンガン化合物を含む金属塩を含有し、かつ水溶性炭素材料を含有するスラリー水Ｙを水熱反応に付して、複合体Ｙを得る。得られた複合体Ｘを、混合物のまま、上記（Ａ）〜（Ｃ）で表される酸化物の前駆体として用い、これに少なくとも鉄化合物又はマンガン化合物を含む金属塩、及び水溶性炭素材料を添加して、スラリー水Ｙとして用いるのが好ましい。これにより、工程を簡略化させつつ、上記（Ａ）〜（Ｃ）で表される酸化物に効率的に水溶性炭素材料が炭化してなる炭素を担持させることができるとともに、極めて微細な粒子とすることが可能となり、非常に有用な二次電池用正極活物質を得ることができる。 In the step (I) or (Ib), the obtained complex X and a slurry water Y containing at least an iron compound or a manganese compound and containing a water-soluble carbon material are subjected to a hydrothermal reaction. Thus, the complex Y is obtained. The obtained complex X is used as a precursor of the oxide represented by the above (A) to (C) as a mixture, and a metal salt containing at least an iron compound or a manganese compound, and a water-soluble carbon material Is preferably used as slurry water Y. As a result, while simplifying the process, the oxides represented by the above (A) to (C) can efficiently carry carbon formed by carbonizing the water-soluble carbon material, and extremely fine particles. And a very useful positive electrode active material for a secondary battery can be obtained.
用い得る鉄化合物としては、酢酸鉄、硝酸鉄、硫酸鉄等が挙げられる。これらは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。なかでも、電池特性を高める観点から、硫酸鉄が好ましい。 Examples of iron compounds that can be used include iron acetate, iron nitrate, and iron sulfate. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving battery characteristics.
用い得るマンガン化合物としては、酢酸マンガン、硝酸マンガン、硫酸マンガン等が挙げられる。これらは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。なかでも、電池特性を高める観点から、硫酸マンガンが好ましい。 Examples of manganese compounds that can be used include manganese acetate, manganese nitrate, and manganese sulfate. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving battery characteristics.
金属塩として、鉄化合物とマンガン化合物の双方を用いる場合、これらマンガン化合物及び鉄化合物の使用モル比（マンガン化合物：鉄化合物）は、好ましくは９９：１〜１：９９であり、より好ましくは９０：１０〜１０：９０である。また、これら鉄化合物及びマンガン化合物の合計添加量は、スラリー水Ｙ中に含有されるＬｉ3ＰＯ4１モルに対し、好ましくは０．９９〜１．０１モルであり、より好ましくは０．９９５〜１．００５モルである。 When both an iron compound and a manganese compound are used as the metal salt, the use molar ratio of these manganese compound and iron compound (manganese compound: iron compound) is preferably 99: 1 to 1:99, more preferably 90. : 10 to 10:90. The total amount of these iron compounds and manganese compounds is preferably 0.99 to 1.01 moles, more preferably 0.995, with respect to 1 mole of Li 3 PO 4 contained in the slurry water Y. ~ 1.005 mol.
さらに、必要に応じて、金属塩として、鉄化合物及びマンガン化合物以外の金属（Ｍ、Ｎ又はＱ）塩を用いてもよい。金属（Ｍ、Ｎ又はＱ）塩におけるＭ、Ｎ及びＱは、上記式（Ａ）〜（Ｃ）中のＭ、Ｎ及びＱと同義であり、かかる金属塩として、硫酸塩、ハロゲン化合物、有機酸塩、及びこれらの水和物等を用いることができる。これらは１種単独で用いてもよく、２種以上用いてもよい。なかでも、電池物性を高める観点から、硫酸塩を用いるのがより好ましい。
これら金属（Ｍ、Ｎ又はＱ）塩を用いる場合、鉄化合物、マンガン化合物、及び金属（Ｍ、Ｎ又はＱ）塩の合計添加量は、上記工程（Ｉ）において得られた混合物中のリン酸又はケイ酸１モルに対し、好ましくは０．９９〜１．０１モルであり、より好ましくは０．９９５〜１．００５モルである。
Furthermore, you may use metal (M, N, or Q) salts other than an iron compound and a manganese compound as a metal salt as needed. M, N, and Q in the metal (M, N, or Q) salt have the same meanings as M, N, and Q in the above formulas (A) to (C), and as the metal salt, sulfate, halogen compound, organic Acid salts and hydrates thereof can be used. These may be used alone or in combination of two or more. Among them, it is more preferable to use a sulfate from the viewpoint of improving battery physical properties.
When these metal (M, N, or Q) salts are used, the total amount of iron compound, manganese compound, and metal (M, N, or Q) salt added is phosphoric acid in the mixture obtained in the above step (I). Or it is preferably 0.99 to 1.01 mole, and more preferably 0.995 to 1.005 mole relative to 1 mole of silicic acid.
スラリーＹ中における水溶性炭素材料は、好ましくは０．０３〜３．４質量％であり、より好ましくは０．０３〜２．４質量％である。 The water-soluble carbon material in the slurry Y is preferably 0.03 to 3.4% by mass, and more preferably 0.03 to 2.4% by mass.
水熱反応に付する際に用いる水の使用量は、用いる金属塩の溶解性、撹拌の容易性、及び合成の効率等の観点から、スラリー水Ｙ中に含有されるリン酸又はケイ酸イオン１モルに対し、好ましくは１０〜５０モルであり、より好ましくは１２．５〜４５モルである。より具体的には、スラリー水Ｙ中に含有されるイオンがリン酸イオンの場合、水熱反応に付する際に用いる水の使用量は、好ましくは１０〜３０モルであり、より好ましくは１２．５〜２５モルである。また、スラリー水Ｙ中に含有されるイオンがケイ酸イオンの場合、水熱反応に付する際に用いる水の使用量は、好ましくは１０〜５０モルであり、より好ましくは１２．５〜４５モルである。 The amount of water used for the hydrothermal reaction is phosphoric acid or silicate ions contained in the slurry water Y from the viewpoint of the solubility of the metal salt used, the ease of stirring, the efficiency of synthesis, etc. Preferably it is 10-50 mol with respect to 1 mol, More preferably, it is 12.5-45 mol. More specifically, when the ions contained in the slurry water Y are phosphate ions, the amount of water used for the hydrothermal reaction is preferably 10 to 30 mol, more preferably 12 .5 to 25 moles. Moreover, when the ion contained in slurry water Y is a silicate ion, the usage-amount of the water used when attaching | subjecting to a hydrothermal reaction becomes like this. Preferably it is 10-50 mol, More preferably, it is 12.5-45. Is a mole.
工程（Ｉ）又は（Ｉｂ）において、鉄化合物、マンガン化合物及び金属（Ｍ、Ｎ又はＱ）塩、並びに水溶性炭素材料の添加順序は特に制限されない。また、これらの金属塩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、上記式（Ａ）〜（Ｃ）で表される酸化物の生成が抑制されるのを防止する観点から、鉄化合物、マンガン化合物及び必要に応じて用いる金属（Ｍ、Ｎ又はＱ）塩の合計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。 In the step (I) or (Ib), the order of addition of the iron compound, the manganese compound and the metal (M, N or Q) salt, and the water-soluble carbon material is not particularly limited. Moreover, while adding these metal salts, 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. From the viewpoint of preventing the generation of oxides represented by the above formulas (A) to (C) from being added in excess, the addition amount of the antioxidant is an iron compound, a manganese compound, and Preferably it is 0.01-1 mol with respect to the total of 1 mol of metal (M, N, or Q) salt used as needed, More preferably, it is 0.03-0.5 mol.
