JP4260572B2 - Method for producing lithium iron phosphorus composite oxide carbon composite containing Mn atom - Google Patents
Method for producing lithium iron phosphorus composite oxide carbon composite containing Mn atom Download PDFInfo
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- JP4260572B2 JP4260572B2 JP2003281561A JP2003281561A JP4260572B2 JP 4260572 B2 JP4260572 B2 JP 4260572B2 JP 2003281561 A JP2003281561 A JP 2003281561A JP 2003281561 A JP2003281561 A JP 2003281561A JP 4260572 B2 JP4260572 B2 JP 4260572B2
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- lithium
- iron
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- manganese
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- 239000002131 composite material Substances 0.000 title claims description 86
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 title claims description 44
- 229910052799 carbon Inorganic materials 0.000 title claims description 40
- 229910052748 manganese Inorganic materials 0.000 title claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000011572 manganese Substances 0.000 claims description 87
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910052742 iron Inorganic materials 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 27
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 26
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003575 carbonaceous material Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 150000002505 iron Chemical class 0.000 claims description 16
- 150000002696 manganese Chemical class 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 5
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 46
- 125000004429 atom Chemical group 0.000 description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- 239000002994 raw material Substances 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000010304 firing Methods 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002341 toxic gas Substances 0.000 description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011570 LiFe 1-x Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NVCJWNQIUCTSAJ-UHFFFAOYSA-J P(O)(O)(O)=O.S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Fe+2] Chemical compound P(O)(O)(O)=O.S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Fe+2] NVCJWNQIUCTSAJ-UHFFFAOYSA-J 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PPADPHPGTKCFIT-UHFFFAOYSA-L [Li+].[Li+].O.OP([O-])([O-])=O Chemical compound [Li+].[Li+].O.OP([O-])([O-])=O PPADPHPGTKCFIT-UHFFFAOYSA-L 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
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- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
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- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical group [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法、更に詳しくは特にリチウム二次電池正極活物質として有用なＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法に関するものである。 The present invention relates to a method for producing a lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms, and more specifically, a lithium iron phosphorus composite oxide carbon containing Mn atoms particularly useful as a positive electrode active material for a lithium secondary battery. The present invention relates to a method for producing a composite.
近年、家庭電器においてポータブル化、コードレス化が急速に進むに従い、ラップトップ型パソコン、携帯電話、ビデオカメラ等の小型電子機器の電源としてリチウムイオン二次電池が実用化されている。このリチウムイオン二次電池については、１９８０年に水島等によりコバルト酸リチウムがリチウムイオン二次電池の正極活物質として有用であるとの報告（「マテリアル リサーチブレティン」vol15,P783-789(1980)）がなされて以来、コバルト酸リチウムに関する研究開発が活発に進められており、これまで多くの提案がなされている。 In recent years, as home appliances have become portable and cordless, lithium ion secondary batteries have been put to practical use as power sources for small electronic devices such as laptop computers, mobile phones, and video cameras. Regarding this lithium ion secondary battery, in 1980, Mizushima et al. Reported that lithium cobalt oxide was useful as a positive electrode active material for lithium ion secondary batteries ("Material Research Bulletin" vol15, P783-789 (1980)). Since then, research and development on lithium cobaltate has been actively promoted, and many proposals have been made so far.
しかしながら、Ｃｏは地球上に偏在し、希少な資源であるため、コバルト酸リチウムに代わる新たな正極活物質として、例えば、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＦｅＯ2、ＬｉＦｅＰＯ4等の開発が進められている。 However, Co is unevenly distributed on the earth and is a scarce resource. Therefore, for example, LiNiO 2 , LiMn 2 O 4 , LiFeO 2 , LiFePO 4, etc. are being developed as new positive electrode active materials to replace lithium cobalt oxide. ing.
この中、リチウム鉄リン系複合酸化物に関して、ＬｉＦｅＰＯ4のＦｅをＭｎで置換したＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体が提案され（特許文献１〜３参照。）、このＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を正極活物質として用いたリチウム二次電池は、高放電容量となることが報告されている（例えば、特許文献１〜４参照。）。 Among these, regarding the lithium iron phosphorus composite oxide, a lithium iron phosphorus composite oxide carbon composite containing a Mn atom obtained by substituting Fe of LiFePO 4 with Mn has been proposed (see Patent Documents 1 to 3). It has been reported that a lithium secondary battery using a lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms as a positive electrode active material has a high discharge capacity (see, for example, Patent Documents 1 to 4). .
従来このＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法としては、例えば、炭酸リチウム、シュウ酸鉄、リン酸二水素アンモニウム、炭酸マンガン及び導電性炭素材料を反応原料とする方法（例えば、特許文献１〜３参照。）が提案されている。この炭酸リチウム、シュウ酸鉄、リン酸二水素アンモニウム及び炭酸マンガンの反応は、下記反応式（１）
また、リン酸を含む溶液中で、鉄、コバルト、マンガン、ニッケル、銅及びバナジウムから選ばれる金属を含有する１種又は複数種の化合物と、酢酸リチウム等のリチウムを含有する１種又は複数種の化合物を反応させ、その後所定の温度で焼成するリチウム鉄リン系複合酸化物の製造方法も提案されている（特許文献４参照。）。しかしこの方法は、少なくともＬｉ、Ｆｅ、Ｍｎ、Ｐの全ての組成調整を溶液中で行うものであり、各元素の組成調整が難しいという問題がある。 Further, in a solution containing phosphoric acid, one or more compounds containing a metal selected from iron, cobalt, manganese, nickel, copper and vanadium, and one or more kinds containing lithium such as lithium acetate There has also been proposed a method for producing a lithium iron-phosphorus composite oxide in which the above compound is reacted and then fired at a predetermined temperature (see Patent Document 4). However, this method has a problem that it is difficult to adjust the composition of each element, since at least all the composition adjustments of Li, Fe, Mn, and P are performed in a solution.
