JP2023125434A - Spinel type lithium manganese oxide, method for producing the same, and use thereof - Google Patents
Spinel type lithium manganese oxide, method for producing the same, and use thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims description 35
- 239000011029 spinel Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 105
- -1 phosphorus compound Chemical class 0.000 claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000011163 secondary particle Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910006554 Li1+xMn2-x-yMyO4 Inorganic materials 0.000 abstract 1
- 229910006601 Li1+xMn2−x−yMyO4 Inorganic materials 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 32
- 235000021317 phosphate Nutrition 0.000 description 32
- 239000010452 phosphate Substances 0.000 description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 30
- 238000005259 measurement Methods 0.000 description 29
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 20
- 238000003860 storage Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- 238000007600 charging Methods 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000009616 inductively coupled plasma Methods 0.000 description 8
- 238000010280 constant potential charging Methods 0.000 description 7
- 150000002642 lithium compounds Chemical class 0.000 description 7
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910012258 LiPO Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001766 barrel sputter deposition Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical class [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本開示は、スピネル型マンガン酸リチウム及びその製造方法並びにその用途に関するものであり、より詳しくは、リン化合物を含有したスピネル型マンガン酸リチウム及びその製造方法、並びにリチウムイオン二次電池に関する。 The present disclosure relates to a spinel-type lithium manganate, a method for producing the same, and a use thereof, and more particularly relates to a spinel-type lithium manganate containing a phosphorus compound, a method for producing the same, and a lithium ion secondary battery.
リチウムイオン二次電池はエネルギー密度が高いことから、携帯電話等の小型の電子機器に用いる電池として幅広く使用されている。最近では、定置用や車載用といった大型で大容量と高出力が必要とされる用途への適用が進められており、更なる高性能化が期待されている。 Lithium ion secondary batteries have a high energy density and are therefore widely used as batteries for small electronic devices such as mobile phones. Recently, they have been applied to applications that require large size, large capacity, and high output, such as stationary use and on-vehicle use, and further improvements in performance are expected.
現在のリチウムイオン二次電池の正極材料として、携帯電話等の民生用小型電池には主にコバルト系材料（ＬｉＣｏＯ２）が、定置用や車載用にはニッケル系材料（ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２）やニッケル－コバルト－マンガン三元系材料（ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２等）が主に使用されている。しかし、コバルト原料やニッケル原料は埋蔵量が少なく高価であり、多量の確保が難しいことに加え、出力特性があまり高くない。 As positive electrode materials for current lithium-ion secondary batteries, cobalt-based materials (LiCoO 2 ) are mainly used for small consumer batteries such as mobile phones, and nickel-based materials (LiNi 0.8 Co 0 ) are used for stationary and automotive applications. .15 Al 0.05 O 2 ) and nickel-cobalt-manganese ternary materials (LiNi 0.5 Co 0.2 Mn 0.3 O 2 etc.) are mainly used. However, cobalt raw materials and nickel raw materials have small reserves and are expensive, making it difficult to secure large quantities, and their output characteristics are not very high.
一方、マンガン系材料の一つであるスピネル型マンガン酸リチウムは、原料のマンガンが安価かつ豊富に存在するため多量に入手可能であり、また、安全性に優れることから、大型電池に適した材料の一つである。 On the other hand, spinel-type lithium manganate, which is a manganese-based material, can be obtained in large quantities because the raw material manganese is cheap and abundant, and it is also highly safe, making it a material suitable for large batteries. one of.
しかしながら、スピネル型マンガン酸リチウムは高温安定性、すなわち、高温における電池特性、特に保存特性や充放電特性に問題があり、この課題の解決が検討されていた。例えば、特許文献１及び特許文献２では、いずれもリン酸塩を含有したスピネル型マンガン酸リチウムが提案されているが、高温における電池特性に改善の余地を残している。 However, spinel-type lithium manganate has a problem with high-temperature stability, that is, battery characteristics at high temperatures, particularly storage characteristics and charge/discharge characteristics, and solutions to this problem have been investigated. For example, in Patent Document 1 and Patent Document 2, spinel-type lithium manganate containing phosphate is proposed, but there is still room for improvement in battery characteristics at high temperatures.
本開示の目的は、二次電池の電極として使用した際に、高温における電池特性、特に保存特性及び充放電特性に優れるスピネル型マンガン酸リチウム及びその製造方法の少なくともいずれかを提供することであり、さらには、該スピネル型マンガン酸リチウムを用いた電極、またはリチウムイオン二次電池を提供するものである。 An object of the present disclosure is to provide a spinel-type lithium manganate that has excellent battery characteristics at high temperatures, particularly storage characteristics and charge/discharge characteristics when used as an electrode of a secondary battery, and at least a method for producing the same. Furthermore, the present invention provides an electrode or a lithium ion secondary battery using the spinel type lithium manganate.
すなわち、本発明は特許請求の範囲のとおりであり、また、本開示の要旨は以下のとおりである。
（１） リン化合物を含有し、化学式Ｌｉ１＋ＸＭｎ２－Ｘ－ＹＭＹＯ４（式中、０．０２≦Ｘ≦０．２０、０．０５≦Ｙ≦０．３０であり、ＭはＡｌまたはＭｇである。）で表されるスピネル型マンガン酸リチウムであって、前記リン化合物のＢＥＴ比表面積が１０ｍ２／ｇ以上８０ｍ２／ｇ以下であるスピネル型マンガン酸リチウム。
（２） 前記リン化合物の含有量が０．１質量％以上１０質量％以下である（１）に記載のスピネル型マンガン酸リチウム。
（３） ＢＥＴ比表面積が０．２ｍ２／ｇ以上１．５ｍ２／ｇ以下である（１）又は（２）に記載のスピネル型マンガン酸リチウム。
（４） 二次粒子の平均粒子径が４．０μｍ以上２０．０μｍ以下である（１）乃至（３）のいずれかに記載のスピネル型マンガン酸リチウム。
（５） ＳＯ４の含有量が０．８質量％以下である（１）乃至（４）のいずれかに記載のスピネル型マンガン酸リチウム。
（６） Ｎａの含有量が３０００質量ｐｐｍ以下である（１）乃至（５）のいずれかに記載のスピネル型マンガン酸リチウム。
（７） マンガン源、リチウム源、並びに、アルミニウム及びマグネシウムの少なくともいずれかを含む金属源、を含む組成物を７５０℃以上９７０℃以下で焼成して焼成物を得る焼成工程と、該焼成物に前記リン化合物を含有させるリン化合物含有工程と、を有する、（１）乃至（６）のいずれかに記載のスピネル型マンガン酸リチウムの製造方法。
（８） （１）乃至（６）のいずれかに記載のスピネル型マンガン酸リチウムを含む電極。
（９） （８）に記載の電極を含むリチウムイオン二次電池。
That is, the present invention is as defined in the claims, and the gist of the present disclosure is as follows.
(1) Contains a phosphorus compound and has the chemical formula Li 1+X Mn 2-X-Y M Y O 4 (wherein, 0.02≦X≦0.20, 0.05≦Y≦0.30, and M is ), wherein the phosphorus compound has a BET specific surface area of 10 m 2 /g or more and 80 m 2 /g or less.
(2) The spinel type lithium manganate according to (1), wherein the content of the phosphorus compound is 0.1% by mass or more and 10% by mass or less.
(3) The spinel type lithium manganate according to (1) or (2), which has a BET specific surface area of 0.2 m 2 /g or more and 1.5 m 2 /g or less.
(4) The spinel type lithium manganate according to any one of (1) to (3), wherein the secondary particles have an average particle diameter of 4.0 μm or more and 20.0 μm or less.
(5) The spinel type lithium manganate according to any one of (1) to (4), wherein the content of SO 4 is 0.8% by mass or less.
(6) The spinel type lithium manganate according to any one of (1) to (5), wherein the Na content is 3000 mass ppm or less.
(7) A firing step of obtaining a fired product by firing a composition containing a manganese source, a lithium source, and a metal source containing at least one of aluminum and magnesium at a temperature of 750°C or higher and 970°C or lower; The method for producing spinel-type lithium manganate according to any one of (1) to (6), comprising a phosphorus compound-containing step of containing the phosphorus compound.
(8) An electrode containing the spinel-type lithium manganate according to any one of (1) to (6).
(9) A lithium ion secondary battery comprising the electrode according to (8).
本開示によれば、二次電池の電極として使用した際に、高温における電池特性、特に保存特性及び充放電特性に優れるスピネル型マンガン酸リチウム及びその製造方法の少なくともいずれかを提供することが可能になり。さらには、該スピネル型マンガン酸リチウムを用いた電極、またはリチウムイオン二次電池を提供することが可能になる。 According to the present disclosure, it is possible to provide at least one of a spinel-type lithium manganate and a method for producing the same, which has excellent battery characteristics at high temperatures, particularly storage characteristics and charge/discharge characteristics when used as an electrode of a secondary battery. become. Furthermore, it becomes possible to provide an electrode or a lithium ion secondary battery using the spinel type lithium manganate.
本開示について、一実施形態を示して詳細に説明するが、本開示は以下の実施形態に限定されるものではない。 Although the present disclosure will be described in detail by showing one embodiment, the present disclosure is not limited to the following embodiment.