鉄化合物、マンガン化合物及び必要に応じて用いる金属（Ｍ、Ｎ又はＱ）塩、並びに水溶性炭素材料や酸化防止剤を添加することにより得られるスラリーＹ中における複合体Ｙの含有量は、好ましくは１０〜５０質量％であり、より好ましくは１５〜４５質量％であり、さらに好ましくは２０〜４０質量％である。 The content of the complex Y in the slurry Y obtained by adding an iron compound, a manganese compound and a metal (M, N or Q) salt used as necessary, and a water-soluble carbon material or an antioxidant is preferable. Is 10-50 mass%, More preferably, it is 15-45 mass%, More preferably, it is 20-40 mass%.
工程（Ｉ）又は（Ｉｂ）における水熱反応は、１００℃以上であればよく、１３０〜１８０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０〜１８０℃で反応を行う場合、この時の圧力は０．３〜０．９ＭＰａであるのが好ましく、１４０〜１６０℃で反応を行う場合の圧力は０．３〜０．６ＭＰａであるのが好ましい。水熱反応時間は０．１〜４８時間が好ましく、さらに０．２〜２４時間が好ましい。
得られた複合体Ｙは、上記式（Ａ）〜（Ｃ）で表される酸化物及び水溶性炭素材料を含む複合体であり、ろ過後、水で洗浄し、乾燥することによりこれを複合体粒子として単離できる。なお、乾燥手段は、凍結乾燥、真空乾燥が用いられる。
The hydrothermal reaction in process (I) or (Ib) should just be 100 degreeC or more, and 130-180 degreeC is preferable. The hydrothermal reaction is preferably carried out in a pressure vessel, and when the reaction is carried out at 130 to 180 ° C, the pressure at this time is preferably 0.3 to 0.9 MPa, and the reaction is carried out at 140 to 160 ° C. The pressure is preferably 0.3 to 0.6 MPa. The hydrothermal reaction time is preferably 0.1 to 48 hours, more preferably 0.2 to 24 hours.
The obtained composite Y is a composite containing the oxides represented by the above formulas (A) to (C) and a water-soluble carbon material. After filtration, the composite Y is washed with water and dried. It can be isolated as body particles. As the drying means, freeze drying or vacuum drying is used.
得られる複合体ＹのＢＥＴ比表面積は、水溶性炭素材料由来の炭素及び金属フッ化物を効率よく担持して吸着水分量を効果的に低減する観点から、好ましくは５〜４０ｍ２／ｇであり、より好ましくは５〜２０ｍ２／ｇである。複合体ＹのＢＥＴ比表面積が５ｍ２／ｇ未満であると、二次電池用正極活物質の一次粒子が大きくなりすぎ、電池特性が低下してしまうおそれがある。また、ＢＥＴ比表面積が４０ｍ２／ｇを超えると、二次電池用正極活物質の吸着水分量が増大して電池特性に影響を与えるおそれがある。 The BET specific surface area of the obtained composite Y is preferably 5 to 40 m 2 / g from the viewpoint of efficiently carrying the carbon and metal fluoride derived from the water-soluble carbon material and effectively reducing the amount of adsorbed water. More preferably, it is 5-20 m < 2 > / g. If the BET specific surface area of the composite Y is less than 5 m 2 / g, the primary particles of the positive electrode active material for the secondary battery become too large, and the battery characteristics may be deteriorated. On the other hand, if the BET specific surface area exceeds 40 m 2 / g, the amount of adsorbed moisture of the positive electrode active material for secondary batteries may increase and affect battery characteristics.
工程（II）では、工程（Ｉ）で得られた複合体Ｙに、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体を添加して湿式混合し、焼成する工程である。これにより、上記（Ａ）〜（Ｃ）で表される酸化物表面が露出するのを有効に抑制しつつ、かかる酸化物に水溶性炭素材料由来の炭素と金属フッ化物とを、共に堅固に担持させることができる。 In step (II), 0.1 to 40 parts by weight of a metal fluoride precursor is added to 100 parts by weight of the composite Y obtained in step (I), wet-mixed, and fired. It is a process to do. Thereby, while effectively suppressing the exposure of the oxide surface represented by the above (A) to (C), both the carbon derived from the water-soluble carbon material and the metal fluoride are firmly attached to the oxide. It can be supported.
金属フッ化物の前駆体の添加量は、水溶性炭素材料が存在しない酸化物の表面に金属フッ化物を０．１〜５質量％の量で有効に担持させる観点から、複合体Ｙ１００質量部に対し、０．１〜４０質量部であり、好ましくは０．２〜３６質量部であり、より好ましくは０．３〜３２質量部である。また、金属フッ化物を有効に担持させる観点から、金属フッ化物の前駆体とともに、水を添加するのが好ましい。水の添加量は、複合体Ｙ１００質量部に対し、好ましくは３０〜３００質量部であり、より好ましくは５０〜２５０質量部であり、さらに好ましくは７５〜２００質量部である。 The amount of the metal fluoride precursor added is 100 parts by mass of the composite Y from the viewpoint of effectively supporting the metal fluoride in an amount of 0.1 to 5% by mass on the surface of the oxide in which no water-soluble carbon material is present. On the other hand, it is 0.1-40 mass parts, Preferably it is 0.2-36 mass parts, More preferably, it is 0.3-32 mass parts. Further, from the viewpoint of effectively supporting the metal fluoride, it is preferable to add water together with the metal fluoride precursor. The amount of water added is preferably 30 to 300 parts by mass, more preferably 50 to 250 parts by mass, and even more preferably 75 to 200 parts by mass with respect to 100 parts by mass of the composite Y.
金属フッ化物の前駆体とは、後に焼成されることにより、酸化物に担持させるための金属フッ化物を形成することのできる化合物であればよく、具体的には、金属フッ化物の前駆体として、金属フッ化物以外の化合物である、フッ素化合物及び金属化合物を併用するのが好ましい。かかる金属フッ化物以外の化合物であるフッ素化合物としては、フッ化水素酸、フッ化アンモニウム、次亜フッ素酸等が挙げられ、なかでもフッ化アンモニウムを用いるのが好ましい。かかる金属フッ化物以外の化合物である金属化合物としては、酢酸金属塩、硝酸金属塩、乳酸金属塩、シュウ酸金属塩、金属水酸化物、金属エトキシド、金属イソプロポキシド、金属ブトキシド等が挙げられ、なかでも金属水酸化物が好ましい。なお、金属化合物の金属とは、上記金属フッ化物の金属と同義である。 The metal fluoride precursor may be any compound that can be fired later to form a metal fluoride to be supported on an oxide. Specifically, as a metal fluoride precursor, It is preferable to use a fluorine compound and a metal compound which are compounds other than the metal fluoride in combination. Examples of the fluorine compound that is a compound other than the metal fluoride include hydrofluoric acid, ammonium fluoride, and hypofluoric acid. Among them, ammonium fluoride is preferably used. Examples of the metal compound which is a compound other than the metal fluoride include metal acetate, metal nitrate, metal lactate, metal oxalate, metal hydroxide, metal ethoxide, metal isopropoxide, metal butoxide and the like. Of these, metal hydroxides are preferred. In addition, the metal of a metal compound is synonymous with the metal of the said metal fluoride.