本発明者らは、かかる実情に鑑み、製造時に副生する有毒ガスの発生がなく、Ｌｉ、Ｆｅ、Ｍｎ、Ｐの各元素の組成調整が容易で、尚且つリチウム二次電池の正極活物質として使用することができるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を得る方法について鋭意研究を重ねた結果、２価の鉄塩と２価のマンガン塩及びリン酸を溶解した水溶液にアルカリを添加すると、定量的に鉄、マンガン及びリンを含む共沈体を得ることができ、この得られた共沈体とリン酸リチウム及び導電性炭素材料とを混合し得られる混合物を特定比容積まで粉砕処理して反応前駆体としたものを特定温度範囲で焼成することにより、リチウム二次電池の正極活物質として必要な平均粒径０．５μｍ以下の微細な粒子でＸ線回折分析からみて単相のリチウム鉄リン系複合酸化物炭素複合体となることを見出し、本発明を完成するに至った。 In view of such circumstances, the present inventors have no generation of toxic gas produced as a by-product during production, easy composition adjustment of each element of Li, Fe, Mn, and P, and a positive electrode active material for a lithium secondary battery As a result of diligent research on a method for obtaining a lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms that can be used as an aqueous solution in which a divalent iron salt, a divalent manganese salt, and phosphoric acid are dissolved When an alkali is added to the product, a coprecipitate containing iron, manganese and phosphorus can be quantitatively obtained, and a mixture obtained by mixing the obtained coprecipitate with lithium phosphate and a conductive carbon material is specified. X-ray diffraction analysis of fine particles with an average particle size of 0.5 μm or less required as a positive electrode active material for lithium secondary batteries by firing a reaction precursor that has been pulverized to a specific volume within a specific temperature range Single view It found that the lithium-iron-phosphorus complex oxide-carbon composite, and have completed the present invention.
即ち、本発明の目的は、製造時に有毒ガスの発生もなく、Ｌｉ、Ｆｅ、Ｍｎ、Ｐの各元素の組成調整が容易で、且つ平均粒径が０．５μｍ以下でＸ線回折分析からみて単相の、Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を工業的に有利な方法で製造する方法の提供にある。 That is, the object of the present invention is that no toxic gas is generated during production, the composition of each element of Li, Fe, Mn, and P can be easily adjusted, and the average particle size is 0.5 μm or less from the viewpoint of X-ray diffraction analysis. The object is to provide a method for producing a single-phase lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms in an industrially advantageous manner.
本発明が提供しようとするＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法は、２価の鉄塩と２価のマンガン塩及び該２価の鉄塩と該２価のマンガン塩中の鉄原子とマンガン原子の総量（Ｆｅ＋Ｍｎ）に対するモル比で０．６０〜０．７５のリン酸を溶解した水溶液にアルカリを添加し、鉄、マンガン及びリンを含む共沈体を得る第一工程、次いで得られた鉄、マンガン及びリンを含む共沈体、リン酸リチウム及び導電性炭素材料を混合する第二工程、次いで、得られた混合物を乾式で粉砕処理して比容積が１．５ｍL／ｇ以下の反応前駆体を得る第三工程、次いで、該反応前駆体を５００〜７００℃で焼成する第四工程を含むことを特徴とする、Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法である。
かかるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法において、前記第三工程後、得られた反応前駆体を加圧成形する工程を設けることが好ましい。
また、前記第二工程のリン酸リチウムは、平均粒径が１０μｍ以下で、格子面（０１０）面の半値幅が０．２°以上のものを用いることが好ましい。
The method for producing a lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms to be provided by the present invention includes a divalent iron salt, a divalent manganese salt, the divalent iron salt, and the divalent iron salt. Alkali is added to an aqueous solution in which phosphoric acid having a molar ratio of 0.60 to 0.75 is dissolved with respect to the total amount of iron atoms and manganese atoms (Fe + Mn) in the manganese salt to obtain a coprecipitate containing iron, manganese and phosphorus. The first step, then the second step of mixing the obtained coprecipitate containing iron, manganese and phosphorus, lithium phosphate and the conductive carbon material, and then the resulting mixture is pulverized by a dry process to obtain a specific volume. A lithium iron phosphorous system containing Mn atoms, comprising a third step of obtaining a reaction precursor of 1.5 mL / g or less, and then a fourth step of firing the reaction precursor at 500 to 700 ° C. In the manufacturing method of composite oxide carbon composite is there.
In the method for producing a lithium iron phosphorus composite oxide-carbon composite containing Mn atoms, it is preferable to provide a step of pressure-molding the obtained reaction precursor after the third step.
Moreover, it is preferable to use the lithium phosphate of said 2nd process whose average particle diameter is 10 micrometers or less and whose half value width of a lattice plane (010) plane is 0.2 degrees or more.
本発明のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法によれば、製造時に有毒ガスの発生もなく、また、Ｌｉ、Ｆｅ、Ｍｎ、Ｐの各元素の組成調整が容易で、且つリチウム二次電池の正極活物質としての用途に期待できる平均粒径が０．５μｍ以下の粒子で、Ｘ線回折分析からみて単相のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を工業的に有利に製造することができる。 According to the method for producing a lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms of the present invention, no toxic gas is generated during production, and composition adjustment of each element of Li, Fe, Mn, and P is possible. Lithium iron-phosphorus composite oxide that is easy and has an average particle size of 0.5 μm or less that can be expected for use as a positive electrode active material of a lithium secondary battery, and that contains single-phase Mn atoms as seen from X-ray diffraction analysis A carbon composite can be produced industrially advantageously.
以下、本発明をその好ましい実施形態に基づき詳細に説明する。
本発明の第一工程は、２価の鉄塩と２価のマンガン塩及びリン酸を溶解した水溶液に、アルカリを添加し、鉄、マンガン及びリンを含む共沈体を得る工程である。
Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
The first step of the present invention is a step of obtaining a coprecipitate containing iron, manganese and phosphorus by adding an alkali to an aqueous solution in which a divalent iron salt, a divalent manganese salt and phosphoric acid are dissolved.
第一工程で用いる２価の鉄塩としては、例えば、硫酸第一鉄、酢酸鉄、蓚酸鉄等が挙げられ、これらは、含水物であっても無水物であってもよい。 Examples of the divalent iron salt used in the first step include ferrous sulfate, iron acetate, and iron oxalate, and these may be hydrated or anhydrous.
また、用いることができる２価のマンガン塩としては、例えば、硝酸マンガン、硫酸マンガン、塩化マンガン、酢酸マンガン等が挙げられ、これらは、含水物であっても無水物であってもよい。 Examples of the divalent manganese salt that can be used include manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, and the like, and these may be hydrated or anhydrous.
また、用いることができるリン酸としては、工業的に入手できるものであれば特に制限なく用いることができる。 Moreover, as phosphoric acid that can be used, any industrially available phosphoric acid can be used without particular limitation.