本実施形態のスピネル型マンガン酸リチウムは、表面にリン化合物を有する。リン化合物としては、本願発明の効果が得られるものであれば特に限定されるものではないが、無機化合物であることが好ましく、さらにはリン酸塩であることが好ましく、例えば、Ｌｉ３ＰＯ４、ＬｉＰＯ３等のリチウムのリン酸塩、Ｎａ３ＰＯ４、ＮａＨ２ＰＯ４、Ｎａ２ＨＰＯ４等のナトリウムのリン酸塩、Ｋ３ＰＯ４、ＫＨ２ＰＯ４、Ｋ２ＨＰＯ４等のカリウムのリン酸塩等が挙げられる。好ましくはＬｉ３ＰＯ４、ＬｉＰＯ３であり、より好ましくはＬｉ３ＰＯ４である。以下、本明細書においては、リン化合物はリン酸塩として記載する。リン酸塩がスピネル型マンガン酸リチウムに含有されることにより、リチウムイオン二次電池の正極活物質として使用した際に優れた電池性能を示し、特に高温において優れた保存特性及び充放電特性を得ることが可能となる。含有されるリン酸塩の性状には特に制限はなく、結晶質性のもの、結晶質性で多孔性のもの、結晶質性で緻密なもの、非晶質性のもの、非晶質性で多孔性のもの、非晶質性で緻密な状態のもの等が例示されるが、これらに限定されない。 The spinel type lithium manganate of this embodiment has a phosphorus compound on the surface. The phosphorus compound is not particularly limited as long as it can achieve the effects of the present invention, but is preferably an inorganic compound, more preferably a phosphate, for example Li 3 PO 4 , lithium phosphates such as LiPO 3 , sodium phosphates such as Na 3 PO 4 , NaH 2 PO 4 , Na 2 HPO 4 , potassium phosphates such as K 3 PO 4 , KH 2 PO 4 , K 2 HPO 4 phosphates, etc. Preferred are Li 3 PO 4 and LiPO 3 , more preferred is Li 3 PO 4 . Hereinafter, in this specification, a phosphorus compound will be described as a phosphate. By containing phosphate in spinel-type lithium manganate, it exhibits excellent battery performance when used as a positive electrode active material for lithium ion secondary batteries, and provides excellent storage and charge/discharge characteristics, especially at high temperatures. becomes possible. There are no particular restrictions on the properties of the phosphates contained, and they may be crystalline, crystalline and porous, crystalline and dense, amorphous, or amorphous. Examples include porous ones and amorphous and dense ones, but are not limited to these.
本実施形態のスピネル型マンガン酸リチウムは、化学式Ｌｉ１＋ＸＭｎ２－Ｘ－ＹＭＹＯ４（式中、０．０２≦Ｘ≦０．２０、０．０５≦Ｙ≦０．３０であり、ＭはＡｌまたはＭｇである。）で表される。Ｘの値が０．０２未満であることで高温における保存及び充放電での容量低下が発生し、０．２０を超えることで十分な充放電容量が得られなくなる。また、Ｙの値が０．０５未満であると高温における保存及び充放電での容量低下が発生し、０．３０を超えると十分な充放電容量が得られなくなる。Ｘ及びＹはスピネル型マンガン酸リチウムを組成分析することで求めることができる。組成分析の方法としては、例えば、誘導結合プラズマ発光分析（以下、「ＩＣＰ」ともいう。）、原子吸光分析等が挙げられる。 The spinel-type lithium manganate of this embodiment has the chemical formula Li 1+X Mn 2-X-Y M Y O 4 (wherein, 0.02≦X≦0.20, 0.05≦Y≦0.30, M is Al or Mg.). If the value of Further, if the value of Y is less than 0.05, a capacity decrease occurs during storage and charging/discharging at high temperatures, and if it exceeds 0.30, sufficient charging/discharging capacity cannot be obtained. X and Y can be determined by analyzing the composition of spinel-type lithium manganate. Examples of compositional analysis methods include inductively coupled plasma emission spectroscopy (hereinafter also referred to as "ICP"), atomic absorption spectrometry, and the like.
本実施形態のスピネル型マンガン酸リチウムに含有されるリン酸塩はＢＥＴ比表面積が１０ｍ２／ｇ以上８０ｍ２／ｇ以下である。これにより、リチウムイオン二次電池の正極活物質として使用した際に、電解液中に含まれるフッ化水素をリン酸塩で捕捉する反応が速やかに進行する。その結果、フッ化水素とスピネル型マンガン酸リチウムの反応に起因するマンガン溶出が抑制され、高温において優れた保存特性及び充放電特性が得られる。リン酸塩のＢＥＴ比表面積が１０ｍ２／ｇ未満であることで、フッ化水素をリン酸塩で捕捉する反応が速やかに進行せず、８０ｍ２／ｇを超えることで、本実施形態のスピネル型マンガン酸リチウムを正極とした際の電極密度が低下する。リン酸塩のＢＥＴ比表面積は１０ｍ２／ｇ以上５０ｍ２／ｇ以下であることが好ましく、１０ｍ２／ｇ以上３０ｍ２／ｇ以下であることがより好ましい。リン酸塩のＢＥＴ比表面積は窒素ガス吸着法（ＢＥＴ法）から求めることができる。 The phosphate contained in the spinel-type lithium manganate of this embodiment has a BET specific surface area of 10 m 2 /g or more and 80 m 2 /g or less. As a result, when used as a positive electrode active material of a lithium ion secondary battery, a reaction in which hydrogen fluoride contained in the electrolyte is captured by the phosphate rapidly proceeds. As a result, manganese elution caused by the reaction between hydrogen fluoride and spinel-type lithium manganate is suppressed, and excellent storage and charge/discharge characteristics can be obtained at high temperatures. When the BET specific surface area of the phosphate is less than 10 m 2 /g, the reaction to capture hydrogen fluoride with the phosphate does not proceed quickly, and when it exceeds 80 m 2 /g, the spinel of this embodiment Electrode density decreases when type lithium manganate is used as a positive electrode. The BET specific surface area of the phosphate is preferably 10 m 2 /g or more and 50 m 2 /g or less, more preferably 10 m 2 /g or more and 30 m 2 /g or less. The BET specific surface area of phosphate can be determined by the nitrogen gas adsorption method (BET method).
本実施形態のスピネル型マンガン酸リチウムのリン酸塩の含有量は、０．１質量％以上１０質量％以下であることが好ましく、０．２質量％以上６質量％以下であることがより好ましい。これにより、本実施形態のスピネル型マンガン酸リチウムをリチウムイオン二次電池の正極活物質として使用した際の充放電容量がより大きくなる。本実施形態におけるリン酸塩の含有量は、スピネル型マンガン酸リチウムの質量に対する、スピネル型マンガン酸リチウムに含まれるＰ元素をＬｉ３ＰＯ４換算した質量の割合（質量％）である。すなわち、リン酸塩の含有量は、ＩＣＰ測定で求めたＰ元素の濃度（質量％）に、Ｌｉ３ＰＯ４／Ｐ（原子量比）をかけてＬｉ３ＰＯ４換算することで求めることができる。 The content of phosphate in the spinel-type lithium manganate of this embodiment is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 6% by mass or less. . Thereby, the charge/discharge capacity becomes larger when the spinel type lithium manganate of this embodiment is used as a positive electrode active material of a lithium ion secondary battery. The content of phosphate in this embodiment is the ratio (mass %) of the mass of the P element contained in the spinel-type lithium manganate in terms of Li 3 PO 4 to the mass of the spinel-type lithium manganate. That is, the content of phosphate can be determined by multiplying the concentration of P element (mass %) determined by ICP measurement by Li 3 PO 4 /P (atomic weight ratio) and converting it into Li 3 PO 4 . .
本実施形態のスピネル型マンガン酸リチウムに含有されるリン酸塩は多孔質であることが好ましい。リン酸塩が多孔質であることにより、リチウムイオン二次電池の正極活物質として使用した際に電解液中に含まれるフッ化水素をより速やかに補足できる。その結果、フッ化水素とスピネル型マンガン酸リチウムの反応に起因するマンガン溶出がさらに抑制され、高温において優れた保存特性及び充放電サイクル特性が得られる。リン酸塩が多孔質であることは、スピネル型マンガン酸リチウム粒子の断面ＴＥＭ－ＥＤＸ測定により判定することができる。 The phosphate contained in the spinel-type lithium manganate of this embodiment is preferably porous. Since the phosphate is porous, it can more quickly capture hydrogen fluoride contained in the electrolyte when used as a positive electrode active material of a lithium ion secondary battery. As a result, manganese elution caused by the reaction between hydrogen fluoride and spinel-type lithium manganate is further suppressed, and excellent storage characteristics and charge/discharge cycle characteristics are obtained at high temperatures. Whether the phosphate is porous can be determined by cross-sectional TEM-EDX measurement of spinel-type lithium manganate particles.