工程（II）における湿式混合手段としては、特に制限されず、常法により行うことができる。複合体Ｙに上記量で金属フッ化物の前駆体を添加した後、混合する際の温度は、好ましくは５〜８０℃であり、より好ましくは１０〜６０℃である。得られる混合物は、焼成するまでの間に乾燥するのが好ましい。乾燥手段としては、噴霧乾燥、真空乾燥、凍結乾燥等が挙げられる。 The wet mixing means in the step (II) is not particularly limited and can be performed by a conventional method. The temperature at the time of mixing after adding the metal fluoride precursor to the composite Y in the above amount is preferably 5 to 80 ° C, more preferably 10 to 60 ° C. The resulting mixture is preferably dried before firing. Examples of the drying means include spray drying, vacuum drying, freeze drying and the like.
工程（II）において、上記湿式混合により得られた混合物を焼成する。焼成は、還元雰囲気又は不活性雰囲気中で行うのが好ましい。焼成温度は、水溶性炭素材料を有効に炭化させる観点から、好ましくは５００〜８００℃であり、より好ましくは６００〜７７０℃であり、さらに好ましくは６５０〜７５０℃である。また、焼成時間は、好ましくは１０分〜３時間、より好ましくは３０分〜１．５時間とするのがよい。 In the step (II), the mixture obtained by the wet mixing is fired. Firing is preferably performed in a reducing atmosphere or an inert atmosphere. The firing temperature is preferably 500 to 800 ° C, more preferably 600 to 770 ° C, and further preferably 650 to 750 ° C, from the viewpoint of effectively carbonizing the water-soluble carbon material. The firing time is preferably 10 minutes to 3 hours, more preferably 30 minutes to 1.5 hours.
本発明の二次電池用正極活物質は、上記水溶性炭素材料由来の炭素と金属フッ化物とが、共に上記酸化物に担持されて相乗的に作用し、二次電池用正極活物質における吸着水分量を有効に低減することができる。具体的には、本発明の二次電池用正極活物質の吸着水分量は、酸化物が上記式（Ａ）又は（Ｃ）で表される二次電池用正極活物質では、二次電池用正極活物質中に、好ましくは１２００ｐｐｍ以下であり、より好ましくは１０００ｐｐｍ以下であり、酸化物が上記式（Ｂ）で表される二次電池用正極活物質では、好ましくは２５００ｐｐｍ以下であり、より好ましくは２０００ｐｐｍ以下である。なお、かかる吸着水分量は、温度２０℃及び相対湿度５０％にて平衡に達するまで水分を吸着させ、温度１５０℃まで昇温して２０分間保持した後、さらに温度２５０℃まで昇温して２０分間保持したときの、１５０℃から昇温を再開するときを始点、及び２５０℃での恒温状態を終えたときを終点とする、始点から終点までの間に揮発した水分量として測定される値であって、二次電池用正極活物質の吸着水分量と、上記始点から終点までの間に揮発した水分量とが、同量であるとみなし、かかる揮発する水分量の測定値を二次電池用正極活物質の吸着水分量とするものである。
このように、本発明の二次電池用正極活物質は、水分を吸着しにくいため、製造環境として強い乾燥条件を必要とすることなく吸着水分量を有効に低減することができ、得られるリチウムイオン二次電池及びナトリウムイオン二次電池の双方において、様々な使用環境下でも優れた電池特性を安定して発現することが可能となる。
なお、温度２０℃及び相対湿度５０％にて平衡に達するまで水分を吸着させ、温度１５０℃まで昇温して２０分間保持した後、さらに温度２５０℃まで昇温して２０分間保持したときの、１５０℃から昇温を再開するときを始点、及び２５０℃での恒温状態を終えたときを終点とする、始点から終点までの間に揮発した水分量は、例えばカールフィッシャー水分計を用いて測定することができる。
The positive electrode active material for a secondary battery of the present invention is such that the carbon derived from the water-soluble carbon material and the metal fluoride are both supported on the oxide and act synergistically to adsorb on the positive electrode active material for the secondary battery. The amount of moisture can be effectively reduced. Specifically, the amount of adsorbed moisture of the positive electrode active material for secondary battery of the present invention is the same for the secondary battery in the case of the positive electrode active material for secondary battery in which the oxide is represented by the above formula (A) or (C). In the positive electrode active material, preferably it is 1200 ppm or less, more preferably 1000 ppm or less, and in the positive electrode active material for a secondary battery in which the oxide is represented by the above formula (B), preferably 2500 ppm or less, and more Preferably it is 2000 ppm or less. The amount of adsorbed moisture is such that moisture is adsorbed until equilibrium is reached at a temperature of 20 ° C. and a relative humidity of 50%, the temperature is raised to 150 ° C. and held for 20 minutes, and further raised to a temperature of 250 ° C. Measured as the amount of water volatilized from the start point to the end point, starting from when the temperature rise is resumed from 150 ° C. when held for 20 minutes and ending at the constant temperature state at 250 ° C. It is assumed that the amount of adsorbed moisture of the positive electrode active material for a secondary battery and the amount of moisture volatilized from the start point to the end point are the same, and the measured value of the volatilized moisture amount is This is the amount of moisture adsorbed on the positive electrode active material for the secondary battery.
Thus, since the positive electrode active material for a secondary battery of the present invention hardly adsorbs moisture, the amount of adsorbed moisture can be effectively reduced without requiring strong drying conditions as a production environment, and the resulting lithium In both the ion secondary battery and the sodium ion secondary battery, it is possible to stably exhibit excellent battery characteristics even under various usage environments.
When water is adsorbed until equilibrium is reached at a temperature of 20 ° C. and a relative humidity of 50%, the temperature is raised to 150 ° C. and held for 20 minutes, and further raised to a temperature of 250 ° C. and held for 20 minutes. The amount of water volatilized between the start point and the end point, starting from when the temperature rise is resumed from 150 ° C. and the end point when the constant temperature state at 250 ° C. is completed, is measured using a Karl Fischer moisture meter, for example. Can be measured.
また、本発明の二次電池用正極活物質のタップ密度は、吸着水分量を効果的に低減する観点から、好ましくは０．５〜１．６ｇ／ｃｍ3であり、より好ましくは０．８〜１．６ｇ／ｃｍ3である。 Moreover, the tap density of the positive electrode active material for a secondary battery of the present invention is preferably 0.5 to 1.6 g / cm 3 , more preferably 0.8, from the viewpoint of effectively reducing the amount of adsorbed moisture. ˜1.6 g / cm 3 .
さらに、本発明の二次電池用正極活物質のＢＥＴ比表面積は、吸着水分量を効果的に低減する観点から、好ましくは５〜２１ｍ2／ｇであり、より好ましくは７〜２０ｍ2／ｇである。 Furthermore, the BET specific surface area of the positive electrode active material for secondary batteries of the present invention is preferably 5 to 21 m 2 / g, more preferably 7 to 20 m 2 / g, from the viewpoint of effectively reducing the amount of adsorbed moisture. It is.