また、用いることができるアルカリとしては、特に制限はなく、例えば、アンモニアガス、アンモニア水、水酸化ナトリウム、水酸化カリウム、ＮａＨＣＯ3、Ｎａ2ＣＯ3、ＬｉＯＨ、Ｋ2ＣＯ3、ＫＨＣＯ3、Ｃａ（ＯＨ）2等の無機アルカリ、またはエタノールアミン等の有機アルカリ等が挙げられる。これらのアルカリは１種又は２種以上で用いることができ、この中、水酸化ナトリウムが安価で工業的に入手しやすいことから特に好ましい。 As the alkali which can be used is not particularly limited, for example, ammonia gas, aqueous ammonia, sodium hydroxide, potassium hydroxide, NaHCO 3, Na 2 CO 3 , LiOH, K 2 CO 3, KHCO 3, Ca An inorganic alkali such as (OH) 2 or an organic alkali such as ethanolamine can be used. These alkalis can be used alone or in combination of two or more. Among them, sodium hydroxide is particularly preferable because it is inexpensive and easily available industrially.
これらの原料の２価の鉄塩、２価のマンガン塩、リン酸及びアルカリは、高純度のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を得る上で不純物含有量が少ないものを用いることが特に好ましい The divalent iron salt, divalent manganese salt, phosphoric acid, and alkali of these raw materials have a small impurity content in obtaining a lithium iron-phosphorus-based composite oxide carbon composite containing high-purity Mn atoms. It is particularly preferable to use
第一工程の操作は、まず、リン酸を２価の鉄塩と２価のマンガン塩中のＦｅ原子とＭｎ原子の総量（Ｆｅ＋Ｍｎ）に対するモル比で０．６０〜０．７５、好ましくは０．６５〜０．７０となるように２価の鉄塩、２価のマンガン塩及びリン酸を溶解した水溶液を調整する。なお、本発明において、水溶液中のＦｅ原子とＭｎ原子の配合割合は任意に設定することができる。２価の鉄塩、２価のマンガン塩及びリン酸を溶解した水溶液濃度は、２価の鉄塩、２価のマンガン塩及びリン酸を溶解できる濃度であれば特に制限はないが、通常、２価の鉄塩と２価のマンガン塩を総量で０．１モル／Ｌ以上、好ましくは０．１〜１．０モル／Ｌとすることが好ましい。 In the operation of the first step, first, phosphoric acid is 0.60 to 0.75 in terms of molar ratio to the total amount of Fe atoms and Mn atoms (Fe + Mn) in divalent iron salt and divalent manganese salt, preferably 0. An aqueous solution in which a divalent iron salt, a divalent manganese salt, and phosphoric acid are dissolved is prepared so that the pH is 65 to 0.70. In the present invention, the mixing ratio of Fe atoms and Mn atoms in the aqueous solution can be arbitrarily set. The concentration of the aqueous solution in which the divalent iron salt, divalent manganese salt and phosphoric acid are dissolved is not particularly limited as long as it is a concentration capable of dissolving the divalent iron salt, divalent manganese salt and phosphoric acid. The total amount of divalent iron salt and divalent manganese salt is 0.1 mol / L or more, preferably 0.1 to 1.0 mol / L.
次いで、この水溶液にアルカリを添加し、鉄、マンガン及びリンを含む共沈体を析出させる。鉄、マンガン及びリンを含む共沈体の析出反応は、このアルカリの添加により速やかに進行する。アルカリの添加量は、２価の鉄塩及び２価のマンガン塩の総量に対するモル比で１．８〜２．０、好ましくは１．９５〜２．０である。 Next, an alkali is added to the aqueous solution to precipitate a coprecipitate containing iron, manganese and phosphorus. The precipitation reaction of the coprecipitate containing iron, manganese and phosphorus proceeds rapidly by the addition of this alkali. The addition amount of the alkali is 1.8 to 2.0, preferably 1.95 to 2.0 as a molar ratio with respect to the total amount of the divalent iron salt and the divalent manganese salt.
このアルカリの添加温度は、特に制限はなく、通常５〜８０℃、好ましくは１５〜３５℃である。また、アルカリの滴下速度等は特に制限されるものではないが、安定した品質のものを得るため一定の滴下速度で除々に反応系内に導入することが好ましい。 There is no restriction | limiting in particular in the addition temperature of this alkali, Usually, 5-80 degreeC, Preferably it is 15-35 degreeC. The alkali dropping rate is not particularly limited, but it is preferable to gradually introduce it into the reaction system at a constant dropping rate in order to obtain a stable quality.
反応終了後、常法により固液分離して、共沈体を回収し、洗浄、乾燥して製品とする。 After completion of the reaction, solid-liquid separation is performed by a conventional method, and the coprecipitate is recovered, washed and dried to obtain a product.
なお、洗浄は、特に、アルカリとして水酸化ナトリウムを用いた場合には、析出した共沈体のＮａ含有量が１重量％以下、好ましくは０．８重量％以下となるまで水で十分に洗浄することが好ましい。 In particular, when sodium hydroxide is used as the alkali, the washing is sufficiently performed with water until the Na content of the precipitated coprecipitate is 1% by weight or less, preferably 0.8% by weight or less. It is preferable to do.
また、乾燥は、３５℃未満では乾燥に時間がかかり、５０℃を超えると２価の鉄及び２価のマンガン塩の酸化や結晶水の脱離が起こるため３５〜５０℃で行うことが好ましい。 In addition, drying is preferably performed at 35 to 50 ° C. since drying takes time when the temperature is lower than 35 ° C., and oxidation of divalent iron and divalent manganese salts and elimination of crystal water occur when the temperature exceeds 50 ° C. .
第二工程は、第一工程で得られた共沈体とリン酸リチウム及び導電性炭素材料を混合する工程である。 The second step is a step of mixing the coprecipitate obtained in the first step, lithium phosphate and a conductive carbon material.
