JP6749884B2 - Positive electrode material for lithium secondary batteries - Google Patents
Positive electrode material for lithium secondary batteries Download PDFInfo
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- JP6749884B2 JP6749884B2 JP2017233463A JP2017233463A JP6749884B2 JP 6749884 B2 JP6749884 B2 JP 6749884B2 JP 2017233463 A JP2017233463 A JP 2017233463A JP 2017233463 A JP2017233463 A JP 2017233463A JP 6749884 B2 JP6749884 B2 JP 6749884B2
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- positive electrode
- lithium secondary
- electrode material
- secondary battery
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- 239000007774 positive electrode material Substances 0.000 title claims description 91
- 229910052744 lithium Inorganic materials 0.000 title claims description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 65
- 239000002245 particle Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 229910052788 barium Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 239000011163 secondary particle Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
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- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
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- 238000001035 drying Methods 0.000 claims description 4
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- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000010354 integration Effects 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000011572 manganese Substances 0.000 description 26
- 238000009826 distribution Methods 0.000 description 17
- 239000011575 calcium Substances 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
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- 239000000843 powder Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- -1 LiCoO 2 Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 238000005259 measurement Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910018212 Ni—Co—Mn—(OH)2 Inorganic materials 0.000 description 4
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- 239000006230 acetylene black Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910006463 Li—Ni—Co—O Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
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- 238000001354 calcination Methods 0.000 description 2
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- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent 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
- 230000006866 deterioration Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000005001 laminate film 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
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910006421 Li—Ni—Co Inorganic materials 0.000 description 1
- 229910006685 Li—Ni—Mn—Co—O Inorganic materials 0.000 description 1
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 102000005717 Myeloma Proteins Human genes 0.000 description 1
- 108010045503 Myeloma Proteins Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical class B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- CUZMQPZYCDIHQL-VCTVXEGHSA-L calcium;(2s)-1-[(2s)-3-[(2r)-2-(cyclohexanecarbonylamino)propanoyl]sulfanyl-2-methylpropanoyl]pyrrolidine-2-carboxylate Chemical compound [Ca+2].N([C@H](C)C(=O)SC[C@@H](C)C(=O)N1[C@@H](CCC1)C([O-])=O)C(=O)C1CCCCC1.N([C@H](C)C(=O)SC[C@@H](C)C(=O)N1[C@@H](CCC1)C([O-])=O)C(=O)C1CCCCC1 CUZMQPZYCDIHQL-VCTVXEGHSA-L 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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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)
Description
本発明は、リチウム含有複合酸化物からなる新規なリチウム二次電池用正極材料およびその製造方法に関する。 The present invention relates to a novel positive electrode material for lithium secondary batteries comprising a lithium-containing composite oxide and a method for producing the same.
近年、機器のポータブル化、コードレス化が進むにつれ、小型、軽量でかつ高エネルギー密度を有する非水電解液二次電池、特にリチウム二次電池に対する期待が高まっている。リチウム二次電池用の正極活物質には、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＮｉ0.8Ｃｏ0.2Ｏ2、ＬｉＭｎ2Ｏ4、ＬｉＭｎＯ2などのリチウムと遷移金属の複合酸化物が知られている。ＬｉＮｉ0.8Ｃｏ0.2Ｏ2のようにコバルトやニッケルを固溶させた岩塩層状複合酸化物を正極活物質に用いたリチウム二次電池は、１８０〜２００ｍＡｈ／ｇと比較的高い容量密度を達成できる。また、２．５〜４．５Ｖといった高い電圧域で良好な可逆性を示す。 In recent years, with the progress of portable devices and cordless devices, expectations for non-aqueous electrolyte secondary batteries, especially lithium secondary batteries, which are small, lightweight and have high energy density have been increased. Known positive electrode active materials for lithium secondary batteries are lithium-transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiMn 2 O 4 , and LiMnO 2 . A lithium secondary battery using a rock salt layered composite oxide in which cobalt or nickel is solid-dissolved like LiNi 0.8 Co 0.2 O 2 as a positive electrode active material can achieve a relatively high capacity density of 180 to 200 mAh/g. Further, it exhibits good reversibility in a high voltage range of 2.5 to 4.5V.
特に最近では、高容量を発現できる材料として、ＬｉＮｉ0.8Ｃｏ0.2Ｏ2に代表されるリチウム−ニッケル−コバルト複合酸化物の採用が始まっている。これらを正極材料に用い、リチウムを吸蔵、放出することができる炭素材料等を負極材料として使用することによる、高電圧、高エネルギー密度のリチウム二次電池の商品化が進められている。 In particular, recently, the adoption of a lithium-nickel-cobalt composite oxide typified by LiNi 0.8 Co 0.2 O 2 has begun as a material capable of exhibiting a high capacity. Commercialization of a high voltage, high energy density lithium secondary battery is being promoted by using these as a positive electrode material and using a carbon material or the like capable of inserting and extracting lithium as a negative electrode material.
正極材料は、リチウム二次電池の電池特性および安全性に最も重要な役割を果たす物質である。近年 ＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4、ＬｉＮｉＯ2、ＬｉＮｉ１−ｘＣｏｘＯ２、ＬｉＭｎＯ2等の複合金属酸化物が研究されている。 The positive electrode material is a substance that plays the most important role in the battery characteristics and safety of the lithium secondary battery. In recent years, complex metal oxides such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiNi 1-x Co x O 2 , and LiMnO 2 have been studied.
これらの正極材料のうちＬｉＭｎ2Ｏ4、ＬｉＭｎＯ2等のＭｎ系正極材料は合成が容易であり、比較的安価であるが、放電容量が小さいという欠点を持っている。ＬｉＣｏＯ2、等のＣｏ系正極材料は、良好な電気伝導度と高い電池電圧、さらに優れた電極特性を持つが、主原料であるＣｏ金属が希少であり、高価であるという問題がある。ＬｉＮｉＯ2、等のＮｉ系正極材料は、上述した正極材料のうちでは比較的安価なＮｉ金属を主原料として使用し、理論放電量においてはＬｉＣｏＯ2と大差がないが、電池を構成した場合に実際に取り出すことのできる容量である実効容量において優れる。しかし合成が困難であるという欠点がある。 Of these positive electrode materials, Mn-based positive electrode materials such as LiMn 2 O 4 and LiMnO 2 are easy to synthesize and relatively inexpensive, but have a drawback that the discharge capacity is small. Co-based positive electrode materials such as LiCoO 2 have good electric conductivity, high battery voltage, and excellent electrode characteristics, but there is a problem that Co metal as a main raw material is rare and expensive. Ni-based positive electrode materials such as LiNiO 2 use relatively inexpensive Ni metal as a main raw material among the above-mentioned positive electrode materials, and have a theoretical discharge amount that is not much different from that of LiCoO 2 , but when a battery is constructed. It is excellent in the effective capacity that can be actually taken out. However, it has the drawback of being difficult to synthesize.
特許文献１には、ＬｉａＭｂＯ２よりなる電極活物質で、Ｍ ＝ＡzＡ’z’Ｍ’1- z - z’であり、Ｍ’は、Ｍｎ，Ｎｉ，Ｃｏであり、Ａは、Ａｌ、Ｍｇ、Ｔｉ、Ｃｒから選ばれた金属であり、Ａ’ は、Ｆ、Ｃｌ、Ｓ、Ｚｒ、Ｂａ、Ｙ、Ｃａ、Ｂ、Ｂｅ、Ｓｎ、Ｓｂ、Ｎａ、Ｚｎから選ばれたマイナードーパントである電極活物質が記載されている（請求項３）。この電極活物質は粒度分布を有する粉体であり、粒度に応じて組成Ｍを変化させる（請求項５）技術である。 Patent Document 1 discloses an electrode active material made of Li a M b O 2 , where M =A z A'z'M'1 -z -z' , and M'is Mn, Ni, Co, A is a metal selected from Al, Mg, Ti and Cr, and A′ is selected from F, Cl, S, Zr, Ba, Y, Ca, B, Be, Sn, Sb, Na and Zn. An electrode active material which is a minor dopant is described (Claim 3). This electrode active material is a powder having a particle size distribution, and is a technique of changing the composition M according to the particle size (claim 5).