本発明の二次電池用正極活物質を含む二次電池用正極を適用できる二次電池としては、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 secondary battery to which the positive electrode for a secondary battery including the positive electrode active material for a 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、リチウムイオン又はナトリ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、ナトリウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムイオン又はナトリウムイオン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 for the negative electrode, as long as lithium ions or sodium ions can be occluded at the time of charging and can be released at the time of discharging, the material configuration is not particularly limited, and those having a known material configuration can be used. . For example, a carbon material such as lithium metal, sodium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium ions or sodium ions, 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やナトリ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 or a sodium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones Nitriles, lactones, oxolane compounds and 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、リチウムイオン二次電池の場合、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ３ＣＦ３、ＬｉＣ（ＳＯ３ＣＦ３）２、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。また、ナトリウムイオン二次電池の場合、ＮａＰＦ６、ＮａＢＦ４、ＮａＣｌＯ４及びＮａＡｓＦ６から選ばれる無機塩、該無機塩の誘導体、ＮａＳＯ３ＣＦ３、ＮａＣ（ＳＯ３ＣＦ３）２及びＮａＮ（ＳＯ３ＣＦ３）２、ＮａＮ（ＳＯ２Ｃ２Ｆ５）２及びＮａＮ（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 in the case of a lithium ion secondary battery, an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , an organic material selected from LiC (SO 3 CF 3 ) 2 , 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 ) It is preferably at least one of a salt and a derivative of the organic salt. In the case of a sodium ion secondary battery, an inorganic salt selected from NaPF 6 , NaBF 4 , NaClO 4 and NaAsF 6 , a derivative of the inorganic salt, NaSO 3 CF 3 , NaC (SO 3 CF 3 ) 2 and NaN (SO 3 CF 3 ) 2 , NaN (SO 2 C 2 F 5 ) 2 and NaN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and at least one of derivatives of the organic salt It is preferable.
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１−１］
ＬｉＯＨ・Ｈ2Ｏ １２．７２ｇ、及び水 ９０ｍＬ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５分間撹拌しつつ８５％のリン酸水溶液 １１．５３ｇを３５ｍＬ／分で滴下し、続いて窒素ガスパージ下で１２時間、４００ｒｐｍの速度で撹拌することにより、複合体Ｘ1を含有する混合物Ｘ1（スラリー水Ｘ1、溶存酸素濃度０．５ｍｇ／Ｌ）を得た。かかるスラリー水Ｘ1は、リン１モルに対し、２．９７モルのリチウムを含有していた。
[Example 1-1]
12.72 g of LiOH.H 2 O and 90 mL of water were mixed to obtain slurry water. Next, 11.53 g of 85% aqueous phosphoric acid solution was added dropwise at 35 mL / min while stirring the resulting slurry water at a temperature of 25 ° C. for 5 minutes, followed by 12 hours under a nitrogen gas purge at 400 rpm. By stirring at a speed, a mixture X 1 (slurry water X 1 , dissolved oxygen concentration 0.5 mg / L) containing the complex X 1 was obtained. The slurry water X 1 contained 2.97 mol of lithium with respect to 1 mol of phosphorus.
次に、得られたスラリー水Ｘ1１１４．２ｇに対し、ＦｅＳＯ4・７Ｈ2Ｏ ５．５６ｇ、ＭｎＳＯ4・５Ｈ2Ｏ １９．２９ｇ及びグルコース１．１８ｇ（リチウムイオン二次電池用正極活物質中における炭素原子換算量で３．０質量％に相当）を添加し、２５℃の温度に保持しながら速度４００ｒｐｍにて３０分間撹拌してスラリー水Ｙ1を得た。このとき、添加したＦｅＳＯ4・７Ｈ2ＯとＭｎＳＯ4・Ｈ2Ｏのモル比（ＦｅＳＯ4・７Ｈ2Ｏ：ＭｎＳＯ4・Ｈ2Ｏ）は、２０：８０であった。
次いで、得られたスラリー水Ｙ1を蒸気加熱式オートクレーブ内に設置した合成容器に投入した。投入後、隔膜分離装置により水（溶存酸素濃度０．５ｍｇ／Ｌ未満）を加熱して得た飽和蒸気を用いて、１７０℃で１時間攪拌しながら加熱した。オートクレーブ内の圧力は、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−５０℃で１２時間凍結乾燥して複合体Ｙ1（粉末、式（Ａ）で表される酸化物の化学組成：ＬｉＦｅ0.2Ｍｎ0.8ＰＯ4、ＢＥＴ比表面積２１ｍ2／ｇ、平均粒径６０ｎｍ）を得た。
Next, 5.56 g of FeSO 4 .7H 2 O, 19.29 g of MnSO 4 .5H 2 O and 1.18 g of glucose (positive electrode active material for a lithium ion secondary battery) with respect to 114.2 g of the obtained slurry water X 1 And equivalent to 3.0% by mass in terms of carbon atoms) was added and stirred at a speed of 400 rpm for 30 minutes while maintaining the temperature at 25 ° C. to obtain slurry water Y 1 . In this case, the added FeSO 4 · 7H 2 O and MnSO 4 · H 2 O molar ratio of (FeSO 4 · 7H 2 O: MnSO 4 · H 2 O) is 20: was 80.
Next, the obtained slurry water Y 1 was put into a synthesis container installed in a steam heating autoclave. After the addition, the mixture was heated with stirring at 170 ° C. for 1 hour using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The 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 freeze-dried at −50 ° C. for 12 hours to give a composite Y 1 (powder, chemical composition of oxide represented by formula (A): LiFe 0.2 Mn 0.8 PO 4 , BET specific surface area 21 m 2 / g, An average particle size of 60 nm) was obtained.
得られた複合体Ｙ1 ４．０ｇと、ＬｉＯＨを０．０３３ｇ及びフッ化アンモニウムを０．０２９ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で０．５質量％に相当）を水５ｍｌと混合し、１時間の撹拌によりＬｉＦコートされた複合体Ｙ1を得た。次いで、還元雰囲気下で７００℃で１時間焼成して、リチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＬｉＦの量＝０．５質量％）を得た。 4.0 g of the obtained composite Y 1 , 0.033 g of LiOH and 0.029 g of ammonium fluoride (corresponding to 0.5% by mass in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery) ) Was mixed with 5 ml of water, and LiF-coated composite Y 1 was obtained by stirring for 1 hour. Next, it was calcined at 700 ° C. for 1 hour in a reducing atmosphere, and a positive electrode active material for a lithium ion secondary battery (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0 mass%, amount of LiF = 0.5 mass) %).
［実施例１−２］
複合体Ｙ1に添加するＬｉＯＨを０．０６６ｇ、フッ化アンモニウムを０．０５９ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で１．０質量％に相当）とした以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＬｉＦの量＝１．０質量％）を得た。
[Example 1-2]
Except for 0.066 g of LiOH added to the composite Y 1 and 0.059 g of ammonium fluoride (corresponding to 1.0 mass% in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), A positive electrode active material for lithium ion secondary batteries (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0 mass%, amount of LiF = 1.0 mass%) was obtained in the same manner as in Example 1-1. .
［実施例１−３］
複合体Ｙ1に添加するＬｉＯＨを０．１３２ｇ、フッ化アンモニウムを０．１１８ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で２．０質量％に相当）とした以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＬｉＦの量＝２．０質量％）を得た。
[Example 1-3]
Except for 0.132 g of LiOH added to the composite Y 1 and 0.118 g of ammonium fluoride (corresponding to 2.0 mass% in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), A positive electrode active material for lithium ion secondary batteries (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0 mass%, amount of LiF = 2.0 mass%) was obtained in the same manner as in Example 1-1. .