本実施形態のスピネル型マンガン酸リチウムのＢＥＴ比表面積は、０．２ｍ２／ｇ以上１．５ｍ２／ｇ以下であることが好ましく、０．２ｍ２／ｇ以上１．０ｍ２／ｇ以下であることがより好ましく、０．３ｍ２／ｇ以上０．８ｍ２／ｇ以下であることがさらに好ましい。これにより、リチウムイオン二次電池の正極活物質として使用した際に、高温においてより優れた保存特性及び充放電特性を得ることが可能になる。 The BET specific surface area of the spinel type lithium manganate of this embodiment is preferably 0.2 m 2 /g or more and 1.5 m 2 /g or less, and preferably 0.2 m 2 /g or more and 1.0 m 2 /g or less. It is more preferable that the area is 0.3 m 2 /g or more and 0.8 m 2 /g or less. Thereby, when used as a positive electrode active material of a lithium ion secondary battery, it becomes possible to obtain better storage characteristics and charge/discharge characteristics at high temperatures.
本実施形態のスピネル型マンガン酸リチウムの二次粒子の平均粒子径が４．０μｍ以上２０．０μｍ以下であることが好ましく、５．０μｍ以上１５．０μｍ以下であることがより好ましい。これにより、リチウムイオン二次電池の正極活物質として使用した際に、スピネル型マンガン酸リチウム粒子内のリチウム拡散距離がより小さくなり、より優れた出力特性を得ることが可能になるとともに、正極合剤の充填性をより高くすることが可能となる。 The average particle diameter of the spinel-type lithium manganate secondary particles of this embodiment is preferably 4.0 μm or more and 20.0 μm or less, and more preferably 5.0 μm or more and 15.0 μm or less. As a result, when used as a positive electrode active material in a lithium-ion secondary battery, the lithium diffusion distance within the spinel-type lithium manganate particles becomes smaller, making it possible to obtain better output characteristics, and It becomes possible to further improve the filling property of the agent.
ここで、「二次粒子」とはＬＭＯ粉末の一次粒子同士が凝集して焼結した粒子であり、「一次粒子」とは独立した結晶粒子である。本実施形態における二次粒子の平均粒子径は、粒度分布測定装置（例えば、ＭｉｃｒｏｔｒａｃＢＥＬ製 ＭＴ３０００ＩＩ）によって測定されるＤ５０である。二次粒子の平均粒子径はレーザー回折・散乱法によって測定される。 Here, the "secondary particles" are particles obtained by agglomerating and sintering the primary particles of the LMO powder, and are crystal particles independent of the "primary particles." The average particle diameter of the secondary particles in this embodiment is D50 measured by a particle size distribution measuring device (for example, MT3000II manufactured by MicrotracBEL). The average particle diameter of the secondary particles is measured by laser diffraction/scattering method.
本実施形態のスピネル型マンガン酸リチウムのＳＯ４の含有量は、０．８質量％以下であることが好ましく、０．５質量％以下であることがより好ましい。これにより、リチウムイオン二次電池の正極活物質として使用した際の充放電容量をより大きくするとともに、高温においてより優れた保存特性及び充放電特性を得ることができる。ＳＯ４の含有量は、０．０１質量％以上または０．０２質量％以上であることが例示できる。ＳＯ４の含有量（質量％）は、スピネル型マンガン酸リチウムの質量に対する、スピネル型マンガン酸リチウムに含まれるＳ元素をＳＯ４換算した質量の割合（質量％）である。すなわち、ＳＯ４の含有量は、ＩＣＰ測定で求めたＳ元素の濃度（質量％）に、ＳＯ４／Ｓ（原子量比）をかけてＳＯ４換算することで求めることができる。 The content of SO 4 in the spinel-type lithium manganate of this embodiment is preferably 0.8% by mass or less, more preferably 0.5% by mass or less. Thereby, it is possible to increase the charge/discharge capacity when used as a positive electrode active material of a lithium ion secondary battery, and to obtain better storage characteristics and charge/discharge characteristics at high temperatures. An example of the content of SO 4 is 0.01% by mass or more or 0.02% by mass or more. The SO 4 content (mass %) is the ratio (mass %) of the mass of the S element contained in the spinel-type lithium manganate in terms of SO 4 to the mass of the spinel-type lithium manganate. That is, the SO 4 content can be determined by multiplying the S element concentration (mass %) determined by ICP measurement by SO 4 /S (atomic weight ratio) and converting it into SO 4 .
含有されるＳＯ４の状態としては限定されるものではなく、例えば硫酸イオン及びＳＯ４基を含む化合物の少なくともいずれかが挙げられ、具体的には、Ｌｉ２ＳＯ４、Ｎａ２ＳＯ４等が例示できる。 The state of SO 4 contained is not limited, and includes, for example, at least one of a sulfate ion and a compound containing an SO 4 group, and specifically, Li 2 SO 4 , Na 2 SO 4 , etc. I can give an example.
本実施形態のスピネル型マンガン酸リチウムのＮａの含有量は、３０００質量ｐｐｍ以下であることが好ましく、１５００質量ｐｐｍ以下であることがより好ましく、１０００質量ｐｐｍ以下であることがさらに好ましい。これにより、リチウムイオン二次電池の正極活物質として使用した際の充放電容量をより大きくするとともに、高温においてより優れた保存特性及び充放電特性を得ることができる。Ｎａの含有量は、１０質量ｐｐｍ以上または２０質量ｐｐｍ以上であることが例示できる。Ｎａの含有量は、ＩＣＰ測定によって求めることができる。 The Na content of the spinel-type lithium manganate of this embodiment is preferably 3000 mass ppm or less, more preferably 1500 mass ppm or less, and even more preferably 1000 mass ppm or less. Thereby, it is possible to increase the charge/discharge capacity when used as a positive electrode active material of a lithium ion secondary battery, and to obtain better storage characteristics and charge/discharge characteristics at high temperatures. An example of the content of Na is 10 mass ppm or more or 20 mass ppm or more. The content of Na can be determined by ICP measurement.
含有されるＮａの状態としては限定されるものではなく、例えばＮａ金属、Ｎａを含む化合物及びＮａイオンからなる群より選ばれる少なくとも１つが挙げられ、具体的には、Ｎａ２ＳＯ４等が例示できる。 The state of Na contained is not limited, and includes, for example, at least one selected from the group consisting of Na metal, Na-containing compounds, and Na ions, and specific examples include Na 2 SO 4 and the like. can.
本実施形態のスピネル型マンガン酸リチウムのホウ素の含有量は、１０００質量ｐｐｍ以下であることが好ましく、５００質量ｐｐｍ以下であることがより好ましく、３００質量ｐｐｍ以下であることがさらに好ましい。これにより、リチウムイオン二次電池の正極活物質として使用した際の充放電容量をより大きくするとともに、高温においてより優れた保存特性及び充放電特性を得ることができる。ホウ素の含有量は、０質量ｐｐｍ以上であればよく、すなわち本実施形態のスピネル型マンガン酸リチウムに含まれていなくともよい。ホウ素の含有量は、ＩＣＰ測定によって求めることができる。 The boron content of the spinel-type lithium manganate of this embodiment is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 300 mass ppm or less. Thereby, it is possible to increase the charge/discharge capacity when used as a positive electrode active material of a lithium ion secondary battery, and to obtain better storage characteristics and charge/discharge characteristics at high temperatures. The content of boron may be 0 mass ppm or more, that is, it may not be contained in the spinel-type lithium manganate of this embodiment. The boron content can be determined by ICP measurement.
含有されるホウ素の状態としては限定されるものではなく、例えばホウ素金属、ホウ素を含む化合物及びホウ素イオンからなる群より選ばれる少なくとも１つが挙げられ、具体的には、Ｂ２Ｏ３、Ｌｉ２Ｂ４Ｏ７等が例示できる。 The state of boron contained is not limited, and includes, for example, at least one selected from the group consisting of boron metal, boron-containing compounds, and boron ions, and specifically, B 2 O 3 , Li 2 Examples include B 4 O 7 and the like.
次に、本実施形態のスピネル型マンガン酸リチウムの製造方法について説明する。 Next, a method for producing spinel-type lithium manganate of this embodiment will be described.
本実施形態のスピネル型マンガン酸リチウムは、マンガン源、リチウム源、並びに、アルミニウム及びマグネシウムの少なくともいずれかを含む金属Ｍ源、を混合して混合物を得る混合工程と、該混合物を７５０℃以上９７０℃以下で焼成して焼成物を得る焼成工程と、該焼成物にリン化合物を含有させるリン化合物含有工程と、を有する製造方法によって製造することができる。 The spinel-type lithium manganate of the present embodiment includes a mixing step of obtaining a mixture by mixing a manganese source, a lithium source, and a metal M source containing at least one of aluminum and magnesium, and heating the mixture at a temperature of 750° C. or higher and 970° C. It can be manufactured by a manufacturing method including a firing step of obtaining a fired product by firing at a temperature of ˚C or lower, and a phosphorus compound-containing step of making the fired product contain a phosphorus compound.
混合工程では、少なくともマンガン源、リチウム源、並びに、アルミニウム及びマグネシウムの少なくともいずれかを含む金属Ｍ源、を混合して混合物を得る。マンガン源、リチウム源、及び、金属Ｍ源が均一に混合されれば、混合方法は湿式混合又は乾式混合のいずれであってもよい。より均一な混合粉末が得られるため、混合方法は湿式混合であることが好ましい。 In the mixing step, at least a manganese source, a lithium source, and a metal M source containing at least one of aluminum and magnesium are mixed to obtain a mixture. As long as the manganese source, lithium source, and metal M source are mixed uniformly, the mixing method may be either wet mixing or dry mixing. The mixing method is preferably wet mixing because a more uniform mixed powder can be obtained.