従来技術では、成分の異なる種々の正極材料が検討されている、しかし、従来技術の正極材料で得られるリチウム二次電池では、放電容量、充放電効率、レート特性および安全性について、さらなる改良が求められている。特に正極材料が大気雰囲気下で経時の質量変化が大きい組成物であるとそれを使用したリチウム二次電池の品質に影響するという問題がある。 In the prior art, various positive electrode materials having different components have been studied, but in the lithium secondary battery obtained with the conventional positive electrode material, further improvement is made in discharge capacity, charge/discharge efficiency, rate characteristics and safety. It has been demanded. In particular, if the positive electrode material is a composition having a large change in mass over time in the air, there is a problem that the quality of a lithium secondary battery using the composition is affected.
本発明は、安全性が高く容量が大きく、レート特性に優れ、劣化しない、Ｌｉ−Ｎｉ−Ｃｏ−Ｏ系、Ｌｉ−Ｎｉ−Ｍｎ−Ｏ系、またはＬｉ−Ｎｉ−Ｍｎ−Ｃｏ−Ｏ系の組成を有する新規なリチウム二次電池の正極活物質に用いられる材料（以下、正極材料という）を提供する。 INDUSTRIAL APPLICABILITY The present invention is of a Li-Ni-Co-O system, a Li-Ni-Mn-O system, or a Li-Ni-Mn-Co-O system, which is highly safe, has a large capacity, is excellent in rate characteristics and does not deteriorate. Provided is a material (hereinafter, referred to as a positive electrode material) used as a positive electrode active material of a novel lithium secondary battery having a composition.
上記課題を解決するために、本発明は、Ｌｉ−Ｎｉ−Ｃｏ（またはＭｎ）−Ｏ材料に、さらに２種以上の他元素成分を有する複合酸化物組成よりなるリチウム二次電池用正極材料、その製造方法、及びこの新規な材料を用いたリチウム二次電池を提供する。 In order to solve the above problems, the present invention provides a Li-Ni-Co (or Mn)-O material, a positive electrode material for a lithium secondary battery, which comprises a composite oxide composition further containing two or more other element components. A method for producing the same and a lithium secondary battery using the novel material are provided.
（１）全体組成がＬｉａＮｉｂＭｃＮｄＬｅＯｘで表される複合酸化物であることを特徴とするリチウム二次電池用正極材料：
但し、
Ｍ：ＭｎおよびＣｏから選ばれる１種又は２種の元素、
Ｎ：Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれる１種又は２種以上の元素、
Ｌ：Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれる１種又は２種以上の元素であり、
ａ／（ｂ＋ｃ＋ｄ） ： ０．８０〜１．３０
ｂ／（ｂ＋ｃ＋ｄ） ： ０．３０〜０．９５
ｃ／（ｂ＋ｃ＋ｄ） ： ０．０５〜０．６０
ｄ／（ｂ＋ｃ＋ｄ） ： ０．００５〜０．１０
ｅ／（ｂ＋ｃ＋ｄ） ： ０．０００５〜０．０１０
ｂ＋ｃ＋ｄ＝１、
ｘ ： １．５〜２．５
である。
（２）大気雰囲気、２５℃、湿度６０％の環境下において、２４０時間後の質量変化が０．６０質量％以下である、（１）に記載のリチウム二次電池用正極材料。
（３）荷重を９５．５ＭＰａ与えた時の成型体の密度が３．２０ｇ／ｃｃ以上である、（１）または（２）に記載のリチウム二次電池用正極材料。
（４）平均粒径が０．１μｍ以上の一次粒子が凝集して二次粒子を形成している、（１）〜（３）のいずれか１つに記載のリチウム二次電池用正極材料。
（５）前記複合酸化物の二次粒子の粒度分布において、個数基準のＤ９０とＤ１０との差が５．０μｍ以上である（４）に記載のリチウム二次電池用正極材料。
（６）上記（１）に記載のリチウム二次電池用正極材料の製造方法であって、原料元素または原料元素を含む化合物を混合し、７００〜９５０℃で焼成する焼成工程の後に水洗工程を含むリチウム二次電池用正極材料の製造方法。
（７）上記（１）〜（５）のいずれか１つに記載のリチウム二次電池用正極材料を含む正極活物質を有する正極と、負極活物質を有する負極と、前記正極と前記負極との間に介在しリチウムイオンを伝導するイオン伝導媒体とを備えたリチウム二次電池。
（８）前記複合酸化物が、Ｌｉ化合物と、Ｎｉ元素と共に、ＭｎおよびＣｏから選ばれた１種又は２種以上の元素を共沈させた水酸化物と、前記以外の元素の酸化物、硝酸塩、硫酸塩、炭酸塩、酢酸塩、およびリン酸塩から選ばれた１種又は２種以上の化合物を混合、焼成して製造される複合酸化物である（１）〜（５）のいずれか１つに記載のリチウム二次電池用正極材料。
(1) A positive electrode material for a lithium secondary battery, which is a composite oxide whose entire composition is represented by Li a Ni b M c N d L e O x :
However,
M: one or two elements selected from Mn and Co,
N: one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe,
L: one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba,
a/(b+c+d): 0.80 to 1.30
b/(b+c+d): 0.30 to 0.95
c/(b+c+d): 0.05-0.60
d/(b+c+d): 0.005-0.10
e/(b+c+d): 0.0005 to 0.010
b+c+d=1,
x: 1.5 to 2.5
Is.
(2) The positive electrode material for a lithium secondary battery according to (1), which has a mass change of 0.60 mass% or less after 240 hours in an atmosphere of 25° C. and a humidity of 60%.
(3) The positive electrode material for a lithium secondary battery according to (1) or (2), wherein the molded body has a density of 3.20 g/cc or more when a load of 95.5 MPa is applied.
(4) The positive electrode material for a lithium secondary battery according to any one of (1) to (3), in which primary particles having an average particle diameter of 0.1 μm or more are aggregated to form secondary particles.
(5) The positive electrode material for a lithium secondary battery according to (4), wherein in the particle size distribution of the secondary particles of the complex oxide, the number-based difference between D 90 and D 10 is 5.0 μm or more.
(6) The method for producing a positive electrode material for a lithium secondary battery according to (1) above, which comprises mixing a raw material element or a compound containing the raw material element and firing at 700 to 950° C., followed by a water washing step. A method for producing a positive electrode material for a lithium secondary battery containing the same.
(7) A positive electrode having a positive electrode active material containing the positive electrode material for a lithium secondary battery according to any one of (1) to (5), a negative electrode having a negative electrode active material, the positive electrode and the negative electrode. A lithium secondary battery having an ion conductive medium interposed between and for conducting lithium ions.
(8) The complex oxide is a Li compound, a hydroxide obtained by coprecipitating one or more elements selected from Mn and Co together with a Ni element, and an oxide of an element other than the above, Any of (1) to (5), which is a composite oxide produced by mixing and firing one or more compounds selected from nitrates, sulfates, carbonates, acetates, and phosphates. The positive electrode material for a lithium secondary battery according to any one of the above.
本発明のリチウム二次電池用正極材料は、安全性が高く、容量が大きく、レート特性に優れ、劣化しないバランスの良い優れた正極材料である。 INDUSTRIAL APPLICABILITY The positive electrode material for a lithium secondary battery of the present invention is a positive electrode material having high safety, large capacity, excellent rate characteristics, and good balance with no deterioration.
以下に本発明を説明する。
〔リチウム二次電池用正極材料〕
本発明の正極材料は、全体組成がＬｉａＮｉｂＭｃＮｄＬｅＯｘで表される複合酸化物である。ここで、
Ｍ：ＭｎおよびＣｏから選ばれた１種又は２種の元素
Ｎ：Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれた１種又は２種以上の元素
Ｌ：Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれた１種又は２種以上の元素であり、
ａ／（ｂ＋ｃ＋ｄ） ： ０．８０〜１．３０
ｂ／（ｂ＋ｃ＋ｄ） ： ０．３０〜０．９５
ｃ／（ｂ＋ｃ＋ｄ） ： ０．０５〜０．６０
ｄ／（ｂ＋ｃ＋ｄ） ： ０．００５〜０．１０
ｅ／（ｂ＋ｃ＋ｄ） ： ０．０００５〜０．０１０
ｂ＋ｃ＋ｄ＝１、および ｘ ： １．５〜２．５である。
ここで、Ｌｉ（リチウム）、Ｎｉ（ニッケル）、Ｍｎ（マンガン）、Ｃｏ（コバルト）、Ｍｇ（マグネシウム）、Ａｌ（アルミニウム）、Ｔｉ（チタン）、Ｃｒ（クロム）、Ｆｅ（鉄）、Ｂ（ホウ素）、Ｃ（炭素）、Ｎａ（ナトリウム）、Ｓｉ（ケイ素）、Ｐ（リン）、Ｓ（硫黄）、Ｋ（カリウム）、Ｃａ（カルシウム）、Ｂａ（バリウム）、Ｏ（酸素）である。
The present invention will be described below.