［実施例１−４］
複合体Ｙ1に添加するＬｉＯＨの代わりにＡｌ（ＯＨ）３を０．０７８ｇ、フッ化アンモニウムを０．３５３ｇ（リチウムイオン二次電池用正極活物質中におけるＡｌＦ3の担持量換算で２．０質量％に相当）とした以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＡｌＦ3の量＝２．０質量％）を得た。
[Example 1-4]
Instead of LiOH added to the composite Y 1 , 0.078 g of Al (OH) 3 and 0.353 g of ammonium fluoride (2.0 in terms of the amount of AlF 3 supported in the positive electrode active material for a lithium ion secondary battery) The positive electrode active material for a lithium ion secondary battery (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0 mass%, amount of AlF 3 ) = 2.0% by mass).
［実施例１−５］
複合体Ｙ1に添加するＬｉＯＨの代わりにＭｇ（ＣＨ３ＣＯＯ）２・４Ｈ２Ｏを０．２７７ｇ、フッ化アンモニウムを０．２３６ｇ（リチウムイオン二次電池用正極活物質中におけるＭｇＦ2の担持量換算で２．０質量％に相当）とした以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＭｇＦ2の量＝２．０質量％）を得た。
[Example 1-5]
Instead of LiOH added to the composite Y 1 , 0.277 g of Mg (CH 3 COO) 2 .4H 2 O and 0.236 g of ammonium fluoride (support of MgF 2 in the positive electrode active material for a lithium ion secondary battery) Except that the amount was equivalent to 2.0% by mass), a positive electrode active material for a lithium ion secondary battery (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0% by mass) in the same manner as in Example 1-1. %, The amount of MgF 2 = 2.0 mass%).
［比較例１−１］
複合体Ｙ1に添加するＬｉＯＨを０．３９６ｇ、フッ化アンモニウムを０．３５３ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で５．７質量％に相当）とした以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、ＬｉＦの量＝５．７質量％）を得た。
[Comparative Example 1-1]
Except for 0.396 g of LiOH added to the composite Y 1 and 0.353 g of ammonium fluoride (corresponding to 5.7 mass% in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), A positive electrode active material for a lithium ion secondary battery (LiFe 0.2 Mn 0.8 PO 4 , the amount of carbon = 3.0 mass%, the amount of LiF = 5.7 mass%) was obtained in the same manner as in Example 1-1. .
［比較例１−２］
金属フッ化物を添加しなかった以外、実施例１−１と同様の方法でリチウムイオン二次電池用正極活物質（ＬｉＦｅ0.2Ｍｎ0.8ＰＯ４、炭素の量＝３．０質量％、金属フッ化物担持なし）を得た。
[Comparative Example 1-2]
A positive electrode active material for a lithium ion secondary battery (LiFe 0.2 Mn 0.8 PO 4 , amount of carbon = 3.0 mass%, metal fluoride, in the same manner as in Example 1-1, except that no metal fluoride was added. Not supported).
［実施例２−１］
ＬｉＯＨ・Ｈ2Ｏ ４．２８ｇ、Ｎａ4ＳｉＯ4・ｎＨ2Ｏ １３．９７ｇに超純水３７．５ｍＬを混合してスラリー水Ｘ２を得た。このスラリー水Ｘ２に、ＦｅＳＯ4・７Ｈ2Ｏ ３．９２ｇ、ＭｎＳＯ4・５Ｈ2Ｏ ７．９３ｇ、及びＺｒ（ＳＯ4）２・４Ｈ2Ｏ ０．５３ｇを添加し、２５℃の温度に保持しながら速度４００ｒｐｍにて３０分間撹拌して、スラリー水Ｙ２を得た。このとき、添加したＦｅＳＯ4・７Ｈ2Ｏ、ＭｎＳＯ4・５Ｈ2Ｏ及びＺｒ（ＳＯ4）２・４Ｈ2Ｏのモル比（ＦｅＳＯ4・７Ｈ2Ｏ：ＭｎＳＯ4・５Ｈ2Ｏ：Ｚｒ（ＳＯ4）２・４Ｈ2Ｏ）は、２８：６６：３であった。
次いで、得られたスラリー水Ｙ２を蒸気加熱式オートクレーブ内に設置した合成容器に投入した。投入後、隔膜分離装置により水（溶存酸素濃度０．５ｍｇ／Ｌ未満）を加熱して得た飽和蒸気を用いて、１５０℃で１２時間攪拌しながら加熱した。オートクレーブの圧力は０．４ＭＰａ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−５０℃で１２時間凍結乾燥して複合体Ｙ２（粉末、式（Ｂ）で表される酸化物の化学組成：Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、ＢＥＴ比表面積３５ｍ2／ｇ、平均粒径５０ｎｍ）を得た。
[Example 2-1]
LiOH · H 2 O 4.28g, was obtained slurry water X 2 were mixed ultrapure water 37.5mL to Na 4 SiO 4 · nH 2 O 13.97g. To this slurry water X 2, FeSO 4 · 7H 2 O 3.92g, MnSO 4 · 5H 2 O 7.93g, and Zr (SO 4) was added to 2 · 4H 2 O 0.53g, at a temperature of 25 ° C. It was stirred for 30 minutes at speed 400rpm while maintaining, to obtain a slurry water Y 2. At this time, the molar ratio of FeSO 4 · 7H 2 O, MnSO 4 · 5H 2 O and Zr (SO 4 ) 2 · 4H 2 O added (FeSO 4 · 7H 2 O: MnSO 4 · 5H 2 O: Zr (SO 4) 2 · 4H 2 O) is 28: 66: 3.
Then, the resulting slurry water Y 2 was charged into the synthesis vessel installed in a steam-heated autoclave. After the addition, the mixture was heated with stirring at 150 ° C. for 12 hours using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The pressure in the autoclave was 0.4 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 freeze-dried at −50 ° C. for 12 hours to obtain a composite Y 2 (powder, chemical composition of an oxide represented by the formula (B): Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , BET specific surface area of 35 m. 2 / g, average particle size 50 nm).
得られた複合体Ｙ２を４．０ｇ分取し、これにグルコース１．０ｇ（リチウムイオン二次電池用正極活物質中における炭素原子換算量で１０．０質量％に相当）、ＬｉＯＨ０．０３３ｇ、及びフッ化アンモニウム０．０２９ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で０．５質量％に相当）、及び水５ｍＬを混合し、１時間の撹拌によりグルコースとＬｉＦをコートした後、還元雰囲気下で６５０℃で１時間焼成して、リチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＬｉＦの量＝０．５質量％）を得た。 4.0 g of the obtained complex Y 2 was fractionated, and 1.0 g of glucose (corresponding to 10.0% by mass in terms of carbon atom in the positive electrode active material for a lithium ion secondary battery) was obtained. , And 0.029 g of ammonium fluoride (corresponding to 0.5% by mass in terms of the amount of LiF supported in the positive electrode active material for lithium ion secondary batteries) and 5 mL of water are mixed, and glucose and LiF are stirred by stirring for 1 hour. After being coated, it was baked at 650 ° C. for 1 hour in a reducing atmosphere to obtain a positive electrode active material for a lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , amount of carbon = 10.0 mass%, LiF Of 0.5% by mass).