マンガン源は特に限定されるものではなく、例えば、ＭｎＯ２、Ｍｎ３Ｏ４、Ｍｎ２Ｏ３のほか、酢酸マンガンのような有機酸塩が挙げられる。 The manganese source is not particularly limited, and includes, for example, MnO 2 , Mn 3 O 4 , Mn 2 O 3 and organic acid salts such as manganese acetate.
リチウム源は特に限定されるものではなく、例えば、炭酸リチウム、水酸化リチウム、硝酸リチウム、塩化リチウム、ヨウ化リチウム、シュウ酸リチウムのようなリチウム塩が挙げられる。 The lithium source is not particularly limited, and examples thereof include lithium salts such as lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium iodide, and lithium oxalate.
金属Ｍ源は、マグネシウム源及びアルミニウム源の少なくともいずれかを含む。 The metal M source includes at least one of a magnesium source and an aluminum source.
マグネシウム源としては、例えば、水酸化マグネシウム、酸化マグネシウム、炭酸マグネシウムの少なくともいずれかが挙げられる。 Examples of the magnesium source include at least one of magnesium hydroxide, magnesium oxide, and magnesium carbonate.
アルミニウム源としては、例えば、水酸化アルミニウム、オキシ水酸化アルミニウム、酸化アルミニウムの少なくともいずれかが挙げられる。 Examples of the aluminum source include at least one of aluminum hydroxide, aluminum oxyhydroxide, and aluminum oxide.
混合物は、必要に応じてバインダー、導電助剤、その他の添加物を含んでいてもよい。例えば、融剤としてホウ素化合物を混合することが好ましい。これにより、本実施形態のスピネル型マンガン酸リチウムのＢＥＴ比表面積を低下させることができる。ホウ素化合物は特に制限はなく、例えば、Ｈ３ＢＯ３、Ｂ２Ｏ３、Ｌｉ２Ｏ・ｎＢ２Ｏ３（ｎ＝１～５）等が挙げられる。 The mixture may contain a binder, a conductive aid, and other additives as necessary. For example, it is preferable to mix a boron compound as a fluxing agent. Thereby, the BET specific surface area of the spinel type lithium manganate of this embodiment can be reduced. The boron compound is not particularly limited, and examples thereof include H 3 BO 3 , B 2 O 3 , Li 2 O·nB 2 O 3 (n=1 to 5), and the like.
焼成工程は、混合工程で得られた混合物を焼成することにより、焼成物を得る工程である。焼成温度は、７５０℃以上９７０℃以下で行う。焼成温度が７５０℃未満であることで、スピネル型マンガン酸リチウムのＢＥＴ比表面積が大きくなる。その結果、リチウムイオン二次電池の正極活物質として使用した際にマンガンの溶出が進行しやすく、保存特性及び充放電特性が低下しやすい。焼成温度が９７０℃を超えることで、スピネル型マンガン酸リチウムの酸素欠損が増加する。その結果、リチウムイオン二次電池の正極活物質として使用した際に保存特性及び充放電特性が低下しやすい。さらには、焼成温度は８００℃以上９５０℃以下で行うことが好ましい。焼成時間は、製造コストを下げるため、３時間以上１２時間以下であることが好ましい。 The firing step is a step of obtaining a fired product by firing the mixture obtained in the mixing step. The firing temperature is 750°C or higher and 970°C or lower. When the firing temperature is less than 750° C., the BET specific surface area of the spinel-type lithium manganate increases. As a result, when used as a positive electrode active material of a lithium ion secondary battery, manganese tends to be eluted, and storage characteristics and charge/discharge characteristics tend to deteriorate. When the firing temperature exceeds 970° C., oxygen vacancies in the spinel-type lithium manganate increase. As a result, when used as a positive electrode active material of a lithium ion secondary battery, storage characteristics and charge/discharge characteristics tend to deteriorate. Furthermore, the firing temperature is preferably 800°C or higher and 950°C or lower. The firing time is preferably 3 hours or more and 12 hours or less in order to reduce manufacturing costs.
焼成雰囲気は特に限定されないが、例えば、大気中、又は、高濃度酸素雰囲気中（純粋酸素雰囲気中を含む）、すなわち、酸素含有量が１８ｖｏｌ％以上１００ｖｏｌ％以下の酸素雰囲気中で行うことが好ましい。 The firing atmosphere is not particularly limited, but it is preferable to perform the firing in the air or in a high concentration oxygen atmosphere (including a pure oxygen atmosphere), that is, in an oxygen atmosphere with an oxygen content of 18 vol% or more and 100 vol% or less. .
リン化合物含有工程は、焼成工程で得られた焼成物にリン化合物を含有させる工程である。以下、本明細書においては、リン化合物含有工程はリン酸塩含有工程として記載する。焼成物へリン酸塩を含有させる方法としては特に限定されないが、例えば、リチウム化合物の溶液及びリン化合物の溶液を添加して混合した後、ろ過及び乾燥を行う、晶析法が挙げられる。 The phosphorus compound-containing step is a step in which the fired product obtained in the firing step contains a phosphorus compound. Hereinafter, in this specification, the phosphorus compound-containing step will be described as a phosphate-containing step. The method for incorporating phosphate into the fired product is not particularly limited, but includes, for example, a crystallization method in which a solution of a lithium compound and a solution of a phosphorus compound are added and mixed, and then filtered and dried.
リチウム化合物は水溶性であれば特に制限はなく、例えば、水酸化リチウム、炭酸リチウム、硝酸リチウム、塩化リチウム、ヨウ化リチウム、シュウ酸リチウム等が挙げられる。 The lithium compound is not particularly limited as long as it is water-soluble, and examples thereof include lithium hydroxide, lithium carbonate, lithium nitrate, lithium chloride, lithium iodide, lithium oxalate, and the like.
リン化合物は水溶性であれば特に制限はなく、Ｌｉ３ＰＯ４、ＬｉＰＯ３等のリチウムのリン酸塩、Ｎａ３ＰＯ４、ＮａＨ２ＰＯ４、Ｎａ２ＨＰＯ４等のナトリウムのリン酸塩、Ｋ３ＰＯ４、ＫＨ２ＰＯ４、Ｋ２ＨＰＯ４等のカリウムのリン酸塩等、Ｍｇ３（ＰＯ４）２、ＭｇＨＰＯ４、Ｍｇ（Ｈ２ＰＯ４）２等のマグネシウムのリン酸塩、ＮＨ４Ｈ２ＰＯ４、（ＮＨ４）２ＨＰＯ４等のアンモニウムのリン酸等が例示される。 The phosphorus compound is not particularly limited as long as it is water-soluble, and includes lithium phosphates such as Li 3 PO 4 and LiPO 3 , sodium phosphates such as Na 3 PO 4 , NaH 2 PO 4 , and Na 2 HPO 4 , potassium phosphates such as K 3 PO 4 , KH 2 PO 4 , K 2 HPO 4 , magnesium phosphates such as Mg 3 (PO 4 ) 2 , MgHPO 4 , Mg(H 2 PO 4 ) 2 ; Examples include ammonium phosphoric acid such as NH 4 H 2 PO 4 and (NH 4 ) 2 HPO 4 .
スピネル型マンガン酸リチウムにリチウム化合物の溶液及びリン酸化合物の溶液を添加する方法は、スピネル型マンガン酸リチウムにリチウム化合物の溶液を添加した後にリン酸化合物の溶液を添加する方法、スピネル型マンガン酸リチウムのスラリーを調製した後にリチウム化合物の溶液とリン酸化合物の溶液を同時に添加する方法等が例示される。スピネル型マンガン酸リチウムにリチウム化合物の溶液及びリン酸化合物の溶液を添加する際には、スピネル型マンガン酸リチウムからリチウムが脱離することを抑制するため、溶液のｐＨを７以上とすることが好ましい。 A method of adding a solution of a lithium compound and a solution of a phosphoric acid compound to spinel-type lithium manganate is a method of adding a solution of a lithium compound to spinel-type lithium manganate, and then a solution of a phosphoric acid compound. Examples include a method in which a lithium compound solution and a phosphoric acid compound solution are added simultaneously after preparing a lithium slurry. When adding a solution of a lithium compound and a solution of a phosphoric acid compound to spinel-type lithium manganate, the pH of the solution should be set to 7 or more in order to suppress desorption of lithium from spinel-type lithium manganate. preferable.
リチウム化合物及びリン酸化合物を加える溶液は、例えば、純水、水等が挙げられる。 Examples of the solution to which the lithium compound and phosphoric acid compound are added include pure water and water.
スピネル型マンガン酸リチウムは、焼成時に二次粒子同士が固結し易いため、目的の粒子径を得るために解砕を行うことが好ましい。解砕方法は、微粉生成をより抑制するため、せん断力による解砕が好ましい。 Since secondary particles of spinel-type lithium manganate tend to solidify together during firing, it is preferable to crush the secondary particles to obtain the desired particle size. As for the crushing method, crushing using shear force is preferable in order to further suppress the generation of fine powder.
スピネル型マンガン酸リチウムは、正極の厚みを超える粗大粒子を除去するため、篩を通過させることが好ましい。篩の目開きは２００μｍ以下であることが好ましく、１５０μｍ以下であることがより好ましい。 The spinel-type lithium manganate is preferably passed through a sieve in order to remove coarse particles exceeding the thickness of the positive electrode. The opening of the sieve is preferably 200 μm or less, more preferably 150 μm or less.