[Cathode material for lithium secondary batteries]
The positive electrode material of the present invention is a composite oxide whose overall composition is represented by Li a Ni b M c N d Le O x . here,
M: one or two elements selected from Mn and Co N: one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe L: B, C, Na, One or more elements selected from the group consisting of Si, P, S, K, Ca and Ba,
a/(b+c+d): 0.80 to 1.30
b/(b+c+d): 0.30 to 0.95
c/(b+c+d): 0.05-0.60
d/(b+c+d): 0.005-0.10
e/(b+c+d): 0.0005 to 0.010
b+c+d=1, and x: 1.5 to 2.5.
Here, Li (lithium), Ni (nickel), Mn (manganese), Co (cobalt), Mg (magnesium), Al (aluminum), Ti (titanium), Cr (chromium), Fe (iron), B( Boron), C (carbon), Na (sodium), Si (silicon), P (phosphorus), S (sulfur), K (potassium), Ca (calcium), Ba (barium), and O (oxygen).
上記成分は、ＮｉとＭとＮの合計が１モル（すなわちｂ＋ｃ＋ｄ＝１）とした時の成分のモル数を表す。
Ｌｉ成分は、０．８０〜１．３０モルとする。Ｌｉが少ないとリチウム欠損が多い結晶構造となり、リチウム二次電池用正極に用いたときに電池の容量が低下する。多すぎると水酸化リチウムや炭酸リチウム等の水和物や炭酸化物を生成し、電極製造時にゲル化状態となるため、０．８０〜１．３０モルの範囲とする。好ましくは０．８５〜１．２０モルの範囲とする。
Ｎｉ成分は、０．３０〜０．９５モルとする。少なすぎると電池の容量が低下し、多すぎると安定性が劣る。好ましくは０．５０〜０．９５モルの範囲、より好ましくは０．６０〜０．９５モルの範囲とする。
Ｍ成分のＭｎおよびＣｏは、熱安定性を高めるが、多すぎると放電容量を低下させるため、０．０５〜０．６０モルの範囲とする。好ましくは０．０５〜０．４０モルである。Ｍ成分とＮ成分とは、予めＮｉと共沈水和物を生成し、正極材料用原料とすることもできる。
Ｎ成分のＭｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれた１種又は２種以上の成分は、０．００５〜０．１０モルの範囲とする。好ましくは０．００５〜０．０７モルである。この範囲であると結晶性が適度に低下しＬｉイオン拡散を良好にできる効果がある。０．１０モルを超えて配分すると電池の容量低下を招く。
The above component represents the number of moles of the component when the total of Ni, M and N is 1 mol (that is, b+c+d=1).
The Li component is 0.80 to 1.30 mol. When the amount of Li is small, the crystal structure has a large amount of lithium deficiency, and the capacity of the battery decreases when it is used as a positive electrode for a lithium secondary battery. If the amount is too large, hydrates and carbonates such as lithium hydroxide and lithium carbonate are generated, and a gelled state is formed at the time of manufacturing the electrode. The preferred range is 0.85 to 1.20 mol.
The Ni component is 0.30 to 0.95 mol. If it is too small, the battery capacity will decrease, and if it is too large, the stability will be poor. The range is preferably 0.50 to 0.95 mol, more preferably 0.60 to 0.95 mol.
Mn and Co, which are M components, increase the thermal stability, but if they are too much, they reduce the discharge capacity, so the amount is made 0.05 to 0.60 mol. It is preferably 0.05 to 0.40 mol. The M component and the N component can be used as a raw material for the positive electrode material by previously forming a coprecipitated hydrate with Ni.
One or more components selected from the group consisting of N component Mg, Al, Ti, Cr and Fe are in the range of 0.005 to 0.10 mol. It is preferably 0.005 to 0.07 mol. Within this range, the crystallinity is appropriately reduced, and there is an effect that Li ion diffusion can be improved. If it is distributed over 0.10 mol, the capacity of the battery is lowered.
Ｌ成分のＢ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれた１種又は２種以上の元素を含むと、得られる正極材料が、大気雰囲気、常温環境下において、経時の質量変化が少ない。Ｌ成分としてＣ、Ｓ、Ｂａが好ましい。Ｌ成分は熱安定性を向上させるために、０．０００５〜０．０１０モルの範囲で含有させる。少な過ぎると、製造される二次電池の正極が適正な熱安定性を得ることが困難であり、大気雰囲気、常温環境下において、経時の質量変化が大きくなる。また、０．０１０モルを超えて配分すると容量が極度に低下する。好ましくは０．００１〜０．００８モルの範囲とする。 When one or more elements selected from the group consisting of L, B, C, Na, Si, P, S, K, Ca, and Ba are contained, the obtained positive electrode material has an atmospheric atmosphere and a normal temperature environment. Below, there is little change in mass over time. C, S and Ba are preferable as the L component. The L component is contained in an amount of 0.0005 to 0.010 mol in order to improve thermal stability. If the amount is too small, it is difficult for the positive electrode of the secondary battery to be manufactured to obtain proper thermal stability, and the mass change over time becomes large in the air atmosphere and the normal temperature environment. Further, when the amount is distributed over 0.010 mol, the capacity is extremely reduced. The range is preferably 0.001 to 0.008 mol.
本発明のリチウム二次電池用正極材料は、Ｌｉ、Ｎｉ、Ｍｎおよび・またはＣｏを基本とする酸化物組成に、Ｎ成分として、Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれる１種又は２種以上の元素と、Ｌ成分としてのＢ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれる１種または２種以上の元素を加えることが特徴である。Ｎ成分とＬ成分とを加えることによる作用効果については必ずしも明らかではないが、Ｎ成分の添加によって高率放電性能に特に顕著な効果が得られるため、好ましい。しかし、成分の組合せとそれらの量比によっては電池の性能のバランスや安全性を損なう場合があり、そのような場合はＮ成分の添加によっても放電性能が上がらない場合がある。このためＮ成分とＬ成分とを組み合わせることが有効である。
Ｎ成分元素を添加することで、正極材料の結晶性が適度に低下して、Ｌｉイオンの移動経路へ影響し、Ｌｉイオン伝導性が向上するのではないかと考えられる。Ｌ成分元素は、余剰に存在するＬｉを固定化する効果と正極材料結晶系における各主要元素の結合状態に影響を及ぼし、正極材料結晶中のＬｉの脱落を防ぐ効果があると考えられ、その結果、大気雰囲気、常温環境下において経時の質量変化を少なくして大気中における正極材料の劣化を防止するものと推定している。
The positive electrode material for a lithium secondary battery of the present invention has an oxide composition based on Li, Ni, Mn and/or Co, and is selected from the group consisting of Mg, Al, Ti, Cr and Fe as the N component. One or two or more elements and one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba as the L component are characterized by being added. is there. Although the effect of adding the N component and the L component is not always clear, the addition of the N component is preferable because a particularly remarkable effect can be obtained in the high rate discharge performance. However, depending on the combination of components and the amount ratio thereof, the balance of the performance of the battery and the safety may be impaired, and in such a case, the addition of the N component may not improve the discharge performance. Therefore, it is effective to combine the N component and the L component.
It is considered that the addition of the N component element may appropriately reduce the crystallinity of the positive electrode material, affect the migration path of Li ions, and improve the Li ion conductivity. It is considered that the L component element has an effect of fixing excess Li and influences the bonding state of each main element in the positive electrode material crystal system, and an effect of preventing Li from falling out in the positive electrode material crystal. As a result, it is presumed that the deterioration of the positive electrode material in the air is prevented by reducing the change in mass over time in the air atmosphere and the room temperature environment.