［実施例２−２］
複合体Ｙ２に添加するＬｉＯＨを０．０６６ｇ、フッ化アンモニウムを０．０５９ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で１．０質量％に相当）とした以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＬｉＦの量＝１．０質量％）を得た。
[Example 2-2]
Except for 0.066 g of LiOH added to the composite Y 2 and 0.059 g of ammonium fluoride (corresponding to 1.0 mass% in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), Positive electrode active material for lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , amount of carbon = 10.0% by mass, amount of LiF = 1.0% by mass in the same manner as in Example 2-1. )
［実施例２−３］
複合体Ｙ２に添加するＬｉＯＨを０．１３２ｇ、フッ化アンモニウムを０．１１８ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で２．０質量％に相当）とした以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＬｉＦの量＝２．０質量％）を得た。
[Example 2-3]
Except for 0.132 g of LiOH added to the composite Y 2 and 0.118 g of ammonium fluoride (corresponding to 2.0% by mass in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), Positive electrode active material for lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , amount of carbon = 10.0% by mass, amount of LiF = 2.0% by mass in the same manner as in Example 2-1. )
［実施例２−４］
複合体Ｙ２に添加するＬｉＯＨの代わりにＡｌ（ＯＨ）３を０．０７８ｇ、フッ化アンモニウムを０．３５３ｇ（リチウムイオン二次電池用正極活物質中におけるＡｌＦ２の担持量換算で２．０質量％に相当）とした以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＡｌＦ２の量＝２．０質量％）を得た。
[Example 2-4]
2.0 Al (OH) 3 in place of LiOH added to the complex Y 2 0.078 g, in a loading amount in terms of AlF 2 in the positive electrode active material in a 0.353 g (lithium ion secondary battery of ammonium fluoride Except for the equivalent to mass%), a positive electrode active material for a lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , the amount of carbon = 10.0 mass%) in the same manner as in Example 2-1. Amount of AlF 2 = 2.0% by mass) was obtained.
［実施例２−５］
複合体Ｙ２に添加するＬｉＯＨの代わりにＭｇ（ＣＨ３ＣＯＯ）２・４Ｈ２Ｏを０．２７７ｇ、フッ化アンモニウムを０．２３６ｇ（リチウムイオン二次電池用正極活物質中におけるＭｇＦ２の担持量換算で２．０質量％に相当）とした以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＭｇＦ２の量＝２．０質量％）を得た。
[Example 2-5]
0.277 g of Mg (CH 3 COO) 2 .4H 2 O and 0.236 g of ammonium fluoride instead of LiOH added to the composite Y 2 (support of MgF 2 in the positive electrode active material for a lithium ion secondary battery) The amount of carbon = a positive electrode active material for lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , carbon = 10.0% by mass, the amount of MgF 2 = 2.0% by mass).
［比較例２−１］
複合体Ｙ２に添加するＬｉＯＨを０．３９６ｇ、フッ化アンモニウムを０．３５３ｇ（リチウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で６．０質量％に相当）とした以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、ＬｉＦの量＝６．０質量％）を得た。
[Comparative Example 2-1]
Except for 0.396 g of LiOH added to the composite Y 2 and 0.353 g of ammonium fluoride (corresponding to 6.0% by mass in terms of the amount of LiF supported in the positive electrode active material for a lithium ion secondary battery), Positive electrode active material for lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , amount of carbon = 10.0 mass%, amount of LiF = 6.0 mass% in the same manner as in Example 2-1. )
［比較例２−２］
金属フッ化物を添加しなかった以外、実施例２−１と同様の方法でリチウムイオン二次電池用正極活物質（Ｌｉ2Ｆｅ0.28Ｍｎ0.66Ｚｒ0.03ＳｉＯ4、炭素の量＝１０．０質量％、金属フッ化物担持なし）を得た。
[Comparative Example 2-2]
A positive electrode active material for a lithium ion secondary battery (Li 2 Fe 0.28 Mn 0.66 Zr 0.03 SiO 4 , amount of carbon = 10.0% by mass) in the same manner as in Example 2-1, except that no metal fluoride was added. No metal fluoride was supported).
［実施例３−１］
ＮａＯＨ ６．００ｇ、水 ９０ｍＬを混合して溶液を得た。次いで、得られた溶液を、２５℃の温度に保持しながら５分間撹拌しつつ８５％のリン酸水溶液 ５．７７ｇを３５ｍＬ／分で滴下し、続いて１２時間、４００ｒｐｍの速度で撹拌することにより、複合体Ｘ３を含有するスラリーＸ３を得た。かかるスラリーＸ３は、リン１モルに対し、３．００モルのナトリウムを含有していた。得られたスラリーＸ３に対し、窒素ガスをパージして溶存酸素濃度を０．５ｍｇ／Ｌに調整した後、ＦｅＳＯ4・７Ｈ2Ｏ １．３９ｇ、ＭｎＳＯ4・５Ｈ2Ｏ ９．６４ｇ、ＭｇＳＯ４・７Ｈ２Ｏ １．２４ｇ、及びグルコース０．５９ｇ（ナトリウムイオン二次電池用正極活物質中における炭素原子換算量で１．４質量％に相当）を添加してスラリー水Ｙ３を得た。このとき、添加したＦｅＳＯ4・７Ｈ2Ｏ、ＭｎＳＯ4・５Ｈ2Ｏ及びＭｇＳＯ４・７Ｈ２Ｏのモル比（ＦｅＳＯ4・７Ｈ2Ｏ：ＭｎＳＯ4・５Ｈ2Ｏ：ＭｇＳＯ４・７Ｈ２Ｏは、１０：８０：１０であった。
次いで、得られたスラリー水Ｙ３を蒸気加熱式オートクレーブ内に設置した、窒素ガスでパージした合成容器に投入した。投入後、隔膜分離装置により水（溶存酸素濃度０．５ｍｇ／Ｌ未満）を加熱して得た飽和蒸気を用いて、２００℃で３時間攪拌しながら加熱した。オートクレーブ内の圧力は、１．４ＭＰａ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−５０℃で１２時間凍結乾燥して複合体Ｙ３（式（Ｃ）で表される酸化物の化学組成：ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、ＢＥＴ比表面積１５ｍ2／ｇ、平均粒径１００ｎｍ）を得た。
[Example 3-1]
A solution was obtained by mixing 6.00 g of NaOH and 90 mL of water. The resulting solution is then stirred for 5 minutes while maintaining the temperature at 25 ° C., and 5.77 g of 85% aqueous phosphoric acid solution is added dropwise at 35 mL / min, followed by stirring at a speed of 400 rpm for 12 hours. gave a slurry X 3 containing complex X 3. Such slurry X 3, compared per mole of phosphorus and contained sodium 3.00 mol. To slurry X 3 obtained after the dissolved oxygen concentration with nitrogen gas was purged and adjusted to 0.5mg / L, FeSO 4 · 7H 2 O 1.39g, MnSO 4 · 5H 2 O 9.64g, MgSO 4 · 7H 2 O 1.24g, and glucose 0.59 g (corresponding to 1.4 wt% in terms of carbon atoms content in the sodium ion secondary battery positive electrode active material in) was added to obtain a slurry solution Y 3 . At this time, the molar ratio of FeSO 4 · 7H 2 O, MnSO 4 · 5H 2 O and MgSO 4 · 7H 2 O added (FeSO 4 · 7H 2 O: MnSO 4 · 5H 2 O: MgSO 4 · 7H 2 O is 10:80:10.