本実施形態のリン酸塩を含有したスピネル型マンガン酸リチウムをリチウムイオン二次電池の正極に使用することで、従来では得ることができなかった、高温における保存特性及び充放電特性に優れるリチウムイオン二次電池を構成することが可能になる。 By using the spinel-type lithium manganate containing the phosphate of this embodiment as the positive electrode of a lithium ion secondary battery, lithium ions with excellent storage characteristics and charge/discharge characteristics at high temperatures, which could not be obtained conventionally, can be obtained. It becomes possible to configure a secondary battery.
正極以外のリチウムイオン二次電池の構成としては、特に制限はないが、負極にはＬｉを吸蔵放出する材料、例えば、炭素系材料、酸化錫系材料、Ｌｉ４Ｔｉ５Ｏ１２、ＳｉＯ、Ｌｉと合金を形成する材料等が挙げられる。Ｌｉと合金を形成する材料としては、例えば、シリコン系材料やアルミニウム系材料等が挙げられる。電解質には、例えば、有機溶媒にＬｉ塩や各種添加剤を溶解した有機電解液や、Ｌｉイオン伝導性の固体電解質、これらを組み合わせたもの等が挙げられる。 There are no particular restrictions on the structure of the lithium ion secondary battery other than the positive electrode, but the negative electrode may contain a material that intercalates and releases Li, such as a carbon-based material, a tin oxide-based material, Li 4 Ti 5 O 12 , SiO, Li. Examples include materials that form an alloy with. Examples of materials that form an alloy with Li include silicon-based materials and aluminum-based materials. Examples of the electrolyte include an organic electrolyte in which Li salt and various additives are dissolved in an organic solvent, a solid electrolyte that conducts Li ions, and a combination thereof.
次に、本開示を具体的な実施例で説明するが、本開示はこれらの実施例に限定して解釈されるものではない。 Next, the present disclosure will be explained using specific examples, but the present disclosure should not be construed as being limited to these examples.
＜組成分析＞
実施例および比較例で得られたスピネル型マンガン酸リチウムの組成、リン酸塩含有量、ＳＯ４含有量、Ｎａ含有量、ホウ素含有量は、スピネル型マンガン酸リチウムを硫酸－過酸化水素混合水溶液もしくは塩酸－過酸化水素混合水溶液に溶解した後、誘電結合プラズマ発光分析装置（商品名：ＩＣＰ－ＡＥＳ、パーキンエルマージャパン製）で分析した。
<Composition analysis>
The composition, phosphate content, SO 4 content, Na content, and boron content of the spinel-type lithium manganate obtained in Examples and Comparative Examples are as follows. Alternatively, after dissolving in a mixed aqueous solution of hydrochloric acid and hydrogen peroxide, it was analyzed using an inductively coupled plasma emission spectrometer (trade name: ICP-AES, manufactured by PerkinElmer Japan).
＜ＸＲＤによる結晶相の同定＞
実施例および比較例で得られたスピネル型マンガン酸リチウムの結晶相の同定は、粉末ＸＲＤ測定（商品名：Ｕｌｔｉｍａ ＩＶ、Ｒｉｇａｋｕ製）により行った。測定条件は、以下の通りとした。
<Identification of crystal phase by XRD>
The crystal phase of the spinel-type lithium manganate obtained in Examples and Comparative Examples was identified by powder XRD measurement (trade name: Ultima IV, manufactured by Rigaku). The measurement conditions were as follows.
・ターゲット：Ｃｕ
・出力：１．６ｋＷ（４０ｍＡ－４０ｋＶ）
・フィルター：Ｋβフィルター
・発散スリット：１°
・発散縦制限スリット：１０ｍｍ
・散乱スリット：解放
・受光スリット；解放
・走査モード：連続
・スキャンスピード：４．０００°／分
・サンプリング幅：０．０４°（２θ／θ）
・積算回数：１回
・測定範囲：１０－９０°（２θ／θ）
＜リン酸塩及びスピネル型マンガン酸リチウムのＢＥＴ比表面積の測定＞
実施例および比較例で得られたスピネル型マンガン酸リチウム１．５ｇをＢＥＴ比表面積測定用のガラス製セルに入れ、窒素気流下で１５０℃、３０分間脱水処理を行い、粉体粒子に付着した水分の除去を行った。処理後の試料を、ＢＥＴ測定装置（商品名：ＭＩＣＲＯＭＥＲＩＴＩＣＳ ＤｅＳｏｒｂＩＩＩ、島津製作所製）で、吸着ガスとして、窒素３０％－ヘリウム７０％の混合ガスを用いて、１点法でＢＥＴ比表面積を測定した。
・Target: Cu
・Output: 1.6kW (40mA-40kV)
・Filter: Kβ filter ・Divergence slit: 1°
・Divergence vertical restriction slit: 10mm
・Scattering slit: open ・Light receiving slit: open ・Scanning mode: continuous ・Scanning speed: 4.000°/min ・Sampling width: 0.04° (2θ/θ)
・Number of integration: 1 time ・Measurement range: 10-90° (2θ/θ)
<Measurement of BET specific surface area of phosphate and spinel type lithium manganate>
1.5 g of spinel-type lithium manganate obtained in Examples and Comparative Examples was placed in a glass cell for BET specific surface area measurement, and subjected to dehydration treatment at 150 ° C. for 30 minutes under a nitrogen stream to adhere to powder particles. Water was removed. The BET specific surface area of the treated sample was measured using a BET measurement device (trade name: MICROMERITICS DeSorb III, manufactured by Shimadzu Corporation) using a 1-point method using a mixed gas of 30% nitrogen and 70% helium as the adsorption gas. .
また、リン酸塩を含有していない、すなわち、焼成工程後、リン酸塩含有工程直前のスピネル型マンガン酸リチウムのＢＥＴ比表面積を予め測定しておき、以下の式に基づきリン酸塩（Ｌｉ３ＰＯ４）のＢＥＴ比表面積を算出した。 In addition, the BET specific surface area of spinel-type lithium manganate that does not contain phosphate, that is, after the firing process and immediately before the phosphate-containing process, is measured in advance, and the BET specific surface area of phosphate (Li The BET specific surface area of 3PO4 ) was calculated.
Ｌｉ３ＰＯ４のＢＥＴ比表面積［ｍ２／ｇ］＝（（Ｌｉ３ＰＯ４含有スピネル型マンガン酸リチウムのＢＥＴ比表面積［ｍ２／ｇ］）－（Ｌｉ３ＰＯ４を含有していないスピネル型マンガン酸リチウムのＢＥＴ比表面積［ｍ２／ｇ］））／（Ｌｉ３ＰＯ４含有量（質量％）／１００）
＜断面ＴＥＭ－ＥＤＸの測定＞
電界放射型透過電子顕微鏡（商品名：ＪＥＭ－２１００Ｆ、日本電子製）及びエネルギー分散型Ｘ線分光器（商品名：ＪＥＤ－２３００Ｔ、日本電子製）を使用して、スピネル型マンガン酸リチウム粒子の断面ＴＥＭ－ＥＤＸ測定を行った。測定に先立ち、試料をビームカッターにて切断した。
BET specific surface area of Li 3 PO 4 [m 2 /g] = ((BET specific surface area of spinel-type lithium manganate containing Li 3 PO 4 [m 2 /g]) - (spinel not containing Li 3 PO 4 BET specific surface area of type lithium manganate [ m2 /g]) / ( Li3PO4 content (mass%)/100)
<Cross-sectional TEM-EDX measurement>
Using a field emission transmission electron microscope (product name: JEM-2100F, manufactured by JEOL Ltd.) and an energy dispersive X-ray spectrometer (product name: JED-2300T, manufactured by JEOL Ltd.), spinel-type lithium manganate particles were analyzed. Cross-sectional TEM-EDX measurements were performed. Prior to measurement, the sample was cut with a beam cutter.
＜二次粒子径の測定＞
粒度分布測定装置（商品名：ＭＴ３０００ＩＩシリーズ、ＭｉｃｒｏｔｒａｃＢＥＬ製）を使用して、スピネル型マンガン酸リチウムの二次粒子の平均粒子径（Ｄ５０）を測定した。
<Measurement of secondary particle diameter>
The average particle diameter (D 50 ) of the spinel-type lithium manganate secondary particles was measured using a particle size distribution measuring device (trade name: MT3000II series, manufactured by Microtrac BEL).