本発明のリチウム二次電池用正極材料は、Ｎｉの一部をＣｏおよび・またはＭｎで置換する際に、少量のＮ成分を含有させ、さらにＮ成分より少量のＬ成分を組み合わせて含有させて得られる複合酸化物とするのが特徴である。本発明では、Ｃｏ，Ｍｎ，Ｂａは、リチウム二次電池として高い安全性に寄与している。Ａｌ，Ｍｇは、本発明の系に添加するとサイクル特性を向上させる効果があり、Ａｌ、Ｔｉ，Ｃｒ，Ｆｅは、レート特性を上げる効果があると考えられる。 The positive electrode material for a lithium secondary battery of the present invention contains a small amount of N component when substituting a part of Ni with Co and/or Mn, and further contains a smaller amount of L component than N component in combination. The feature is that the obtained composite oxide is used. In the present invention, Co, Mn, and Ba contribute to high safety as a lithium secondary battery. It is considered that Al and Mg have an effect of improving cycle characteristics when added to the system of the present invention, and Al, Ti, Cr and Fe have an effect of improving rate characteristics.
本発明のリチウム二次電池用正極材料は、大気雰囲気、２５℃、湿度６０％の環境下において、２４０時間後の質量変化が、好ましくは０．６０質量％以下である。より好ましくは０．５０質量％以下、さらに好ましくは０．４５質量％以下である。測定は、大気雰囲気、温度２５±３℃、湿度６０±５％に制御した環境下に、２４０時間経過前後の質量変化を測定する。
一般にニッケルを含むリチウム二次電池用正極材料は、水と二酸化炭素を吸収し易いと言われる。大気中の水分を吸収すると、リチウム水和物が生成し、生成したリチウム水和物が炭酸ガスを吸収した後、炭酸水素リチウムや炭酸リチウムが生成する。
ニッケルを含むリチウム二次電池用正極材料を使用した二次電池において、正極材料が水分を吸収すると一般に用いられる電解質塩であるＬｉＰＦ６の加水分解が発生し、加水分解によりフッ酸やリン酸などの酸が生成する。生成した酸は、電池の構成材料の一部を分解し種々のガスを放出する。そのため、発生したガスの影響で二次電池に膨れが発生し、安全性の低下を招くことがある。
大気雰囲気、２５℃、湿度６０％の一定の環境下において、２４０時間後の質量変化が０．６０質量％以下であれば、上記の現象が起因となる正極合剤ペースト（塗料）のゲル化および電池の膨れが低減する。本発明の系では、Ｌ成分元素である、Ｂａ、Ｃａ、Ｋ、Ｎａ、Ｓ、Ｃ、Ｓｉ、Ｐ、Ｂの少なくとも１つの添加によって、質量変化率を抑えることができる。
The positive electrode material for a lithium secondary battery of the present invention has a mass change of preferably 0.60 mass% or less after 240 hours in an atmosphere of 25° C. and a humidity of 60%. It is more preferably 0.50% by mass or less, still more preferably 0.45% by mass or less. In the measurement, the mass change before and after the lapse of 240 hours is measured in an air atmosphere, an environment controlled at a temperature of 25±3° C. and a humidity of 60±5%.
Generally, a positive electrode material for a lithium secondary battery containing nickel is said to easily absorb water and carbon dioxide. When water in the atmosphere is absorbed, lithium hydrate is generated, and the generated lithium hydrate absorbs carbon dioxide gas, and then lithium hydrogen carbonate or lithium carbonate is generated.
In a secondary battery using a positive electrode material for a lithium secondary battery containing nickel, when the positive electrode material absorbs water, LiPF 6 , which is a commonly used electrolyte salt, is hydrolyzed, and the hydrolysis causes hydrofluoric acid, phosphoric acid, or the like. Acid is produced. The generated acid decomposes a part of the constituent material of the battery and releases various gases. Therefore, the secondary battery may swell due to the generated gas, resulting in a decrease in safety.
If the mass change after 240 hours is 0.60 mass% or less in a constant environment of air atmosphere, 25° C., and humidity of 60%, gelation of the positive electrode mixture paste (paint) that causes the above phenomenon occurs And the swelling of the battery is reduced. In the system of the present invention, the mass change rate can be suppressed by adding at least one of the L component elements Ba, Ca, K, Na, S, C, Si, P, and B.
本発明のリチウム二次電池用正極材料は、平均粒径が０．１μｍ以上の一次粒子が凝集して二次粒子を形成しているのが好ましい。０．１μｍ未満の粒子の存在により、熱安定性が低下することから、平均粒径が０．１μｍ以上の一次粒子が凝集して二次粒子を形成している正極材料が好ましい。本発明の正極材料では、電子顕微鏡で３０００倍で観察して多面体の１次粒子が略球状に凝集している２次粒子が観察される。 In the positive electrode material for a lithium secondary battery of the present invention, it is preferable that primary particles having an average particle diameter of 0.1 μm or more aggregate to form secondary particles. The presence of particles having a particle size of less than 0.1 μm lowers thermal stability. Therefore, a positive electrode material in which primary particles having an average particle size of 0.1 μm or more are aggregated to form secondary particles is preferable. In the positive electrode material of the present invention, secondary particles in which polyhedral primary particles are aggregated in a substantially spherical shape are observed when observed with an electron microscope at 3000 times.
本発明は正極に用いる合剤全体の密度を増加させて正極電極の体積当たりの容量を高め、電池特性を最大限に満足できるリチウム二次電池用正極材料を提供する。
このためには正極材料の粒子間の充填率を増大させることが有効であり、粒子間に適切な粒度分布があることが好ましい。
本発明では、全体組成がＬｉａＮｉｂＭｃＮｄＬｅＯｘで表される複合酸化物で、
Ｍ：ＭｎおよびＣｏから選ばれた１種又は２種の元素
Ｎ：Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれた１種又は２種以上の元素、
Ｌ：Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれた１種又は２種以上の元素であり、
ａ／（ｂ＋ｃ＋ｄ） ： ０．８０〜１．３０
ｂ／（ｂ＋ｃ＋ｄ） ： ０．３０〜０．９５
ｃ／（ｂ＋ｃ＋ｄ） ： ０．０５〜０．６０
ｄ／（ｂ＋ｃ＋ｄ） ： ０．００５〜０．１０
ｅ／（ｂ＋ｃ＋ｄ） ： ０．０００５〜０．０１０
ｂ＋ｃ＋ｄ＝１、および ｘ ： １．５〜２．５
である正極材料の１次粒子の平均粒径を０．１μｍ以上として、１次粒子が凝集した２次粒子を形成させ、その２次粒子が比較的広い粒度分布を持つと粒子の充填率が高い。粒子の充填率は粉末をプレスしてペレットに製造した後、ペレットの密度を測定したプレス密度として測定することができる。１次粒子の平均粒径の上限は特に限定されないが、５μｍ以下とするのが実際的である。
The present invention provides a positive electrode material for a lithium secondary battery, which is capable of increasing the density of the whole mixture used for the positive electrode to increase the capacity per volume of the positive electrode and maximizing the battery characteristics.
For this purpose, it is effective to increase the packing ratio between the particles of the positive electrode material, and it is preferable that the particles have an appropriate particle size distribution.
In the present invention, a composite oxide having an overall composition represented by Li a Ni b M c N d L e O x ,
M: one or two elements selected from Mn and Co N: one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe,
L: one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba,
a/(b+c+d): 0.80 to 1.30
b/(b+c+d): 0.30 to 0.95
c/(b+c+d): 0.05-0.60
d/(b+c+d): 0.005-0.10
e/(b+c+d): 0.0005 to 0.010
b+c+d=1, and x: 1.5 to 2.5
When the average particle size of the primary particles of the positive electrode material is 0.1 μm or more and secondary particles in which the primary particles are aggregated are formed and the secondary particles have a relatively wide particle size distribution, the packing factor of the particles is high. The packing factor of particles can be measured as a press density obtained by measuring the density of pellets after pressing the powder to produce pellets. The upper limit of the average particle size of the primary particles is not particularly limited, but it is practically set to 5 μm or less.
本発明のリチウム二次電池用正極材料は、荷重を９５．５ＭＰａ与えた時の成型体の密度が好ましくは３．２０ｇ／ｃｃ以上である。上限は高いほどよいが４．５０ｇ／ｃｃを越えるのは実際的ではない。プレス密度がこの範囲であると、電極の容積当たりの容量が増加する。より好ましくは、プレス密度は３．４０ｇ／ｃｃ以上である。
加圧成形体の密度は、プレス密度、加圧密度、またはペレット密度（錠剤形としたとき）とも呼ばれるもので、リチウム二次電池正極用材料ではタップ密度より製品に近い特性を示す。本発明の正極材料では、タップ密度と比較するとタップ密度大、小の２つの製品がプレス密度小、大と逆転する場合がある。これは表面状態と粒度分布との総合的な特性をプレス密度が示しているからであると考えられる。本発明の系ではＭｇ、Ｂａ，Ｃａ，Ｋ，Ｎａの添加がプレス密度を向上させ、Ｂａ、Ｃａ、Ｋ，Ｎａ，Ｓ，Ｃ，Ｓｉ，Ｐ，Ｂの添加で質量増加率を抑えられると考えられる。
The positive electrode material for a lithium secondary battery of the present invention preferably has a density of a molded body of 3.20 g/cc or more when a load of 95.5 MPa is applied. The higher the upper limit, the better, but it is not practical to exceed 4.50 g/cc. When the press density is in this range, the capacity per volume of the electrode increases. More preferably, the press density is 3.40 g/cc or more.