Then, the slurry water Y 3 obtained was placed in a steam-heated autoclave was charged in the synthesis vessel was purged with nitrogen gas. After the addition, the mixture was heated with stirring at 200 ° C. for 3 hours using saturated steam obtained by heating water (dissolved oxygen concentration less than 0.5 mg / L) with a membrane separator. The pressure in the autoclave was 1.4 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 freeze-dried at −50 ° C. for 12 hours to give a composite Y 3 (chemical composition of an oxide represented by the formula (C): NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , BET specific surface area 15 m 2 / g, An average particle size of 100 nm) was obtained.
得られた複合体Ｙ３を４．０ｇ分取し、これにＬｉＯＨを０．０３３ｇ、及びフッ化アンモニウムを０．０２９ｇ（ナトリウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で０．５質量％に相当）、及び水５ｍｌを混合し、１時間の撹拌によりＬｉＦコートした後、還元雰囲気下で７００℃で１時間焼成して、ナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＬｉＦの量＝０．５質量％）を得た。 4.0 g of the obtained composite Y 3 was taken, and 0.033 g of LiOH and 0.029 g of ammonium fluoride (0 in terms of the amount of LiF supported in the positive electrode active material for a sodium ion secondary battery) And 5 ml of water, and LiF coating by stirring for 1 hour, followed by firing at 700 ° C. for 1 hour in a reducing atmosphere to obtain a positive electrode active material for sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , carbon amount = 1.4 mass%, LiF amount = 0.5 mass%).
［実施例３−２］
複合体Ｙ2に添加するＬｉＯＨを０．０６６ｇ、フッ化アンモニウムを０．０５９ｇ（ナトリウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で１．０質量％に相当）とした以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＬｉＦの量＝１．０質量％）を得た。
[Example 3-2]
Except for 0.066 g of LiOH added to the composite Y 2 and 0.059 g of ammonium fluoride (corresponding to 1.0% by mass in terms of the amount of LiF supported in the positive electrode active material for sodium ion secondary battery), In the same manner as in Example 3-1, a positive electrode active material for a sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1.4 mass%, amount of LiF = 1.0 mass%) Obtained.
［実施例３−３］
複合体Ｙ2に添加するＬｉＯＨを０．１３２ｇ、フッ化アンモニウムを０．１１８ｇ（ナトリウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で２．０質量％に相当）とした以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＬｉＦの量＝２．０質量％）を得た。
[Example 3-3]
Except for 0.132 g of LiOH added to the composite Y 2 and 0.118 g of ammonium fluoride (corresponding to 2.0 mass% in terms of the amount of LiF supported in the positive electrode active material for a sodium ion secondary battery), In the same manner as in Example 3-1, a positive electrode active material for a sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1.4 mass%, amount of LiF = 2.0 mass%) Obtained.
［実施例３−４］
複合体Ｙ2に添加するＬｉＯＨの代わりにＡｌ（ＯＨ）３を０．０７８ｇ、フッ化アンモニウムを０．３５３ｇ（ナトリウムイオン二次電池用正極活物質中におけるＡｌＦ３の担持量換算で２．０質量％に相当）とした以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＡｌＦ３の量＝２．０質量％）を得た。
[Example 3-4]
Instead of LiOH added to the composite Y 2 , 0.078 g of Al (OH) 3 and 0.353 g of ammonium fluoride (2.0 in terms of the amount of AlF 3 supported in the positive electrode active material for a sodium ion secondary battery) The positive electrode active material for a sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1.4 mass%, AlF 3) Of 2.0% by mass).
［実施例３−５］
複合体Ｙ2に添加するＬｉＯＨの代わりにＭｇ（ＣＨ３ＣＯＯ）２・４Ｈ２Ｏを０．２７７ｇ、フッ化アンモニウムを０．２３６ｇ（ナトリウムイオン二次電池用正極活物質中におけるＭｇＦ３の担持量換算で２．０質量％に相当）とした以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＭｇＦ３の量＝２．０質量％）を得た。
[Example 3-5]
Instead of LiOH added to the composite Y 2 , 0.277 g of Mg (CH 3 COO) 2 .4H 2 O and 0.236 g of ammonium fluoride (support of MgF 3 in the positive electrode active material for a sodium ion secondary battery) A positive electrode active material for sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1. 4 mass%, the amount of MgF 3 = 2.0 mass%).
［比較例３−１］
複合体Ｙ2に添加するＬｉＯＨを０．３９６ｇ、フッ化アンモニウムを０．３５３ｇ（ナトリウムイオン二次電池用正極活物質中におけるＬｉＦの担持量換算で６．０質量％に相当）とした以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、ＬｉＦの量＝６．０質量％）を得た。
[Comparative Example 3-1]
Except for 0.396 g of LiOH added to the composite Y 2 and 0.353 g of ammonium fluoride (corresponding to 6.0% by mass in terms of the amount of LiF supported in the positive electrode active material for a sodium ion secondary battery), In the same manner as in Example 3-1, a positive electrode active material for a sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1.4% by mass, amount of LiF = 6.0% by mass) Obtained.
［比較例３−２］
金属フッ化物を添加しなかった以外、実施例３−１と同様の方法でナトリウムイオン二次電池用正極活物質（ＮａＦｅ0.1Ｍｎ0.8Ｍｇ0.1ＰＯ４、炭素の量＝１．４質量％、金属フッ化物担持なし）を得た。
[Comparative Example 3-2]
A positive electrode active material for a sodium ion secondary battery (NaFe 0.1 Mn 0.8 Mg 0.1 PO 4 , amount of carbon = 1.4 mass%, metal, in the same manner as in Example 3-1, except that no metal fluoride was added Without fluoride support).
《吸着水分量の測定》
実施例１−１〜３−５及び比較例１−１〜３−２で得られた各正極活物質の吸着水分量は、下記方法にしたがって測定した。
正極活物質（複合体粒子）について、温度２０℃、相対湿度５０％の環境に１日間静置して平衡に達するまで水分を吸着させ、温度１５０℃まで昇温して２０分間保持した後、さらに温度２５０℃まで昇温して２０分間保持したときの、１５０℃から昇温を再開するときを始点、及び２５０℃での恒温状態を終えたときを終点とし、始点から終点までの間に揮発した水分量を、カールフィッシャー水分計（ＭＫＣ−６１０、京都電子工業（株）製）で測定し、正極活物質における吸着水分量として求めた。
結果を表１に示す。
<Measurement of adsorbed water content>
The adsorbed moisture content of each positive electrode active material obtained in Examples 1-1 to 3-5 and Comparative Examples 1-1 to 3-2 was measured according to the following method.
About the positive electrode active material (composite particle), after allowing it to stand for 1 day in an environment of a temperature of 20 ° C. and a relative humidity of 50% and adsorbing moisture until reaching equilibrium, raising the temperature to 150 ° C. and holding for 20 minutes, Furthermore, when the temperature is raised to 250 ° C. and held for 20 minutes, the start point is when the temperature rise is resumed from 150 ° C., and the end point is when the constant temperature state at 250 ° C. is finished. The amount of water that volatilized was measured with a Karl Fischer moisture meter (MKC-610, manufactured by Kyoto Electronics Industry Co., Ltd.) and determined as the amount of moisture adsorbed in the positive electrode active material.