この第二工程で用いる原料のリン酸リチウムは、工業的に入手できるものであれば特に制限はないが、走査型電子顕微鏡写真から求められる平均粒径が１０μｍ以下、好ましくは１〜５μｍで、更に線源としてCuKα線を用いて該リン酸リチウムをＸ線回折分析したときに２θ＝１６．８°近傍の回折ピーク（０１０）面の半値幅が０．２°以上、好ましくは０．２〜０．３°の結晶性が低く粉砕等の加工性及び反応性に優れたリン酸リチウムを用いると後述する反応前駆体の比容積を容易に１．５ｍＬ／ｇ以下とすることができることから特に好ましく、また、該リン酸リチウムは上記特性に加えて、安息角が５０度以下、好ましくは３０〜５０度の微細な一次粒子が一次粒子の集合体を形成してなり、該一次粒子の集合体の平均粒径が当該範囲の１０μｍ以下のリン酸リチウム凝集体を用いると各原料の均一分散性が良好となるため特に好ましい。 The raw material lithium phosphate used in the second step is not particularly limited as long as it is industrially available, but the average particle size determined from a scanning electron micrograph is 10 μm or less, preferably 1 to 5 μm. Further, when the lithium phosphate is subjected to X-ray diffraction analysis using CuKα ray as a radiation source, the half-value width of the diffraction peak (010) plane near 2θ = 16.8 ° is 0.2 ° or more, preferably 0.2 Since the specific volume of the reaction precursor described later can be easily reduced to 1.5 mL / g or less by using lithium phosphate having a low crystallinity of ˜0.3 ° and excellent workability and reactivity such as pulverization. Particularly preferably, in addition to the above-mentioned characteristics, the lithium phosphate has a repose angle of 50 degrees or less, preferably 30 to 50 degrees, and fine primary particles form an aggregate of primary particles. The average particle size of the aggregate is in this range Particularly preferred for uniform dispersibility of the raw material and using the following lithium phosphate aggregates 10μm is improved.
このようなリン酸リチウムは、水酸化リチウムを含む水溶液とリン酸を含む水溶液との反応によりリン酸リチウムを製造する方法において、用いる水酸化リチウム水溶液の濃度を４〜６重量％とし、更に反応条件において反応温度を７０℃以下、好ましくは５〜４０℃で反応を行うことにより製造することができる。 Such lithium phosphate is used in a method for producing lithium phosphate by a reaction between an aqueous solution containing lithium hydroxide and an aqueous solution containing phosphoric acid. It can be produced by carrying out the reaction at a reaction temperature of 70 ° C. or lower, preferably 5 to 40 ° C. under the conditions.
用いることができる水酸化リチウムは、工業的に入手可能なものであれば特に制限はなく含水物であっても無水物であってもよいが、高純度のリン酸リチウムを得る上で不純物含有量が少ないものを用いることが好ましく、特に工業的に入手可能な水酸化リチウムにはＮａが２０ｐｐｍ以上、Ｃａが６０ｐｐｍ以上、Ａｌが１００ｐｐｍ以上、Ｓｉが１００ｐｐｍ以上含有されていることから、これらの不純物を除去した精製水酸化リチウムを用いることが高純度のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を得る上で特に好ましい。この精製水酸化リチウムは、水酸化リチウムを含む水溶液を精密濾過した後、晶析を行うことによりＮａ、Ｃａ、Ａｌ、Ｓｉ等の不純物を低減した精製水酸化リチウムであることが好ましい（特願２００３−１３１０３２号参照。）。 The lithium hydroxide that can be used is not particularly limited as long as it is industrially available, and may be a hydrate or an anhydride, but it contains impurities to obtain a high purity lithium phosphate. It is preferable to use a small amount of lithium hydroxide, and industrially available lithium hydroxide contains Na of 20 ppm or more, Ca of 60 ppm or more, Al of 100 ppm or more, and Si of 100 ppm or more. It is particularly preferable to use purified lithium hydroxide from which impurities have been removed, in order to obtain a lithium iron-phosphorus composite oxide carbon composite containing high-purity Mn atoms. The purified lithium hydroxide is preferably purified lithium hydroxide in which impurities such as Na, Ca, Al, Si, etc. are reduced by microfiltration of an aqueous solution containing lithium hydroxide and crystallization. 2003-131032).
第二工程で用いる原料の導電性炭素材料としては、例えば、鱗状黒鉛、鱗片状黒鉛及び土状黒鉛等の天然黒鉛及び人工黒鉛等の黒鉛、カーボンブラック、アセチレンブラック、ケッチェンブラック（登録商標）、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等のカーボンブラック類、炭素繊維等が挙げられ、これらは１種又は２種以上で用いることができる。この中、ケッチェンブラック（登録商標）が微粒なものを工業的に容易に入手できるため特に好ましい。 Examples of the conductive carbon material used in the second step include natural graphite such as scaly graphite, scaly graphite, and earth graphite, and graphite such as artificial graphite, carbon black, acetylene black, and ketjen black (registered trademark). , Carbon blacks such as channel black, furnace black, lamp black and thermal black, carbon fibers, and the like, and these may be used alone or in combination of two or more. Among these, ketjen black (registered trademark) with fine particles is particularly preferable because it can be easily obtained industrially.
これらの導電性炭素材料は走査型電子顕微鏡写真から求められる平均粒径が１μｍ以下、好ましくは０．１μｍ以下、特に好ましくは０．０１〜０．１μｍであると得られるＭｎ原子を含有するリチウム鉄リン系複合酸化物の粒子表面に高分散状態で付着させることができることから好ましい。 These conductive carbon materials have an average particle size determined from a scanning electron micrograph of 1 μm or less, preferably 0.1 μm or less, particularly preferably 0.01 to 0.1 μm, and lithium containing Mn atoms. This is preferable because it can be adhered in a highly dispersed state to the particle surface of the iron-phosphorus composite oxide.
第二工程の操作は、まず、前記第一工程で得られた鉄、マンガン及びリンを含む共沈体、リン酸リチウムおよび導電性炭素材料を所定量混合する。 In the operation of the second step, first, a predetermined amount of the coprecipitate containing iron, manganese and phosphorus obtained in the first step, lithium phosphate and a conductive carbon material is mixed.
鉄、マンガン及びリンを含む共沈体及びリン酸リチウムの配合割合は、該共沈体中のＦｅ原子、Ｍｎ原子及びリン酸リチウム中のＬｉ原子のモル比として、Ｌｉ／（Ｆｅ＋Ｍｎ）で０．９〜１．１、好ましくは１．００〜１．０５であると、Ｍｎ原子を含有するリチウム鉄リン系複合酸化物の単相が得られる点で特に好ましい。 The mixing ratio of the coprecipitate containing iron, manganese and phosphorus and the lithium phosphate is 0.9 in terms of Li / (Fe + Mn) as the molar ratio of Fe atom, Mn atom in the coprecipitate and Li atom in the lithium phosphate. -1.1, preferably 1.00-1.05 is particularly preferred in that a single phase of a lithium iron-phosphorus composite oxide containing Mn atoms can be obtained.