The density of the pressure-molded body is also called press density, pressure density, or pellet density (when made into a tablet shape), and a lithium secondary battery positive electrode material exhibits characteristics closer to a product than a tap density. In the positive electrode material of the present invention, two products having a high tap density and a low tap density may be reversed to have a low press density and a high tap density as compared with the tap density. It is considered that this is because the press density shows the overall characteristics of the surface state and the particle size distribution. In the system of the present invention, the addition of Mg, Ba, Ca, K, Na improves the press density, and the addition of Ba, Ca, K, Na, S, C, Si, P, B suppresses the mass increase rate. Conceivable.
本発明のリチウム二次電池用正極材料は、プレス密度が高くなるように二次粒子の粒度分布を調製することができる。プレス密度が高い正極材料を用いると、正極の電極密度が高くなり、体積当たりの放電容量が高くなる。３μｍ未満の二次粒子の割合が多くなると、電極の塗工性が悪くなるので、二次粒子の平均粒子径が３μｍ以上である方が電極の塗工性に優れているため望ましい。
粒度分布の測定は、レーザー回折散乱式測定方法によって全粒度範囲の分布を求める。「Ｄ１０，Ｄ９０」は、個数基準の粒度分布における積算値１０％および９０％での粒径を意味し、レーザー回折散乱式測定方法によって求める。本発明の正極材料では、Ｄ９０−Ｄ１０が５．０μｍ以上であるのがより好ましい。この範囲であるとプレス密度が高くなり、正極材料の体積当たりの容量が増加し、得られる電池容量が高くなる。Ｄ９０−Ｄ１０が７．０μｍ以上２０．０μｍ以下であるのがさらに好ましい。
粒径分布を適切な範囲に調製する方法は、焼成前の粒径範囲を適切に調整したり、焼結後に必要な場合は解砕し、フィルター等で分級して粒径分布の調整を行ってもよい。
In the positive electrode material for a lithium secondary battery of the present invention, the particle size distribution of secondary particles can be adjusted so that the press density becomes high. When a positive electrode material having a high press density is used, the electrode density of the positive electrode increases, and the discharge capacity per volume increases. If the proportion of secondary particles having a particle size of less than 3 μm increases, the coatability of the electrode deteriorates. Therefore, it is desirable that the average particle size of the secondary particles is 3 μm or more because the coatability of the electrode is excellent.
To measure the particle size distribution, the distribution in the entire particle size range is determined by the laser diffraction/scattering measurement method. “D 10 , D 90 ”means the particle size at integrated values 10% and 90% in the number-based particle size distribution, and is determined by a laser diffraction scattering measurement method. In the positive electrode material of the present invention, it is more preferable that D 90 -D 10 is 5.0 μm or more. Within this range, the press density increases, the capacity per volume of the positive electrode material increases, and the obtained battery capacity increases. More preferably, D 90 -D 10 is 7.0 μm or more and 20.0 μm or less.
The method for adjusting the particle size distribution to an appropriate range is to adjust the particle size range before firing appropriately, or crush it if necessary after sintering and classify with a filter etc. to adjust the particle size distribution. May be.
正極材料のプレス密度が高いと、正極の体積当たりの容量が増加して電池容量の増大に寄与できる。しかし圧延工程時に正極材料の粒径および種類によっては、破壊、剥離脱落などが起こり密度を上げられないことがある。必要な場合は製造条件を変えて異なった平均粒径を有する２種以上の粉体を製造し、それを適性範囲で混合してもよい。製造条件における焼成温度、粉砕条件を調製してプレス密度の高い正極材料を得ることができる。 When the press density of the positive electrode material is high, the capacity per volume of the positive electrode increases, which can contribute to an increase in battery capacity. However, depending on the particle size and type of the positive electrode material during the rolling process, the density may not be increased due to breakage, peeling and falling. If necessary, the production conditions may be changed to produce two or more kinds of powders having different average particle sizes, and the powders may be mixed in an appropriate range. It is possible to obtain a positive electrode material having a high press density by adjusting the firing temperature and the crushing conditions in the manufacturing conditions.
〔リチウム二次電池用正極材料の製造方法〕
本発明の正極材料の製造方法を以下に説明するが、以下の説明に限定されるものではない。
本発明の正極材料である複合酸化物を製造するのに用いる原料としては、酸化物又は製造工程における合成時の焼成反応により酸化物となるものを用いることができる。
本発明の正極材料である複合酸化物を製造するのに用いる原料に、Ｌｉおよび、ＭｎおよびＣｏから選ばれた１種又は２種の元素および、Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれた１種又は２種以上の元素および、Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれる１種又は２種以上の元素からなる成分を混合し、これを焼成する。これにより、リチウム二次電池用正極材料を製造することができる。
[Method for producing positive electrode material for lithium secondary battery]
The method for producing the positive electrode material of the present invention will be described below, but the present invention is not limited to the following description.
As a raw material used for producing the composite oxide that is the positive electrode material of the present invention, an oxide or a material that becomes an oxide by a firing reaction during synthesis in the production process can be used.
The raw material used for producing the composite oxide that is the positive electrode material of the present invention includes Li and one or two elements selected from Mn and Co and a group consisting of Mg, Al, Ti, Cr and Fe. A mixture of one or two or more elements selected from the following and one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba are mixed. Then, it is baked. Thereby, the positive electrode material for lithium secondary batteries can be manufactured.
本発明の複合酸化物の合成方法は、特に限定されるものでなく、固相反応法、溶液からの析出を経てそれを焼成する方法、噴霧燃焼法、溶融塩法等種々の方法によって合成することができる。
その一例を示せば、リチウム源、ニッケル源等を、目的とするリチウムニッケル複合酸化物の組成に応じた割合でそれぞれ混合し、形成させる複合酸化物の種類により、焼成温度は適宜選択するが、酸素、窒素、アルゴンおよびヘリウムからなる群から選ばれた１種または２種以上の気体の雰囲気下で７００〜９５０℃程度の温度で焼成することによって合成することができる。上記焼成は酸素雰囲気において３００〜５００℃で２〜６時間の保持を行う予備焼成と、予備焼成後５〜３０℃／ｍｉｎで昇温する昇温段階と、該昇温段階に引き続き７００〜９５０℃で２〜３０時間の保持を行う最終焼成段階を順次行う焼成工程であって、焼成した複合酸化物と水とを混合し攪拌する水洗工程と脱水工程および乾燥工程を含む製造方法で複合酸化物を製造することも好ましい。
Ｎｉ系正極材料は水分を吸収しやすいので、通常水で洗浄しない。しかし、本工程では水洗工程で未反応のＬｉを除去すると、この正極材料を用いて得られるリチウム二次電池の合剤ペースト（塗料）のゲル化および電池の膨れが低減する。
The method for synthesizing the composite oxide of the present invention is not particularly limited, and it can be synthesized by various methods such as a solid phase reaction method, a method of firing it after precipitation from a solution, a spray combustion method, and a molten salt method. be able to.
If one example is shown, a lithium source, a nickel source, and the like are mixed at a ratio according to the composition of the target lithium-nickel composite oxide, and the firing temperature is appropriately selected depending on the type of the composite oxide to be formed. It can be synthesized by firing at a temperature of about 700 to 950° C. in an atmosphere of one or more gases selected from the group consisting of oxygen, nitrogen, argon and helium. The firing is pre-baking in which the temperature is kept at 300 to 500° C. for 2 to 6 hours in an oxygen atmosphere, a temperature raising step of raising the temperature at 5 to 30° C./min after the pre firing, and 700 to 950 subsequent to the temperature raising step It is a calcination process in which a final calcination step of holding at 2° C. for 2 to 30 hours is performed sequentially, and a composite oxidization is performed by a manufacturing method including a washing process of mixing and stirring the calcinated composite oxide and water, a dehydration process and a drying process. It is also preferable to produce a product.