＜電池性能評価＞
正極は、実施例、比較例で得られたスピネル型マンガン酸リチウム４．７ｇとアセチレンブラック（商品名：デンカブラックＬｉ－４００、デンカ製）０．１５ｇと１０質量％ポリフッ化ビニリデン／Ｎ－メチル－２－ピロリドン溶液１．４３４ｍＬ（ポリフッ化ビニリデン０．１５ｇ）（重量比でスピネル型マンガン酸リチウム：アセチレンブラック：ポリフッ化ビニリデン＝９４：３：３）とＮ－メチル－２－ピロリドン１．２３ｍＬを自転公転ミキサー（商品名：ＡＲ－３１０、シンキー製）で混合して正極合剤スラリーを作製し、得られた正極合剤スラリーをアルミニウム箔に塗布し、１２０℃で１０分乾燥後、縦６０ｍｍ、横３０ｍｍの長方形に打ち抜き、ロールプレスを行った。塗布した正極合剤を縦５０ｍｍ、横３０ｍｍとなるようにＮ－メチル－２－ピロリドンを用いてアルミニウム箔から剥がし、剥がした部分にアルミ製タブを溶接して１５０℃で５時間真空乾燥した後、使用した。塗布量はスピネル型マンガン酸リチウム量が１５ｍｇ／ｃｍ２となるようにした。正極合剤密度は２．４ｇ／ｃｍ３とした。
<Battery performance evaluation>
The positive electrode was made of 4.7 g of spinel-type lithium manganate obtained in Examples and Comparative Examples, 0.15 g of acetylene black (product name: Denka Black Li-400, manufactured by Denka), and 10% by mass polyvinylidene fluoride/N-methyl. -2-pyrrolidone solution 1.434 mL (polyvinylidene fluoride 0.15 g) (weight ratio of spinel type lithium manganate: acetylene black: polyvinylidene fluoride = 94:3:3) and N-methyl-2-pyrrolidone 1.23 mL A positive electrode mixture slurry was prepared by mixing with a rotation/revolution mixer (product name: AR-310, manufactured by Shinky).The obtained positive electrode mixture slurry was applied to an aluminum foil, dried at 120°C for 10 minutes, and then vertically It was punched into a rectangle 60 mm wide and 30 mm wide, and roll pressed. The applied positive electrode mixture was peeled off from the aluminum foil using N-methyl-2-pyrrolidone so that it was 50 mm long and 30 mm wide, an aluminum tab was welded to the peeled part, and it was vacuum-dried at 150°C for 5 hours. ,used. The coating amount was such that the amount of spinel type lithium manganate was 15 mg/cm 2 . The positive electrode mixture density was 2.4 g/cm 3 .
負極は、人造黒鉛４．０ｇと１０質量％ポリフッ化ビニリデン／Ｎ－メチル－２－ピロリドン溶液２．００８ｍＬ（ポリフッ化ビニリデン０．２１０ｇ）（重量比で黒鉛：ポリフッ化ビニリデン＝９５：５）とＮ－メチル－２－ピロリドン３．１６０ｍＬを自転公転ミキサー（商品名：ＡＲ－３１０、シンキー製）で混合して負極合剤スラリーを作製し、得られた負極材スラリーを銅箔に塗布し、１２０℃で１０分乾燥後、縦６２ｍｍ、横３２ｍｍの長方形に打ち抜き、ロールプレスを行った。塗布した負極合剤を縦５２ｍｍ、横３２ｍｍとなるようにＮ－メチル－２－ピロリドンを用いて銅箔から剥がし、剥がした部分にニッケル製タブを溶接して１５０℃で５時間真空乾燥した後、使用した。塗布量は、人造黒鉛が５．５ｍｇ／ｃｍ２となるようにした。負極合剤密度は１．３ｇ／ｃｍ３とした。 The negative electrode was made of 4.0 g of artificial graphite and 2.008 mL of a 10% by mass polyvinylidene fluoride/N-methyl-2-pyrrolidone solution (0.210 g of polyvinylidene fluoride) (graphite: polyvinylidene fluoride = 95:5 in weight ratio). A negative electrode mixture slurry was prepared by mixing 3.160 mL of N-methyl-2-pyrrolidone with a rotation-revolution mixer (product name: AR-310, manufactured by Shinky), and the obtained negative electrode material slurry was applied to copper foil. After drying at 120° C. for 10 minutes, it was punched into a rectangle measuring 62 mm long and 32 mm wide, and roll pressed. The applied negative electrode mixture was peeled off from the copper foil using N-methyl-2-pyrrolidone so that it had a length of 52 mm and a width of 32 mm, a nickel tab was welded to the peeled part, and it was vacuum-dried at 150°C for 5 hours. ,used. The amount of artificial graphite applied was 5.5 mg/cm 2 . The density of the negative electrode mixture was 1.3 g/cm 3 .
上記の正極及び負極と、エチレンカーボネートとジメチルカーボネートの混合溶媒（体積比１：２）にＬｉＰＦ６を１ｍｏｌ／ｄｍ３溶解した電解液０．２４ｍＬと、縦６５ｍｍ、横３５ｍｍの長方形に打ち抜いたセパレータ（商品名：セラミックコーティング湿式セパレータ―ＳＨ７１６Ｅ１４、Ｓｈｅｎｚｈｅｎ Ｓｅｎｉｏｒ Ｔｅｃｈｎｏｌｏｇｙ Ｍａｔｅｒｉａｌ製）を用いてラミネートセルを作製した。電池評価の際には、ラミネートセルを２枚のアクリル板で挟み、アクリル板を貫通する４本のネジを用いて１Ｎ／ｍのトルク圧で締め付けを行った。 The above positive and negative electrodes, 0.24 mL of an electrolytic solution containing 1 mol/ dm3 of LiPF 6 dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1:2), and a separator punched into a rectangle 65 mm long and 35 mm wide. (Product name: Ceramic coating wet separator - SH716E14, manufactured by Shenzhen Senior Technology Material) A laminate cell was produced. During battery evaluation, the laminate cell was sandwiched between two acrylic plates, and four screws passing through the acrylic plates were tightened with a torque pressure of 1 N/m.
また、上記正極を１５．９６ｍｍφに打ち抜き、１６ｍｍφに打ち抜いたＬｉ金属を負極として、セパレータ（商品名：セルガード、ポリポア製）を用いてＣＲ２０３２型コインセルを作製した。 Further, the positive electrode was punched out to a size of 15.96 mm, and a CR2032 type coin cell was produced using a separator (trade name: Celguard, manufactured by Polypore) using Li metal punched out to a size of 16 mm as a negative electrode.
作製したＣＲ２０３２型コインセルを用いて、２４℃において、セル電圧４．３Ｖと３．０Ｖの間で電流０．６ｍＡで定電流充電－定電流放電を１サイクル行い、充電容量を初期容量とした。 Using the manufactured CR2032 type coin cell, one cycle of constant current charging and constant current discharging was performed at 24° C. with a cell voltage of 4.3 V and 3.0 V at a current of 0.6 mA, and the charging capacity was set as the initial capacity.
次に、作製したラミネートセルを用いてエージングを行った。エージングは、２４℃において、初期容量の１０％まで定電流で充電して９時間休止し、次に初期容量の６０％まで定電流で充電して２４時間休止し、次にセル電圧４．２Ｖまで定電流定電圧充電を行った後、３．０Ｖまで定電流で放電した。充電時及び放電時の電流は初期容量に対して時間率０．１Ｃとし、定電圧充電の終了条件は、充電電流が時間率０．００５Ｃまで減衰した時点とした。 Next, aging was performed using the produced laminate cell. Aging was performed at 24°C by charging at a constant current to 10% of the initial capacity, resting for 9 hours, then charging at a constant current to 60% of the initial capacity, resting for 24 hours, and then increasing the cell voltage to 4.2V. After performing constant current and constant voltage charging to 3.0V, constant current discharge was performed to 3.0V. The current during charging and discharging was set at a time rate of 0.1C with respect to the initial capacity, and the termination condition for constant voltage charging was the time when the charging current attenuated to a time rate of 0.005C.
エージング終了後、セル容量確認を行った。セル容量確認は、２４℃において、セル電圧が４．２Ｖと３．０Ｖの間で、定電流定電圧充電－定電流放電を１サイクル行い、放電容量をセル容量とした。充電時及び放電時の電流は初期容量に対して時間率０．２Ｃとし、定電圧充電の終了条件は、充電電流が時間率０．０１Ｃまで減衰した時点とした。 After aging, the cell capacity was checked. To confirm the cell capacity, one cycle of constant current/constant voltage charging and constant current discharging was performed at 24° C. at a cell voltage between 4.2 V and 3.0 V, and the discharge capacity was taken as the cell capacity. The current during charging and discharging was set at a time rate of 0.2C relative to the initial capacity, and the termination condition for constant voltage charging was the time when the charging current attenuated to a time rate of 0.01C.
セル容量確認後、保存試験及び充放電サイクル試験を行った。 After confirming the cell capacity, a storage test and a charge/discharge cycle test were conducted.
保存試験は、作製したラミネートセルを２４℃において４．２Ｖまで充電後、６０℃で７日間保存した。次いで、セル電圧３．０Ｖまで放電した後、４．２Ｖと３．０Ｖの間で定電流定電圧充電－定電流放電を１サイクル行い、放電容量を回復容量とし、セル容量に対する回復容量の割合を保存容量回復率とした。なお、充電時及び放電時の電流はセル容量に対して時間率０．２Ｃとし、定電圧充電の終了条件は、充電電流が時間率０．０１Ｃまで減衰した時点とした。 In the storage test, the prepared laminate cell was charged to 4.2V at 24°C and then stored at 60°C for 7 days. Next, after discharging to a cell voltage of 3.0 V, one cycle of constant current constant voltage charging and constant current discharging is performed between 4.2 V and 3.0 V, the discharge capacity is taken as the recovery capacity, and the ratio of the recovery capacity to the cell capacity is calculated. was taken as the storage capacity recovery rate. Note that the current during charging and discharging was set at a time rate of 0.2 C relative to the cell capacity, and the termination condition for constant voltage charging was set at the time when the charging current attenuated to a time rate of 0.01 C.