また、導電性炭素材料は、焼成前に比べて焼成後では導電性炭素材料に含まれるＣ原子の量が若干ながら減少する傾向があることから、導電性炭素材料の配合量が鉄、マンガン及びリンを含む共沈体及びリン酸リチウムの総量に対して０．０８〜１５．５重量％、好ましくは３．８〜９．５重量％であると、導電性炭素材料の被覆量は、Ｍｎ原子を含有するリチウム鉄リン系複合酸化物に対するＣ原子の含有量で０．１〜２０重量％、好ましくは５〜１２重量％となる。この導電性炭素材料の配合量が０．０８重量％未満では、例えば、該Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体をリチウム二次電池の正極活物質として用いた場合に十分に導電性を付与することができなくなるため得られるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を正極活物質とするリチウム二次電池において内部抵抗が上昇しやすくなり、一方、１５．５重量％を超えると逆に重量或いは体積当たりの放電容量が減少しやすくなるため好ましくない。 In addition, since the conductive carbon material has a tendency to slightly decrease the amount of C atoms contained in the conductive carbon material after firing compared to before firing, the compounding amount of the conductive carbon material is iron, manganese and When the amount of the conductive carbon material is 0.08 to 15.5% by weight, preferably 3.8 to 9.5% by weight, based on the total amount of the coprecipitate containing phosphorus and lithium phosphate, The C atom content relative to the lithium iron phosphorus-based composite oxide containing atoms is 0.1 to 20% by weight, preferably 5 to 12% by weight. When the blending amount of the conductive carbon material is less than 0.08% by weight, for example, it is sufficient when the lithium iron phosphorus composite oxide carbon composite containing the Mn atom is used as a positive electrode active material of a lithium secondary battery. In the lithium secondary battery using the obtained lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms as the positive electrode active material, the internal resistance tends to increase. On the other hand, if it exceeds 5% by weight, the discharge capacity per unit weight or volume tends to decrease.
なお、第二工程において、後述する第三工程を実施するに当り予め各原料が均一に混合するようにブレンダー等を用いて乾式で十分に混合しておくことが好ましい。 In the second step, it is preferable that the raw material is sufficiently mixed by a dry method using a blender or the like so that the respective raw materials are uniformly mixed in advance in performing the third step described later.
第三工程は、第二工程で得られた原料混合物を、更に反応性をよくするため粉砕機を用いて乾式で十分に混合及び粉砕処理して反応前駆体を得る工程である。 Third step, a raw material mixture obtained in the second step is a step of obtaining a reaction precursor was thoroughly mixed and pulverized using a further order crusher you good reactivity dry.
この第三工程では、前記原料混合物を後述する比容積の範囲となるまで十分に乾式で混合及び粉砕処理することが重要な要件となる。
ここで前記反応前駆体とは前記原料の鉄、マンガン及びリンを含む共沈体、リン酸リチウム及び導電性炭素材料を含有する混合物を後の焼成に先だって反応性をよくするために、各原料を高分散させると共に各原料間の粒子間距離を可能なかぎり近づけ、各原料の接触面積を高めたものである。
In this third step, it is an important requirement to sufficiently dry and mix and pulverize the raw material mixture until it reaches the specific volume range described below.
Here, in order to improve the reactivity of the mixture containing the raw material iron, manganese and phosphorus containing coprecipitate, lithium phosphate and conductive carbon material prior to the subsequent firing, And the distance between particles between the raw materials is made as close as possible to increase the contact area of the raw materials.
本発明においてこの粉砕処理後の混合物は比容積が１．５ｍｌ／ｇ以下、好ましくは１．０〜１．４ｍｌ／ｇであると５００〜７００℃の低温の焼成温度で焼結による粒成長もなく、走査型電子顕微鏡写真から求められる平均粒径が０．５μｍ以下で、Ｘ線回折分析において単相のＭｎ原子を含有するリチウム鉄リン系複合酸化物の粒子表面を導電性炭素材料で均一に被覆したＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体が得られることから、当該範囲の比容積の原料混合物を反応前駆体とする。 In the present invention, the mixture after the pulverization treatment has a specific volume of 1.5 ml / g or less, preferably 1.0 to 1.4 ml / g. In addition, the average particle size obtained from a scanning electron micrograph is 0.5 μm or less, and the surface of lithium iron phosphorus composite oxide particles containing a single-phase Mn atom in X-ray diffraction analysis is uniformly made of a conductive carbon material. Since a lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms coated on is obtained, a raw material mixture having a specific volume within this range is used as a reaction precursor.
なお、本発明における比容積とはＪＩＳ−Ｋ−５１０１に記載された見掛け密度又は見掛け比容の方法に基づいて、タップ法により５０ｍｌのメスシリンダーにサンプル１０ｇをいれ、５００回タップし静置後、容積を読みとり、下記式により求めたものである。
用いることができる乾式粉砕機としては、強力なせん断力を有する粉砕機が好ましく、このような強力なせん断力を有する粉砕機としては、転動ボールミル、振動ミル、遊星ミル、媒体攪拌ミル等を用いることが好ましい。この種の粉砕機は、容器中にボール、ビーズ等の粉砕媒体が入っており、主として媒体の剪断・摩擦作用によって粉砕を行う粉砕機である。このような装置としては市販されているものを利用することができる。 As the dry pulverizer that can be used, a pulverizer having a strong shearing force is preferable. Examples of the pulverizer having such a strong shearing force include a rolling ball mill, a vibration mill, a planetary mill, and a medium agitating mill. It is preferable to use it. This type of pulverizer is a pulverizer in which a pulverization medium such as balls and beads is contained in a container and pulverization is performed mainly by the shearing and frictional action of the medium. A commercially available apparatus can be used as such an apparatus.
粒状媒体の粒径は１〜２５ｍｍであると粉砕が十分に行えるため好ましい。この粒状媒体の材質は、ジルコニア、アルミナのセラミックビーズが、硬度が高く磨耗に強いこと及び材料の金属汚染を防止することができることから特に好ましい。
また、前記粒状媒体は、空間容積５０〜９０％で容器内に収納し、流動媒体による剪断力と摩擦力を適切に管理するため、粉砕機の運転条件を適宜調整して粉砕処理することが好ましい。
The particle size of the granular medium is preferably 1 to 25 mm because pulverization can be sufficiently performed. As the material of the granular medium, zirconia and alumina ceramic beads are particularly preferable since they have high hardness and resistance to wear and can prevent metal contamination of the material.
In addition, the granular medium is stored in a container with a space volume of 50 to 90%, and the shearing force and frictional force due to the fluid medium are appropriately managed. preferable.