Since the Ni-based positive electrode material easily absorbs water, it is usually not washed with water. However, in this step, when unreacted Li is removed in the water washing step, gelation of the mixture paste (paint) of the lithium secondary battery obtained by using this positive electrode material and swelling of the battery are reduced.
Ｎｉ源、Ｃｏ源、Ｍｎ源としては酸化物、水酸化物、硝酸塩等を利用することができ、Ｎｉ、Ｃｏ、Ｍｎを含む場合は、均一な混合が重要となるため、例えば、湿式合成法によるＮｉ−Ｃｏ−（ＯＨ）2、Ｎｉ−Ｍｎ−（ＯＨ）2、Ｎｉ−Ｃｏ−Ｍｎ−（ＯＨ）2、が原料として特に好ましい。Ｎｉ−Ｃｏ−（ＯＨ）2、Ｎｉ−Ｍｎ−（ＯＨ）2、Ｎｉ−Ｃｏ−Ｍｎ−（ＯＨ）2 は、Ｎｉ、ＣｏおよびＭｎの合計量に対するＣｏおよびＭｎの割合がモル比で０．０５〜０．６０に調製する。その製造に当っては、例えば湿式合成法によって緻密なＮｉ−Ｃｏ−（ＯＨ）2、Ｎｉ−Ｍｎ−（ＯＨ）2、Ｎｉ−Ｃｏ−Ｍｎ−（ＯＨ）2 の二次粒子状の粉状物を製造し、その際平均粒径が５〜２０μｍ、かつタップ密度が１．８ｇ／ｃｃ以上となるように調整することが望ましい。 As the Ni source, Co source, and Mn source, oxides, hydroxides, nitrates, and the like can be used. When Ni, Co, and Mn are contained, uniform mixing is important. Ni-Co-(OH) 2 , Ni-Mn-(OH) 2 , and Ni-Co-Mn-(OH) 2 are particularly preferable as the raw material. Ni-Co-(OH) 2 , Ni-Mn-(OH) 2 , and Ni-Co-Mn-(OH) 2 have a molar ratio of Co and Mn to the total amount of Ni, Co and Mn of 0. It is adjusted to 05 to 0.60. In its production, for example, by a wet synthesis method, dense Ni-Co-(OH) 2 , Ni-Mn-(OH) 2 , and Ni-Co-Mn-(OH) 2 secondary particles in powder form are used. It is desirable to manufacture the product and adjust the average particle size to be 5 to 20 μm and the tap density to be 1.8 g/cc or more.
Ｌｉ源としては、水酸化物、硝酸塩、炭酸塩等が好ましい。Ｎ成分のＭｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅ、およびＬ成分のＢ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａから選択される一つ以上の元素の化合物としては、それぞれの元素の酸化物、水酸化物、炭酸塩、硝酸塩及び有機酸塩などが用いられる。 As the Li source, hydroxides, nitrates, carbonates and the like are preferable. As the compound of one or more elements selected from Mg, Al, Ti, Cr and Fe as the N component and B, C, Na, Si, P, S, K, Ca and Ba as the L component, Elemental oxides, hydroxides, carbonates, nitrates and organic acid salts are used.
好ましい製造方法は、Ｌｉ化合物と、Ｎｉと共にＭ元素（ＭｎおよびＣｏから選ばれた１種又は２種の元素）を共沈させた水酸化物と、その他の元素の原料の酸化物、硝酸塩、硫酸塩、炭酸塩、酢酸塩、リン酸塩から選ばれた１種又は２種以上の各成分の化合物を混合、焼成して複合酸化物を製造することができる。
更に、Ｎ元素（Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれた１種又は２種以上の元素）あるいは、Ｌ元素（Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれた１種又は２種以上の元素）を共沈させた水酸化物と、その他の元素の原料の酸化物、硝酸塩、硫酸塩、炭酸塩、酢酸塩、リン酸塩から選ばれた１種又は２種以上の各成分の化合物を混合し、焼成して複合酸化物を製造してもよい。
A preferred production method is a Li compound, a hydroxide obtained by coprecipitating an M element (one or two elements selected from Mn and Co) with Ni, an oxide of a raw material of other elements, a nitrate, A compound oxide can be produced by mixing and firing one or more compounds of each component selected from sulfates, carbonates, acetates and phosphates.
Further, N element (one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe) or L element (B, C, Na, Si, P, S, K, Ca) And a hydroxide obtained by co-precipitating one or more elements selected from the group consisting of Ba and Ba, and oxides, nitrates, sulfates, carbonates, acetates, phosphates of the raw materials of other elements. You may manufacture the compound oxide by mixing the compound of 1 type(s) or 2 or more types of each component selected from a salt, and baking.
〔リチウム二次電池〕
本発明の正極材料を用いて、リチウム二次電池用の正極を得る方法は、常法に従って実施できる。例えば、本発明の正極活物質の粉末に、アセチレンブラック、黒鉛、ケッチェンブラック等のカーボン系導電材と、結合材とを混合することにより正極合剤が形成される。結合材には、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリアミド、カルボキシメチルセルロース、アクリル樹脂等が用いられる。
[Lithium secondary battery]
The method for obtaining a positive electrode for a lithium secondary battery using the positive electrode material of the present invention can be carried out according to a conventional method. For example, the positive electrode mixture is formed by mixing the powder of the positive electrode active material of the present invention with a carbon-based conductive material such as acetylene black, graphite, Ketjen black, and a binder. Polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethyl cellulose, acrylic resin or the like is used as the binder.
上記の正極合剤を、Ｎ−メチルピロリドンなどの分散媒に分散させたスラリーをアルミニウム箔等の正極集電体に塗工・乾燥及びプレス圧延して正極活物質層を正極集電体上に形成する。 A slurry prepared by dispersing the above positive electrode mixture in a dispersion medium such as N-methylpyrrolidone is applied to a positive electrode current collector such as an aluminum foil, dried and press-rolled to form a positive electrode active material layer on the positive electrode current collector. Form.
本発明の正極活物質を正極に使用するリチウム二次電池において、電解質溶液の溶質としては、ＣｌＯ4−、ＣＦ3ＳＯ3−、ＢＦ4−、ＰＦ6−、ＡｓＦ6−、ＳｂＦ6−、ＣＦ3ＣＯ2−、（ＣＦ3ＳＯ2）2Ｎ−等をアニオンとするリチウム塩のいずれか１種以上を使用することが好ましい。炭酸エステルは環状、鎖状いずれも使用できる。環状炭酸エステルとしては、プロピレンカーボネート、エチレンカーボネート（ＥＣ）等が例示される。鎖状炭酸エステルとしては、ジメチルカーボネート、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート等が例示される。
セパレータには多孔質ポリエチレン、多孔質ポリプロピレンフィルムなどが使用される。
In a lithium secondary battery using the positive electrode active material of the present invention as a positive electrode, as a solute of an electrolyte solution, ClO 4 −, CF 3 SO 3 −, BF 4 −, PF 6 −, AsF 6 −, SbF 6 −, It is preferable to use at least one of lithium salts having CF 3 CO 2 —, (CF 3 SO 2 ) 2 N— or the like as an anion. The carbonic acid ester may be cyclic or linear. Examples of the cyclic carbonic acid ester include propylene carbonate and ethylene carbonate (EC). Examples of the chain carbonic acid ester include dimethyl carbonate, diethyl carbonate (DEC), ethylmethyl carbonate, methylpropyl carbonate, methylisopropyl carbonate and the like.
Porous polyethylene, porous polypropylene film or the like is used for the separator.
本発明の正極材料を正極に使用するリチウム電池の負極活物質は、リチウムイオンを吸蔵、放出可能な材料である。負極活物質を形成する材料は特に限定されないが、例えばリチウム金属、リチウム合金、炭素材料、炭素化合物、炭化ケイ素化合物、酸化ケイ素化合物、硫化チタン、炭化ホウ素化合物、周期表１４、１５族の金属を主体とした酸化物等が挙げられる。
本発明における正極材料を使用するリチウム二次電池の形状には、特に制約はない。筒形（円筒形や角筒形）の外装缶を使用した筒形電池や、扁平形（平面視で円形や角形の扁平形）の外装缶を使用した扁平形電池、ラミネートフィルムを外装体としたソフトパッケージ電池等が用途に応じて選択される。
The negative electrode active material of a lithium battery using the positive electrode material of the present invention as a positive electrode is a material capable of inserting and extracting lithium ions. The material forming the negative electrode active material is not particularly limited, and examples thereof include lithium metal, lithium alloys, carbon materials, carbon compounds, silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds, and metals of Groups 14 and 15 of the periodic table. Examples include oxides mainly composed of these.