The results are shown in Table 1.
《二次電池を用いた充放電特性の評価》
実施例１−１〜３−５及び比較例１−１〜３−２で得られた正極活物質を用い、リチウムイオン二次電池又はナトリ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質量比７５：２０：５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（リチウムイオン二次電池の場合）又はＮａＰＦ６（ナトリウムイオン二次電池の場合）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、コイン型二次電池（ＣＲ−２０３２）を製造した。
<< Evaluation of charge / discharge characteristics using secondary battery >>
Using the positive electrode active materials obtained in Examples 1-1 to 3-5 and Comparative Examples 1-1 to 2-3, positive electrodes of lithium ion secondary batteries or sodium ion secondary batteries were produced. Specifically, the obtained positive electrode active material, ketjen black and polyvinylidene fluoride were mixed at a mass ratio of 75: 20: 5, 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 secondary battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. For the electrolyte, LiPF 6 (in the case of a lithium ion secondary battery) or NaPF 6 (in the case of a sodium ion secondary battery) is mixed in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate are mixed at a volume ratio of 1: 1. Those dissolved at a concentration of 1 mol / L were 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 secondary battery (CR-2032).
製造したコイン型二次電池を用い、充放電試験を行った。リチウムイオン電池の場合には、充電条件を電流１ＣＡ（３３０ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件を１ＣＡ（３３０ｍＡ／ｇ）、終止電圧１．５Ｖの定電流放電として、１ＣＡにおける放電容量を求めた。ナトリウムイオン電池の場合には、充電条件を電流１ＣＡ（１５４ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件を１ＣＡ（１５４ｍＡ／ｇ）、終止電圧２．０Ｖの定電流放電として、１ＣＡにおける放電容量を求めた。さらに、同様の充放電条件において、５０サイクル繰り返し試験を行い、下記式（２）により容量保持率（％）を求めた。なお、充放電試験は全て３０℃で行った。
容量保持率（％）＝（５０サイクル後の放電容量）／（１サイクル後の放
電容量）×１００ ・・・（２）
結果を表１に示す。
A charge / discharge test was performed using the manufactured coin-type secondary battery. In the case of a lithium ion battery, the charging condition is a constant current and constant voltage charge with a current of 1 CA (330 mA / g) and a voltage of 4.5 V, the discharge condition is 1 CA (330 mA / g), and a constant current discharge with a final voltage of 1.5 V. As a result, the discharge capacity at 1 CA was obtained. In the case of a sodium ion battery, the charging conditions are a constant current and constant voltage charging with a current of 1 CA (154 mA / g) and a voltage of 4.5 V, the discharging conditions are a constant current discharge of 1 CA (154 mA / g) and a final voltage of 2.0 V. As a result, the discharge capacity at 1 CA was obtained. Furthermore, 50 cycle repetition tests were performed under the same charge / discharge conditions, and the capacity retention rate (%) was determined by the following formula (2). All charge / discharge tests were performed at 30 ° C.
Capacity retention rate (%) = (discharge capacity after 50 cycles) / (discharge capacity after 1 cycle) × 100 (2)
The results are shown in Table 1.
上記結果より、実施例の正極活物質は、比較例の正極活物質に比して、確実に吸着水分量を低減することができるとともに、得られる電池においても優れた性能を発揮できることがわかる。 From the above results, it can be seen that the positive electrode active material of the example can surely reduce the amount of adsorbed moisture as compared with the positive electrode active material of the comparative example, and can also exhibit excellent performance in the obtained battery.
Claims (6)
ＬｉＦｅaＭｎbＭcＰＯ4・・・（Ａ）
（式（Ａ）中、ＭはＭｇ、Ｃａ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ａ、ｂ及びｃは、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦０．２、及び２ａ＋２ｂ＋（Ｍの価数）×ｃ＝２を満たし、かつａ＋ｂ≠０を満たす数を示す。）
Ｌｉ2ＦｅdＭｎeＮfＳｉＯ4・・・（Ｂ）
（式（Ｂ）中、ＮはＮｉ、Ｃｏ、Ａｌ、Ｚｎ、Ｖ又はＺｒを示す。ｄ、ｅ及びｆは、０≦ｄ≦１、０≦ｅ≦１、及び０≦ｆ＜１、２ｄ＋２ｅ＋（Ｎの価数）×ｆ＝２を満たし、かつｄ＋ｅ≠０を満たす数を示す。）
ＮａＦｅgＭｎhＱiＰＯ4・・・（Ｃ）
（式（Ｃ）中、ＱはＭｇ、Ｃａ、Ｃｏ、Ｓｒ、Ｙ、Ｚｒ、Ｍｏ、Ｂａ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｎｄ又はＧｄを示す。ｇ、ｈ及びｉは、０≦ｇ≦１、０≦ｈ≦１、０≦ｉ＜１、及び２ｇ＋２ｈ＋（Ｑの価数）×ｉ＝２を満たし、かつｇ＋ｈ≠０を満たす数を示す。）
で表される酸化物と水溶性炭素材料由来の炭素とを含む複合体に、０．１〜５質量％の金属フッ化物が担持してなるリチウムイオン二次電池又はナトリウムイオン二次電池用正極活物質。 The following formula (A), (B) or (C) containing at least iron or manganese:
LiFe a Mn b M c PO 4 (A)
(In the formula (A), M represents Mg, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. A, b, and c are 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 0.2, and 2a + 2b + (M valence) × c = 2 and a number satisfying a + b ≠ 0 are shown.)
Li 2 Fe d Mn e N f SiO 4 (B)
(In the formula (B), N represents Ni, Co, Al, Zn, V, or Zr. D, e, and f are 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, and 0 ≦ f <1, 2d + 2e +. (The valence of N) × f = 2 is satisfied, and d + e ≠ 0 is satisfied.)
NaFe g Mn h Q i PO 4 (C)
(In the formula (C), Q represents Mg, Ca, Co, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. G, h, and i are 0 ≦ g ≦. 1, 0 ≦ h ≦ 1, 0 ≦ i <1, and 2g + 2h + (valence of Q) × i = 2 and a number satisfying g + h ≠ 0 are shown.)
A lithium ion secondary battery or a sodium ion secondary battery positive electrode in which 0.1 to 5% by mass of a metal fluoride is supported on a composite comprising an oxide represented by formula (I) and carbon derived from a water-soluble carbon material. Active material.
得られた複合体Ｙに、複合体１００質量部に対して０．１〜４０質量部の金属フッ化物の前駆体を添加して湿式混合し、焼成する工程（II）
を備える、請求項１〜３のいずれか１項に記載のリチウムイオン二次電池又はナトリウムイオン二次電池用正極活物質の製造方法。 A composite Y obtained by subjecting a slurry water containing a lithium compound or sodium compound, a phosphoric acid compound or a silicic acid compound, and a metal salt containing at least an iron compound or a manganese compound and containing a water-soluble carbon material to a hydrothermal reaction. To the obtained composite Y, and 0.1 to 40 parts by weight of a metal fluoride precursor is added to 100 parts by weight of the composite, wet-mixed, and fired ( II)
The manufacturing method of the positive electrode active material for lithium ion secondary batteries or sodium ion secondary batteries of any one of Claims 1-3 provided with these.
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