また、本発明のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法において、必要に応じて、上記粉砕処理に加えて該反応前駆体を加圧成形処理して、更に各原料の接触面積を高めると、より完全に反応を進行させることができる。この場合、成形圧は、プレス機、仕込み量等により異なり、特に限定されるものではないが、通常５〜２００ＭＰaである。プレス成形機は、打錠機、ブリケットマシン、ローラコンパクター等好適に使用できるがプレスできるものであればよく、特に制限はない。 Further, in the method for producing a lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms of the present invention, if necessary, the reaction precursor is subjected to pressure molding treatment in addition to the above pulverization treatment, Increasing the contact area of the raw material allows the reaction to proceed more completely. In this case, the molding pressure varies depending on the press, the amount charged, etc., and is not particularly limited, but is usually 5 to 200 MPa. The press molding machine can be suitably used such as a tableting machine, a briquette machine, a roller compactor, etc., but may be any press as long as it can be pressed, and is not particularly limited.
次いで、第四工程において、前記第三工程で得られた反応前駆体を焼成する。
焼成温度は５００〜７００℃、好ましくは５５０〜６５０℃である。本発明において、この焼成温度を当該範囲とする理由は、焼成温度が５００℃未満では、反応が十分に進行しないため未反応原料が残存し、一方、７００℃を越えると上記したとおり焼結が進行して粒子成長が起こるためリチウム二次電池の正極活物質の用途に適しない特性を有するようになるため好ましくない。
焼成時間は、２〜２０時間、好ましくは５〜１０時間とすることが好ましい。
焼成は、Ｆｅ及びＭｎ元素の酸化を防止するため窒素、アルゴン等の不活性ガス雰囲気中又は水素や一酸化炭素等の還元雰囲気中で行うことが好ましい。また、これらの焼成は必要により何度でも行うことができる。
Next, in the fourth step, the reaction precursor obtained in the third step is baked.
The firing temperature is 500 to 700 ° C, preferably 550 to 650 ° C. In the present invention, the reason for setting the firing temperature in this range is that when the firing temperature is less than 500 ° C., the reaction does not proceed sufficiently, so that the unreacted raw material remains. Since it progresses and particle growth occurs, it is not preferable because it has characteristics that are not suitable for the use of the positive electrode active material of the lithium secondary battery.
The firing time is 2 to 20 hours, preferably 5 to 10 hours.
Firing is preferably performed in an inert gas atmosphere such as nitrogen or argon or in a reducing atmosphere such as hydrogen or carbon monoxide in order to prevent oxidation of Fe and Mn elements. Moreover, these baking can be performed as many times as necessary.
焼成後は、適宜冷却し、必要に応じ粉砕又は分級してＭｎ原子を含有するリチウム鉄リン系複合酸化物の粒子表面を導電性炭素材料で均一に被覆したＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体を得る。なお、ＦｅおよびＭｎ元素の酸化を防止するため、冷却中は反応系内を窒素、アルゴン等の不活性ガス雰囲気又は水素や一酸化炭素等の還元雰囲気として行うことが好ましい。また、必要に応じて行われる粉砕は、焼成して得られるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体がもろく結合したブロック状のものである場合等に適宜行うが、本発明のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の好ましい実施形態の製造方法によれば、該Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の粒子自体は下記の特定の平均粒径、ＢＥＴ比表面積を有するものである。即ち、得られるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体は、走査型電子顕微鏡写真（ＳＥＭ）から求められる平均粒径が０．５μｍ以下、好ましくは０．０５〜０．５μｍであり、ＢＥＴ比表面積が１０〜１００ｍ2／ｇ、好ましくは３０〜７０ｍ2／ｇである。 After firing, it is cooled appropriately, and pulverized or classified as necessary, and the lithium iron phosphorus-based composite oxide containing Mn atoms in which the particle surface of the lithium iron-phosphorus composite oxide containing Mn atoms is uniformly coated with a conductive carbon material. A composite oxide carbon composite is obtained. In order to prevent oxidation of Fe and Mn elements, it is preferable to perform the reaction system in an inert gas atmosphere such as nitrogen or argon or a reducing atmosphere such as hydrogen or carbon monoxide during cooling. In addition, the pulverization performed as necessary is appropriately performed when the lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms obtained by firing is in a brittlely bonded block form. According to the production method of a preferred embodiment of the lithium iron phosphorus-based composite oxide carbon composite containing Mn atoms, the particles of the lithium iron phosphorus composite oxide-carbon composite containing Mn atoms are specified as follows. Having an average particle size of BET and a BET specific surface area. That is, the obtained lithium iron phosphorus composite oxide-carbon composite containing Mn atoms has an average particle size of 0.5 μm or less, preferably 0.05 to 0.5 μm, as determined from a scanning electron micrograph (SEM). The BET specific surface area is 10 to 100 m 2 / g, preferably 30 to 70 m 2 / g.