The shape of the lithium secondary battery using the positive electrode material in the present invention is not particularly limited. A cylindrical battery that uses a tubular (cylindrical or prismatic) outer can, a flat battery that uses a flat (circular or rectangular flat in plan view) outer can, and a laminate film as the outer body The soft package battery or the like is selected according to the application.
（実施例１）
原料のＮｉ源とＣｏ源としてＮｉおよびＣｏのモル比を調整して得たＮｉ−Ｃｏ−（ＯＨ）２を湿式溶液合成法によって作製した。その他の出発原料には市販の試薬を使用した。Ｌｉ源にはリチウム水和物、Ａｌ源にはＡｌ２Ｏ３、Ｂａ源にはＢａ（ＮＯ３）２を用いた。
これらの出発原料を目的の配合組成になるように秤量後、十分に混合し、焼成用の原料とした。焼成は酸素雰囲気で行い、まず４００℃で４時間保持し、主に原料中の水分を除去した後、５℃／分の昇温速度で昇温し、８００℃の焼成温度および保持時間４時間で保持し、冷却後炉内から焼成物を取り出した。取り出した焼成物を解砕して正極材料粉末を得た。得られた粉末と水とを混合し攪拌後、脱水、乾燥した。後に記載する条件で、粒度分布測定、化学組成分析、およびその他の評価測定を行った。評価結果を表１に示す。表における「―」は、その項目が未実施であり、測定されていないことを示している。
(Example 1)
Ni-Co-(OH) 2 obtained by adjusting the molar ratio of Ni and Co as the raw material Ni source and Co source was prepared by the wet solution synthesis method. Commercially available reagents were used for the other starting materials. Lithium hydrate was used as the Li source, Al 2 O 3 was used as the Al source, and Ba(NO 3 ) 2 was used as the Ba source.
These starting raw materials were weighed so as to have a desired composition and then sufficiently mixed to obtain raw materials for firing. Firing is carried out in an oxygen atmosphere, and is first held at 400° C. for 4 hours to mainly remove water in the raw materials, then heated at a heating rate of 5° C./min, and baked at 800° C. and held for 4 hours. The temperature was maintained and the fired product was taken out from the furnace after cooling. The fired product taken out was crushed to obtain a positive electrode material powder. The obtained powder and water were mixed, stirred, dehydrated and dried. Particle size distribution measurement, chemical composition analysis, and other evaluation measurements were performed under the conditions described later. The evaluation results are shown in Table 1. "-" in the table indicates that the item has not been implemented and has not been measured.
（実施例２〜２２、比較例１〜９）
原料のＮｉ源、Ｃｏ源、Ｌｉ源、Ａｌ源、Ｂａ源については、実施例１と同様の原料を用いた。なお、実施例１１、１２、１３、２２および比較例７のＭｎ源には、Ｎｉ、ＣｏおよびＭｎのモル比を調整して得たＮｉ−Ｃｏ−Ｍｎ−（ＯＨ）２を湿式溶液合成法によって作製した原料を用いた。また、比較例５のＮｉ源にはＮｉ−（ＯＨ）２、比較例６のＮｉ源、Ｍｎ源にはＮｉおよびＭｎのモル比を調整して得たＮｉ−Ｍｎ−（ＯＨ）２を湿式溶液合成法によって作製した原料を用いた。その他の出発原料は市販の試薬を使用した。Ｓ源には硫黄粉末、Ｃ源にはカーボンブラック、Ｓｉ源にはＳｉＯ２、Ｋ源にはＫＮＯ３、Ｍｎ源にはＭｎ３Ｏ４、Ｍｇ源にはＭｇＯ、Ｔｉ源にはＴｉＯ２、Ｆｅ源にはＦｅ２Ｏ３、Ｐ源にはＰ２Ｏ５、Ｃａ源にはＣａ（ＮＯ３）２・４Ｈ２Ｏ、Ｃｒ源にはＣｒ２Ｏ３、Ｎａ源にはＮａＮＯ３、Ｂ源にはＨ３ＢＯ３を用いた。配合組成の変更以外は、焼成工程、水洗工程は実施例１と同様に行って正極材料粉末を製造した。また、実施例１と同様の条件で評価し、結果を表１に示す。なお、実施例１３、実施例２２および比較例９は水洗工程を行わなかった。
(Examples 2 to 22, Comparative Examples 1 to 9)
For the Ni source, Co source, Li source, Al source, and Ba source of the raw materials, the same raw materials as in Example 1 were used. For the Mn sources of Examples 11, 12, 13, 22 and Comparative Example 7, Ni-Co-Mn-(OH) 2 obtained by adjusting the molar ratio of Ni, Co and Mn was used in the wet solution synthesis method. The raw material produced by Further, Ni-(OH) 2 was used as the Ni source of Comparative Example 5, Ni source of Comparative Example 6 was used, and Ni—Mn—(OH) 2 obtained by adjusting the molar ratio of Ni and Mn was used as the Mn source. The raw material produced by the solution synthesis method was used. Commercially available reagents were used as other starting materials. S source is sulfur powder, C source is carbon black, Si source is SiO 2 , K source is KNO 3 , Mn source is Mn 3 O 4 , Mg source is MgO, Ti source is TiO 2 . the Fe source Fe 2 O 3, the P source P 2 O 5, Ca in source Ca (NO 3) 2 · 4H 2 O, the Cr source Cr 2 O 3, the Na source NaNO 3, B H 3 BO 3 was used as the source. The firing step and the water washing step were performed in the same manner as in Example 1 except that the composition was changed to produce a positive electrode material powder. Further, the evaluation was performed under the same conditions as in Example 1, and the results are shown in Table 1. In addition, Example 13, Example 22, and Comparative Example 9 did not perform a water washing process.
次に、これらからリチウム二次電池用正極を製作し、後述のように電池特性を評価し、表１に示す。 Next, a positive electrode for a lithium secondary battery was produced from these, and the battery characteristics were evaluated as described below, and shown in Table 1.
実施例、比較例のリチウム二次電池用正極材料粉末９０質量％、アセチレンブラック５質量％及びポリ弗化ビニリデン５質量％にＮ−メチル−２−ピロリドンを添加し、十分混練した後、アルミニウム集電体に約１５０μｍの厚さに塗布し、２００ｋｇ／ｃｍ２程度で加圧後、直径１４ｍｍの円板に打ち抜いたものを１５０℃ にて１５時間の真空乾燥し正極とした。負極にはリチウム金属シートを用い、セパレーターにはポリプロピレン製多孔質膜（商品名セルガード#2400）を用いた。また、エチレンカーボネート（ＥＣ）／ジメチルカーボネート（ＤＭＣ）を体積比で１：１の混合溶液１ＬにＬｉＣｌＯ４を１モル溶解させ非水電解液とした。 N-methyl-2-pyrrolidone was added to 90% by mass of the positive electrode material powder for lithium secondary batteries of Examples and Comparative Examples, 5% by mass of acetylene black and 5% by mass of polyvinylidene fluoride, and sufficiently kneaded, and thereafter, aluminum was collected. A positive electrode was prepared by applying a thickness of about 150 μm to an electric body, applying a pressure of about 200 kg/cm 2 , punching out a disc having a diameter of 14 mm, and vacuum drying at 150° C. for 15 hours. A lithium metal sheet was used for the negative electrode, and a polypropylene porous membrane (trade name Celgard #2400) was used for the separator. Further, 1 mol of LiClO 4 was dissolved in 1 L of a mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) at a volume ratio of 1:1 to obtain a non-aqueous electrolytic solution.
これらを用いてアルゴンで置換したグローブボックス内で試験セルに組み立て、電流密度を０．５ｍＡ／ｃｍ２の一定値とし、かつ電圧を２．７５〜４．２５Ｖの範囲で充放電を行い、初回放電容量を測定した。さらに次式により初回充放電効率を算出した。 These were assembled into a test cell in a glove box substituted with argon, the current density was set to a constant value of 0.5 mA/cm 2 , and the voltage was charged/discharged in the range of 2.75 to 4.25 V. The discharge capacity was measured. Further, the initial charge/discharge efficiency was calculated by the following formula.