充放電サイクル試験は、作製したラミネートセルについて４５℃においてセル電圧４．２Ｖと３．０Ｖの間で定電流定電圧充電－定電流放電を５０サイクル行い、１サイクル目の容量に対する５０サイクル目の容量の割合を充放電サイクル維持率とした。なお、充電時及び放電時の電流はセル容量に対して時間率０．５Ｃとし、定電圧充電の終了条件は、充電電流が時間率０．０２５Ｃまで減衰した時点とした。 In the charge/discharge cycle test, the prepared laminate cell was subjected to 50 cycles of constant current/constant voltage charging and constant current discharging at a cell voltage of 4.2 V and 3.0 V at 45°C, and the capacity at the 50th cycle was The capacity ratio was defined as the charge/discharge cycle retention rate. Note that the current during charging and discharging was set at a time rate of 0.5C relative to the cell capacity, and the termination condition for constant voltage charging was the time when the charging current attenuated to a time rate of 0.025C.
実施例１
平均粒子径１２．０μｍの電解二酸化マンガン８０．００ｇと、平均粒子径３μｍのＬｉ２ＣＯ３１８．８０ｇと、Ｍｇ（ＯＨ）２（和光純薬工業製、平均粒子径０．０７μｍ）１．５６ｇと、Ｈ３ＢＯ３（キシダ化学製）をめのう乳鉢で粉砕したもの０．２４ｇを乳鉢で混合して混合物を得た。この混合物を箱型炉にて空気を５Ｌ／ｍｉｎの速度で流通させながら９３０℃で６時間焼成を行った後、６００℃で２４時間熱処理を行い、室温まで冷却して、スピネル型マンガン酸リチウムを得た。９３０℃までの昇温速度は１００℃／ｈｒとし、降温速度は９３０℃から６００℃までは２０℃／ｈｒ、６００℃から室温までは１００℃／ｈｒとした。得られたスピネル型マンガン酸リチウムを、強力小型粉砕機（商品名：ロータリークラッシャー、大阪ケミカル製）で解砕した。
Example 1
80.00 g of electrolytic manganese dioxide with an average particle size of 12.0 μm, 18.80 g of Li 2 CO 3 with an average particle size of 3 μm, and Mg(OH) 2 (manufactured by Wako Pure Chemical Industries, Ltd., average particle size of 0.07 μm)1. 56 g and 0.24 g of H 3 BO 3 (manufactured by Kishida Chemical) ground in an agate mortar were mixed in a mortar to obtain a mixture. This mixture was fired in a box furnace at 930°C for 6 hours while air was flowing at a rate of 5L/min, then heat treated at 600°C for 24 hours, cooled to room temperature, and spinel-type lithium manganate I got it. The heating rate up to 930°C was 100°C/hr, the cooling rate was 20°C/hr from 930°C to 600°C, and 100°C/hr from 600°C to room temperature. The obtained spinel-type lithium manganate was crushed using a small powerful crusher (trade name: Rotary Crusher, manufactured by Osaka Chemical).
次に、得られたスピネル型マンガン酸リチウム７２．０ｇに、７２ｍＬの純水と２．０ｍｏｌ／ＬのＬｉＯＨ（キシダ化学製）水溶液１８ｍＬを添加し、室温下、６００ｒｐｍで攪拌しながら２６質量％のＨ３ＰＯ４（キシダ化学製）水溶液１０ｍＬを０．０５６ｍＬ／分の速度で添加した。その後、ろ過・乾燥を行い、目開き３２μｍの篩を通過させて粗大な粒子を取り除き、本実施例のスピネル型マンガン酸リチウムを得た。 Next, 72 mL of pure water and 18 mL of a 2.0 mol/L LiOH (manufactured by Kishida Chemical) aqueous solution were added to 72.0 g of the obtained spinel-type lithium manganate, and while stirring at 600 rpm at room temperature, 26% by mass 10 mL of an aqueous solution of H 3 PO 4 (manufactured by Kishida Chemical) was added at a rate of 0.056 mL/min. Thereafter, it was filtered and dried, and coarse particles were removed by passing through a sieve with an opening of 32 μm to obtain a spinel-type lithium manganate of this example.
ＩＣＰの測定結果より、得られたスピネル型マンガン酸リチウムの組成は、化学量論組成Ｌｉ１＋ＸＭｎ２－Ｘ－ＹＭＹＯ４を取ると仮定して、Ｌｉ１．０８Ｍｎ１．８６Ｍｇ０．０６Ｏ４であった。リン酸塩含有量、リン酸塩のＢＥＴ比表面積、スピネル型マンガン酸リチウム二次粒子の平均粒子径、ＳＯ４含有量、Ｎａ含有量、ホウ素含有量の測定結果（以下、単に「測定結果」ともいう。）を表１に示し、電池性能評価結果を表２に示す。 From the ICP measurement results, the composition of the spinel type lithium manganate obtained is Li 1.08 Mn 1.86 Mg, assuming that the stoichiometric composition is Li 1+X Mn 2-X-Y MYO 4 . It was 0.06 O4 . Measurement results of phosphate content, BET specific surface area of phosphate, average particle diameter of spinel-type lithium manganate secondary particles, SO 4 content, Na content, and boron content (hereinafter simply "measurement results") ) are shown in Table 1, and the battery performance evaluation results are shown in Table 2.
また、スピネル型マンガン酸リチウム粒子断面のＴＥＭ－ＥＤＸ像を図１に示す。図１（Ａ）はＰ元素のマッピング結果を、図１（Ｂ）はＭｎ元素のマッピング結果を示す。リン酸塩（Ｌｉ３ＰＯ４）がスピネル型マンガン酸リチウム粒子の表面に存在することが確認された。また、ＸＲＤ測定により、スピネル型マンガン酸リチウムからは、ＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４、ピーク位置：２θ＝１８．６°、３０．７°、３６．１°、３７．８°、４３．９°、４８．１°、５８．１°、６３．８°、６７．１°、７５．６°、７６．６°）とＮｏ．２５－１０３０（Ｌｉ３ＰＯ４、ピーク位置：２θ＝１６．９°、２２．４°、２３．４°、２５．０°、２９．２°、３３．９°）の２つのピークパターンが検出された。図２に実施例１のＸＲＤピークパターンを示す。 Furthermore, a TEM-EDX image of a cross section of a spinel-type lithium manganate particle is shown in FIG. FIG. 1(A) shows the mapping result of P element, and FIG. 1(B) shows the mapping result of Mn element. It was confirmed that phosphate (Li 3 PO 4 ) was present on the surface of the spinel-type lithium manganate particles. Furthermore, XRD measurement revealed that spinel-type lithium manganate was found to be No. 1 in JCPDS. 35-782 (LiMn 2 O 4 , peak position: 2θ = 18.6°, 30.7°, 36.1°, 37.8°, 43.9°, 48.1°, 58.1°, 63 .8°, 67.1°, 75.6°, 76.6°) and No. The two peak patterns of 25-1030 (Li 3 PO 4 , peak positions: 2θ = 16.9°, 22.4°, 23.4°, 25.0°, 29.2°, 33.9°) was detected. FIG. 2 shows the XRD peak pattern of Example 1.
実施例２
ＬｉＯＨ水溶液の濃度を１．０ｍｏｌ／Ｌとしたことと、Ｈ３ＰＯ４水溶液の濃度を１３質量％としたこと以外は実施例１と同様の方法でスピネル型マンガン酸リチウムを得た。
Example 2
Spinel-type lithium manganate was obtained in the same manner as in Example 1, except that the concentration of the LiOH aqueous solution was 1.0 mol/L and the concentration of the H 3 PO 4 aqueous solution was 13% by mass.
得られたスピネル型マンガン酸リチウムの組成はＬｉ１．０８Ｍｎ１．８６Ｍｇ０．０６Ｏ４であった。測定結果を表１に示し、電池性能を表２に示す。また、ＸＲＤ測定から、得られたスピネル型マンガン酸リチウムはＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４）とＮｏ．２５－１０３０（Ｌｉ３ＰＯ４）の２つのピークパターンが検出された。 The composition of the obtained spinel type lithium manganate was Li 1.08 Mn 1.86 Mg 0.06 O 4 . The measurement results are shown in Table 1, and the battery performance is shown in Table 2. Further, from XRD measurement, the obtained spinel type lithium manganate was No. 1 in JCPDS. 35-782 (LiMn 2 O 4 ) and No. Two peak patterns of 25-1030 (Li 3 PO 4 ) were detected.
実施例３
ＬｉＯＨ水溶液の濃度を０．５０ｍｏｌ／Ｌとしたことと、Ｈ３ＰＯ４水溶液の濃度を６．５質量％としたこと以外は実施例１と同様の方法でスピネル型マンガン酸リチウムを得た。
Example 3
Spinel-type lithium manganate was obtained in the same manner as in Example 1, except that the concentration of the LiOH aqueous solution was 0.50 mol/L and the concentration of the H 3 PO 4 aqueous solution was 6.5% by mass.