本発明に係るＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法によれば、２価の鉄塩と２価のマンガン塩及びリン酸を溶解した水溶液にアルカリを添加して、水溶液中の鉄及びマンガンを不溶性のリン酸塩として共沈させることで、共沈体中に鉄及びマンガンの成分を定量的に、且つ高分散状態で存在させることができる。また、この共沈体とリン酸リチウム及び導電性炭素材料を反応原料として用いることで、従来にも増して各原料が均一分散化された反応前駆体を得ることができる。また、この共沈体とリン酸リチウムとの反応は下記反応式（２）
このような微細でＸ線回折分析からみて単相のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体は、特にリチウム二次電池の正極活物質としての用途に期待できる。この場合、その形態は、平均粒径０．０５μｍ以上０．５μｍ以下の一次粒子が集合してなる平均粒径１μｍ以上７５μｍ以下の一次粒子集合体であってもよい。更に、上記一次集合体において全体積の７０％以上、好ましくは８０％以上が粒径１μｍ以上２０μｍ以下であることが好ましく、また、該Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体は大気中で粉砕等を行うと得られる該リチウム鉄リン系複合酸化物炭素複合体には、３０００ｐｐｍ以上の水分が含有されているため、正極活物質として用いる前に真空乾燥等の操作を施して該リチウム鉄リン系複合酸化物炭素複合体の水分含有量を２０００ｐｐｍ以下、好ましくは１５００ｐｐｍ以下として用いることが好ましい。 In view of such fine X-ray diffraction analysis, the lithium iron-phosphorus-based composite oxide-carbon composite containing a single-phase Mn atom can be expected particularly for use as a positive electrode active material of a lithium secondary battery. In this case, the form may be a primary particle aggregate having an average particle diameter of 1 μm or more and 75 μm or less formed by aggregating primary particles having an average particle diameter of 0.05 μm or more and 0.5 μm or less. Furthermore, it is preferable that 70% or more, preferably 80% or more of the total volume in the primary aggregate is a particle size of 1 μm or more and 20 μm or less, and the lithium iron phosphorus composite oxide carbon composite containing the Mn atom. Since the lithium iron phosphorus-based composite oxide carbon composite obtained by pulverizing in the atmosphere contains 3000 ppm or more of water, an operation such as vacuum drying is performed before using as a positive electrode active material. Thus, it is preferable to use the lithium iron phosphorus composite oxide-carbon composite at a moisture content of 2000 ppm or less, preferably 1500 ppm or less.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。
[合成例１]；リン酸リチウムの合成
水酸化リチウムは、市販の水酸化リチウム１水塩を下記の精製操作を施したものを使用し、リン酸リチウムの合成原料とした。
この市販の水酸化リチウム試料中の主な不純物含有量を表１に示す。
なお、この不純物含有量は、ＩＣＰ質量分析法及び比濁法によって求めた値である。
次いで、上記で調製した粗製水酸化リチウムを溶解した水溶液を４０℃で孔径０．５μｍのＰＴＦＥ製メンブランフィルターを使用して濾過を行った。
次いで、９５℃に加温し、減圧下に水分を抑留しながら４時間晶析を行った。なお、回収した水分は３３００ｇであった。冷却後、常法により固液分離して析出した水酸化リチウムを回収し、次いで、減圧下に乾燥を行って精製水酸化リチウム試料とした。また、得られた精製水酸化リチウム（ＬｉＯＨ・Ｈ2Ｏ）試料中の主な不純物含有量を表２に示した。
次いでこの反応容器にリン酸を９．８重量％含むリン酸水溶液１０００ｇを８３ｍＬ／分の速度で反応系の温度を４０℃以下に維持しながら全量を約１２分間かけて滴下しリン酸リチウムを析出させた（ｐＨ １０．５）。
次に、ろ過してリン酸リチウムを回収した。
次いで、回収したリン酸リチウムを温度１１０℃で２０時間乾燥し、微細な一次粒子が集合した集合体の乾燥品を得た。得られた乾燥品をＸ線回折で分析したところＪＣＰＤＳカード番号（２５−１０３０）と回折パターンが一致していることから、この乾燥品はＬｉ3ＰＯ4であることを確認した。
得られたＬｉ3ＰＯ4の諸物性値を表３に示す。不純物含有量はＩＣＰ分光法により求めた。また、得られたＬｉ3ＰＯ4を線源としてＣｕＫα線を用いてＸ線回折分析を行い２θ＝１６．８近傍の回折ピーク（０１０）面の半値幅を測定した。また、一次粒子と一次粒子の集合体の粒径は走査型電子顕微鏡写真（ＳＥＭ）により求めた。
[Synthesis Example 1]; Synthesis of Lithium Phosphate Lithium hydroxide was obtained by subjecting a commercially available lithium hydroxide monohydrate to the following purification operation, and was used as a raw material for the synthesis of lithium phosphate.
Table 1 shows the main impurity contents in this commercially available lithium hydroxide sample.
The impurity content is a value obtained by ICP mass spectrometry and turbidimetry.
Next, the aqueous solution in which the crude lithium hydroxide prepared above was dissolved was filtered at 40 ° C. using a PTFE membrane filter having a pore size of 0.5 μm.
Next, the mixture was heated to 95 ° C. and crystallized for 4 hours while retaining moisture under reduced pressure. The recovered water was 3300 g. After cooling, the precipitated lithium hydroxide was recovered by solid-liquid separation by a conventional method, and then dried under reduced pressure to obtain a purified lithium hydroxide sample. Further, Table 2 shows main impurity contents in the obtained purified lithium hydroxide (LiOH.H 2 O) sample.
Next, 1000 g of an aqueous phosphoric acid solution containing 9.8% by weight of phosphoric acid was added dropwise to the reaction vessel at a rate of 83 mL / min over a period of about 12 minutes while maintaining the temperature of the reaction system at 40 ° C. or less. Precipitated (pH 10.5).
Next, it filtered and lithium phosphate was collect | recovered.
Next, the recovered lithium phosphate was dried at a temperature of 110 ° C. for 20 hours to obtain a dried product of aggregates in which fine primary particles were aggregated. When the obtained dried product was analyzed by X-ray diffraction, the diffraction pattern was in agreement with the JCPDS card number (25-1030), and it was confirmed that this dried product was Li 3 PO 4 .
Various physical properties of the obtained Li 3 PO 4 are shown in Table 3. The impurity content was determined by ICP spectroscopy. Further, X-ray diffraction analysis was performed using the obtained Li 3 PO 4 as a radiation source using CuKα rays, and the half width of the diffraction peak (010) plane in the vicinity of 2θ = 16.8 was measured. Moreover, the particle diameter of the aggregate | assembly of a primary particle and a primary particle was calculated | required by the scanning electron micrograph (SEM).
実施例１〜３及び参考例１〜２
（第一工程）
硫酸第一鉄７水和物と硫酸マンガン１水和物を表４に示したように，鉄とマンガンの総量に対するマンガンの割合 x（＝Ｍｎ／(Ｆｅ＋Ｍｎ)）が0，0.25，0.5，0.75，1.0となるように秤量し，純水25kgに溶解した。この溶液に75％リン酸を697g加えた。別に，25重量％水酸化ナトリウム水溶液を2560gはかり取り，純水を加え16kgとした。硫酸鉄‐硫酸マンガン‐リン酸の混合溶液に水酸化ナトリウム水溶液を定量ポンプで滴下し（温度１１〜１５℃），生じた沈殿を濾過，洗浄，乾燥し，表４に示した量の乾燥粉体を得た。鉄，マンガン，リンの各元素の含有割合をＩＣＰ質量分析法により求め、その結果を表４に示す。
Examples 1-3 and Reference Examples 1-2
(First step)
As shown in Table 4 for ferrous sulfate heptahydrate and manganese sulfate monohydrate, the ratio of manganese to the total amount of iron and manganese x (= Mn / (Fe + Mn)) is 0, 0.25, 0.5, 0.75. , 1.0 and was dissolved in 25 kg of pure water. To this solution, 697 g of 75% phosphoric acid was added. Separately, 2560 g of 25 wt% aqueous sodium hydroxide solution was weighed out and pure water was added to make 16 kg. A sodium hydroxide aqueous solution is dropped into a mixed solution of iron sulfate-manganese sulfate-phosphoric acid with a metering pump (temperature 11 to 15 ° C.), and the resulting precipitate is filtered, washed and dried. Got the body. The content ratio of each element of iron, manganese, and phosphorus was determined by ICP mass spectrometry, and the results are shown in Table 4.
（第二工程〜第四工程）
上記で合成した鉄、マンガン及びリンを含む共沈体，リン酸リチウム及び平均粒径が０．０５μｍのケッチェンブラック（登録商標）（ケッチェンブラックインターナショナル社製、商品名ＥＣＰ）を表５に示した所定量秤量し，ミキサーで混合した。
この混合物を振動ミルを用いて粉砕処理し，反応前駆体を得た。また、振動ミル粉砕品の比容積は、５０ｍＬのメスシリンダーにサンプル１０ｇを入れ、ユアサアイオニクス（株）製、ＤＵＡＬ ＡＵＴＯＴＡＰ装置にセットし、５００回タップした後、容積を読みとり下記式により求めた。
（数２）
比容積（ｍＬ／ｇ）＝Ｖ／Ｆ
（式中、Ｆ；受器内の処理した試料の質量（ｇ）、Ｖ；タップ後の試料の容量（ｍＬ）を示す。）
なお、振動ミルの運転条件は以下の通りである。
・振動数；１０００Ｈｚ
・処理時間；３分
・原料の仕込量；１２ｇ
(Second process to fourth process)
Table 5 shows coprecipitates containing iron, manganese and phosphorus, lithium phosphate, and Ketjen Black (registered trademark) (trade name ECP, manufactured by Ketjen Black International Co., Ltd.) having an average particle size of 0.05 μm. The indicated amount was weighed and mixed with a mixer.
This mixture was pulverized using a vibration mill to obtain a reaction precursor. Further, the specific volume of the vibration mill pulverized product was obtained by putting 10 g of a sample in a 50 mL measuring cylinder, setting it on a Yuasa Ionics Co., Ltd., DUAL AUTOTAP device, tapping 500 times, reading the volume, and obtaining the following formula. .
(Equation 2)
Specific volume (mL / g) = V / F
(Wherein, F represents the mass (g) of the processed sample in the receiver, and V represents the volume (mL) of the sample after tapping.)
The operating conditions of the vibration mill are as follows.
・ Frequency: 1000Hz
・ Processing time: 3 minutes ・ Material charge: 12 g
得られた反応前駆体の主物性を表５に示す。
次に、反応前駆体１０ｇをハンドプレスにより４４ＭＰａでプレス成形した。次いで、得られた粉砕品を窒素雰囲気下に600℃で5時間焼成し，冷却後，粉砕した。得られた粉体の平均粒径を走査型電子顕微鏡写真（ＳＥＭ）で求めた以外は主物性を合成例１と同様に求め，その結果を表５に示す。また，得られた粉体に対して，線源としてＣｕＫα線を用いてＸ線回折分析を行い，得られたＸＲＤパターンを図１に示す。このＸＲＤパターンは，オリビン構造を有する単相であることが分かった。ＸＲＤパターンの（200）面のピーク位置を詳細に見ると，ｘの値が0から1に向かって変化するにつれ，ピーク位置がリン酸鉄リチウムのピーク位置である29. 7°からリン酸マンガンリチウムのピーク位置である29.2°に向かって連続的に変化していることが分かった。これらのことから，得られた粉体は，鉄とマンガンが固溶したオリビン構造単相を示し，組成式ＬｉＦｅ1-xＭｎxＰＯ4で表されるリン酸（鉄‐マンガン）リチウムであるといえる。
Table 5 shows the main physical properties of the obtained reaction precursor.
Next, 10 g of the reaction precursor was press-molded at 44 MPa by hand press. Subsequently, the obtained pulverized product was fired at 600 ° C. for 5 hours in a nitrogen atmosphere, cooled and pulverized. The main physical properties were determined in the same manner as in Synthesis Example 1 except that the average particle size of the obtained powder was determined by scanning electron micrograph (SEM), and the results are shown in Table 5. The obtained powder was subjected to X-ray diffraction analysis using CuKα rays as a radiation source, and the obtained XRD pattern is shown in FIG. This XRD pattern was found to be a single phase having an olivine structure. Looking at the peak position on the (200) plane of the XRD pattern in detail, as the value of x changes from 0 to 1, the peak position is 29.7 °, which is the peak position of lithium iron phosphate, and manganese phosphate. It was found that it continuously changed toward 29.2 ° which is the peak position of lithium. From these results, the obtained powder is lithium phosphate (iron-manganese) which shows an olivine structure single phase in which iron and manganese are solid-solved and is represented by the composition formula LiFe 1-x Mn x PO 4. It can be said.
表５の結果より、本発明のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体の製造方法によれば原料仕込み量から求められる理論的なＭｎ／(Ｆｅ＋Ｍｎ)のモル比と焼成品（Ｍｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体）の実測値から求められるＭｎ／(Ｆｅ＋Ｍｎ)のモル比がほぼ一致していることから、Ｌｉ、Ｆｅ、Ｍｎ、Ｐの組成調整が容易であることが分かる。また、図１及び表６の結果より、本発明の製造方法で得られるＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体は、何れも平均粒径が０．５μｍ以下の微細な粒子で、また、Ｘ線回折分析からみて単相のＭｎ原子を含有するリチウム鉄リン系複合酸化物炭素複合体であることが分かる。 From the results of Table 5, the theoretical Mn / (Fe + Mn) molar ratio determined from the raw material charge and the calcined product according to the method for producing a lithium iron phosphorus composite oxide-carbon composite containing Mn atoms of the present invention Since the molar ratio of Mn / (Fe + Mn) obtained from the actual measurement value of (lithium iron phosphorus-based composite oxide-carbon composite containing Mn atoms) is almost the same, the composition adjustment of Li, Fe, Mn, and P Is easy to understand. From the results shown in FIG. 1 and Table 6, the lithium iron phosphorus composite oxide-carbon composite containing Mn atoms obtained by the production method of the present invention is a fine particle having an average particle size of 0.5 μm or less. From the X-ray diffraction analysis, it can be seen that the lithium iron phosphorus composite oxide-carbon composite contains a single-phase Mn atom.
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