得られたスピネル型マンガン酸リチウムの組成はＬｉ１．０８Ｍｎ１．８６Ｍｇ０．０６Ｏ４であった。測定結果を表１に示し、電池性能を表２に示す。また、ＸＲＤ測定から、得られたスピネル型マンガン酸リチウムはＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４）とＮｏ．２５－１０３０（Ｌｉ３ＰＯ４）の２つのピークパターンが検出された。 The composition of the obtained spinel type lithium manganate was Li 1.08 Mn 1.86 Mg 0.06 O 4 . The measurement results are shown in Table 1, and the battery performance is shown in Table 2. Further, from XRD measurement, the obtained spinel type lithium manganate was No. 1 in JCPDS. 35-782 (LiMn 2 O 4 ) and No. Two peak patterns of 25-1030 (Li 3 PO 4 ) were detected.
比較例１ 平均粒子径４．０μｍのＭｎ３Ｏ４７５．００ｇと、平均粒子径３μｍのＬｉ２ＣＯ３２１．４８ｇと、Ｍｇ（ＯＨ）２（和光純薬工業製、平均粒子径０．０７μｍ）１．７０ｇと、Ｈ３ＢＯ３（キシダ化学製）をめのう乳鉢で粉砕したもの０．６０ｇを混合して混合物を得た。この混合物について箱型炉にて空気を５Ｌ／ｍｉｎの速度で流通させながら８５０℃で６時間焼成を行った後、６００℃で２４時間焼成を行い、室温まで冷却して、スピネル型マンガン酸リチウムを得た。室温から８５０℃までの昇温速度は１００℃／ｈｒとし、降温速度は８５０℃から６００℃までは２０℃／ｈｒ、６００℃から室温までは１００℃／ｈｒとした。得られたスピネル型マンガン酸リチウムを、強力小型粉砕機（商品名：ロータリークラッシャー、大阪ケミカル製）で解砕した。 Comparative Example 1 75.00 g of Mn 3 O 4 with an average particle size of 4.0 μm, 21.48 g of Li 2 CO 3 with an average particle size of 3 μm, and Mg(OH) 2 (manufactured by Wako Pure Chemical Industries, Ltd., with an average particle size of 0.0 μm). 07 μm) and 0.60 g of H 3 BO 3 (manufactured by Kishida Chemical Co., Ltd.) ground in an agate mortar to obtain a mixture. This mixture was fired in a box furnace at 850°C for 6 hours while air was flowing at a rate of 5L/min, then at 600°C for 24 hours, cooled to room temperature, and spinel-type lithium manganate I got it. The temperature increasing rate from room temperature to 850°C was 100°C/hr, the temperature decreasing rate was 20°C/hr from 850°C to 600°C, and 100°C/hr from 600°C to room temperature. The obtained spinel-type lithium manganate was crushed using a small powerful crusher (trade name: Rotary Crusher, manufactured by Osaka Chemical).
次に、得られたスピネル型マンガン酸リチウムに対して、豊島製作所製粉末バレルスパッタリング装置を用いてＬｉ３ＰＯ４の成膜を行った。ターゲットにはＬｉ３ＰＯ４焼結体を用い、使用電源はＲＦ、成膜時出力は２ｋＷ、成膜時間は８時間、使用ガスはＡｒ１００％とした。 Next, a film of Li 3 PO 4 was formed on the obtained spinel type lithium manganate using a powder barrel sputtering device manufactured by Toyoshima Seisakusho. A Li 3 PO 4 sintered body was used as a target, the power source used was RF, the output during film formation was 2 kW, the film formation time was 8 hours, and the gas used was 100% Ar.
得られたスピネル型マンガン酸リチウムの組成はＬｉ１．０９Ｍｎ１．８５Ｍｇ０．０６Ｏ４であった。測定結果を表１に示し、電池性能を表２に示す。また、ＸＲＤ測定から、得られたスピネル型マンガン酸リチウムはＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４）とＮｏ．２５－１０３０（Ｌｉ３ＰＯ４）の２つのピークパターンが検出された。 The composition of the obtained spinel type lithium manganate was Li 1.09 Mn 1.85 Mg 0.06 O 4 . The measurement results are shown in Table 1, and the battery performance is shown in Table 2. Further, from XRD measurement, the obtained spinel type lithium manganate was No. 1 in JCPDS. 35-782 (LiMn 2 O 4 ) and No. Two peak patterns of 25-1030 (Li 3 PO 4 ) were detected.
比較例２
平均粒子径１２μｍの電解二酸化マンガン１００．０ｇと平均粒子径３μｍの炭酸リチウム２３．７ｇと平均粒子径３μｍの水酸化アルミニウム４．３ｇとリン酸三リチウム（和光純薬工業製）０．９ｇとＨ３ＢＯ３（和光純薬工業製）１．８ｇを純水９８．２ｇに溶解して１．８質量％水溶液としたもの０．１１ｇを混合して混合物を得た。この混合物について、箱型炉にて空気を５Ｌ／ｍｉｎの速度で流通させながら８００℃で２０時間焼成を行い、室温まで冷却して、スピネル型マンガン酸リチウムを得た。昇温速度、降温速度はいずれも１００℃／ｈｒとした。次に、強力小型粉砕機（商品名：ロータリークラッシャー、大阪ケミカル製）で解砕し、目開き３２μｍの篩を通過させてスピネル型マンガン酸リチウムを得た。
Comparative example 2
100.0 g of electrolytic manganese dioxide with an average particle size of 12 μm, 23.7 g of lithium carbonate with an average particle size of 3 μm, 4.3 g of aluminum hydroxide with an average particle size of 3 μm, and 0.9 g of trilithium phosphate (manufactured by Wako Pure Chemical Industries). A mixture was obtained by mixing 0.11 g of a 1.8% by mass aqueous solution obtained by dissolving 1.8 g of H 3 BO 3 (manufactured by Wako Pure Chemical Industries) in 98.2 g of pure water. This mixture was fired at 800° C. for 20 hours in a box furnace while air was flowing at a rate of 5 L/min, and then cooled to room temperature to obtain a spinel-type lithium manganate. The temperature increase rate and temperature decrease rate were both 100° C./hr. Next, it was crushed with a powerful small crusher (trade name: Rotary Crusher, manufactured by Osaka Chemical) and passed through a sieve with an opening of 32 μm to obtain a spinel-type lithium manganate.
得られたスピネル型マンガン酸リチウムの組成はＬｉ１．０７Ｍｎ１．８４Ａｌ０．０９Ｏ４であった。測定結果を表１に示し、電池性能を表２に示す。また、ＸＲＤ測定から、得られたスピネル型マンガン酸リチウムはＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４）とＮｏ．２５－１０３０（Ｌｉ３ＰＯ４）の２つのピークパターンが検出された。 The composition of the obtained spinel type lithium manganate was Li 1.07 Mn 1.84 Al 0.09 O 4 . The measurement results are shown in Table 1, and the battery performance is shown in Table 2. Further, from XRD measurement, the obtained spinel type lithium manganate was No. 1 in JCPDS. 35-782 (LiMn 2 O 4 ) and No. Two peak patterns of 25-1030 (Li 3 PO 4 ) were detected.
比較例３
スピネル型マンガン酸リチウムにＬｉＯＨとＨ３ＰＯ４を添加しなかったこと以外は、実施例１と同様の方法でスピネル型マンガン酸リチウムを得た。
Comparative example 3
Spinel-type lithium manganate was obtained in the same manner as in Example 1, except that LiOH and H 3 PO 4 were not added to the spinel-type lithium manganate.
得られたスピネル型マンガン酸リチウムの組成はＬｉ１．０８Ｍｎ１．８６Ｍｇ０．０６Ｏ４であった。測定結果を表１に示し、電池性能を表２に示す。また、ＸＲＤ測定から、得られたスピネル型マンガン酸リチウムはＪＣＰＤＳのＮｏ．３５－７８２（ＬｉＭｎ２Ｏ４）単相であった。図３に比較例３のＸＲＤピークパターンを示す。なお表１において、リン酸塩ＢＥＴ比表面積の欄は「－」で示しているが、リン酸塩（Ｌｉ３ＰＯ４）を含有しないため測定していないことを表す。 The composition of the obtained spinel type lithium manganate was Li 1.08 Mn 1.86 Mg 0.06 O 4 . The measurement results are shown in Table 1, and the battery performance is shown in Table 2. Further, from XRD measurement, the obtained spinel type lithium manganate was No. 1 in JCPDS. 35-782 (LiMn 2 O 4 ) single phase. FIG. 3 shows the XRD peak pattern of Comparative Example 3. In Table 1, the column for phosphate BET specific surface area is indicated by "-", which indicates that it was not measured because it did not contain phosphate (Li 3 PO 4 ).
本実施形態のスピネル型マンガン酸リチウムは、リン酸塩が特異的に大きいＢＥＴ比表面積有するため、高温における電池性能、特に保存特性及び充放電特性に優れるリチウムイオン二次電池の正極活物質として使用することができる。 The spinel-type lithium manganate of this embodiment is used as a positive electrode active material for lithium ion secondary batteries, which has excellent battery performance at high temperatures, especially storage characteristics and charge/discharge characteristics, because the phosphate has a specifically large BET specific surface area. can do.
１…スピネル型マンガン酸リチウム
２…リン酸リチウム（Ｌｉ３ＰＯ４）
1... Spinel type lithium manganate 2... Lithium phosphate (Li 3 PO 4 )
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