初回充放電効率＝［（初回の放電容量）／（初回の充電容量）］×１００
レート特性の測定では、さらに２．０ｍＡ／ｃｍ2の定電流密度にて２．７５〜４．２５Ｖで充放電測定を行い次式により算出した。
First charge/discharge efficiency=[(first discharge capacity)/(first charge capacity)]×100
In the measurement of rate characteristics, charge/discharge measurement was further performed at 2.75 to 4.25 V at a constant current density of 2.0 mA/cm 2 , and the rate was calculated by the following formula.
レート特性（％）＝［（２．０ｍＡ／ｃｍ2での放電容量値）
／（０．５ｍＡ／ｃｍ2での放電容量値）］×１００
Rate characteristic (%)=[(discharge capacity value at 2.0 mA/cm 2 )
/(Discharge capacity value at 0.5 mA/cm 2 )]×100
＜評価方法＞
（１）粉体特性
１）一次粒子の平均粒子径：得られた正極用材料を、電子顕微鏡で観察し、粒子径を測定する。
２）二次粒子の粒度分布
レーザー回折散乱式測定装置によって全粒度範囲の分布を求める。「Ｄ１０，Ｄ９０」は、個数基準の粒度分布における積算値１０％および９０％での粒径を意味する。
３）プレス密度
直径２０ｍｍ の金型に一定量の試料を入れて、９５．５ＭＰａの圧力を加えた時、試料の高さの測定値と試料質量から密度を算出した。
タップ密度は、特に加圧することなく自然に粗粒と微粒が混合している粉体が充填する特性を示す。プレス密度は、加圧下で粗粒と微粒がどのように充填するかの特性を示す。
<Evaluation method>
(1) Powder characteristics 1) Average particle diameter of primary particles: The obtained positive electrode material is observed with an electron microscope to measure the particle diameter.
2) Particle size distribution of secondary particles The distribution in the entire particle size range is determined by a laser diffraction/scattering type measuring device. “D 10 , D 90 ”means the particle size at the integrated value of 10% and 90% in the particle size distribution based on the number.
3) Press Density When a certain amount of the sample was put into a mold having a diameter of 20 mm and a pressure of 95.5 MPa was applied, the density was calculated from the measured value of the sample height and the sample mass.
The tap density has a characteristic of being filled with powder in which coarse particles and fine particles are naturally mixed without applying a pressure. Press density is a characteristic of how coarse and fine particles fill under pressure.
（２）化学組成
得られた粉末を定量組成分析し、Ｎｉ＋Ｍ成分＋Ｎ成分＝１モルに対する各元素のモル比を求め表１に全体組成を示した。
（３）質量増加
得られた正極材料をサンプル瓶に所定量秤量し、大気雰囲気、２５±３℃、湿度６０±５％で一定とした環境に保持した恒温恒湿槽に保管し、２４０時間後の質量の増加率を測定する。複数の試料の測定値の平均値からの計算値を質量増加率とする。
(2) Chemical composition The obtained powder was subjected to quantitative composition analysis, and the molar ratio of each element to Ni+M component+N component=1 mol was determined, and the overall composition is shown in Table 1.
(3) Increase in mass The obtained positive electrode material was weighed in a predetermined amount in a sample bottle and stored in a constant temperature and humidity chamber kept in an atmosphere of 25 ± 3°C and a humidity of 60 ± 5% for 240 hours. The rate of increase in mass afterwards is measured. The calculated value from the average value of the measured values of a plurality of samples is the mass increase rate.
（４）釘さし試験
釘さし試験用電池は、以下のように試作を行った。合成したリチウム二次電池用正極材料粉末８９質量％とアセチレンブラック６質量％およびポリフッ化ビニリデン５質量％の割合で混合し、Ｎ−メチル−２−ピロリドンを添加し十分混練した後、２０μｍ厚みのアルミニウム集電体に塗布・乾燥・加圧して正極を作製した。負極はカーボンブラック９２質量％、アセチレンブラック３質量％およびポリフッ化ビニリデン５質量％にＮ−メチル−２−ピロリドンを添加し十分混練した後、１４μｍ厚みの銅集電体に塗布・乾燥・加圧して作製した。正極および負極のそれぞれの電極厚みは７５μｍおよび１００μｍであった。電解液はエチレンカーボネート（ＥＣ）／メチルエチルカーボネート（ＭＥＣ）との体積比１：１の混合溶液１リットルにＬｉＰＦ６を１ｍｏｌ溶解したもので、セパレータはポリプロピレン製多孔質膜、アルミニウムラミネートを用いて６０ｍｍ×３５ｍｍ×厚み４ｍｍ寸法の角型電池を試作した。１６０ｍＡの電流値で４．２Ｖまで充電し、同じ電流値にて３．０Ｖまで放電容量を測定した結果、８００ｍＡであった。
電池を定電圧にて８時間充電した後、電池の中央部に直径２．５ｍｍの釘を貫通させ、この時の電池の状態を観察した。発火がない場合は合格とし、発火が認められたときは不合格とした。
(4) Nailing test The battery for nailing test was manufactured as follows. 89% by mass of the synthesized positive electrode material powder for a lithium secondary battery, 6% by mass of acetylene black and 5% by mass of polyvinylidene fluoride were mixed, and N-methyl-2-pyrrolidone was added thereto and sufficiently kneaded, and then the mixture having a thickness of 20 μm was mixed. A positive electrode was produced by coating, drying and pressing on an aluminum current collector. For the negative electrode, N-methyl-2-pyrrolidone was added to 92% by mass of carbon black, 3% by mass of acetylene black and 5% by mass of polyvinylidene fluoride and sufficiently kneaded, and then coated, dried and pressed onto a 14 μm-thick copper current collector. It was made. The electrode thickness of each of the positive electrode and the negative electrode was 75 μm and 100 μm. The electrolytic solution was prepared by dissolving 1 mol of LiPF 6 in 1 liter of a mixed solution of ethylene carbonate (EC)/methyl ethyl carbonate (MEC) at a volume ratio of 1:1 and using a polypropylene porous membrane and an aluminum laminate as a separator. A square battery having a size of 60 mm×35 mm×thickness of 4 mm was experimentally manufactured. It was 800 mA as a result of charging to 4.2 V at a current value of 160 mA and measuring the discharge capacity to 3.0 V at the same current value.
After charging the battery at a constant voltage for 8 hours, a nail having a diameter of 2.5 mm was penetrated through the center of the battery and the state of the battery at this time was observed. If there was no ignition, it was judged to be acceptable, and if ignition was recognized, it was judged to be unacceptable.
＜実施例・比較例の説明＞
比較例２のＬｉ−Ｎｉ−Ｃｏ−Ｏ系に対してＮ成分としてＡｌ、Ｌ成分としてＢａを添加した本発明の実施例１は、初回放電容量および初回充放電効率は若干低下したものの、レート特性、プレス密度が向上し、質量増加率が低く、釘刺し試験でも合格した特性バランスの優れた正極材料が得られた。さらにＭ成分としてＭｎ、Ｎ成分としてＭｇを追加添加した実施例５は、各々の特性がさらに向上している。
質量増加率の低減に効果のあるＬ成分を添加している実施例に対してＬ成分の添加のない比較例１、２、８および水洗工程を省略している比較例９は、質量増加率が非常に大きな値を示しており、比較例１、２、８および９を正極材料に使用した場合に、正極電極の製造工程におけるゲル化発生や電池における膨れなどの懸念がある。
個数基準の粒度分布であるＤ９０−Ｄ１０が５．０μｍ以上である実施例１、３、４、５、１７と５．０μｍ未満である比較例３、４、９でプレス密度の測定結果を比較するとその差は顕著であり、例え、質量当りの放電容量が高くても容積当りの容量の向上は困難であり、実施例１、３、４、５、１７は優れた容量特性であると言える。
比較例１、２、８の複合酸化物は、Ｌ成分元素を含まない正極材料であり、熱安定性が低く釘刺し試験が不合格で得られる電池の安全性に問題がある。
<Explanation of Examples and Comparative Examples>
In Example 1 of the present invention in which Al as the N component and Ba as the L component were added to the Li—Ni—Co—O system of Comparative Example 2, the initial discharge capacity and the initial charge/discharge efficiency were slightly reduced, but the rate A positive electrode material having improved characteristics and press density, a low mass increase rate, and an excellent property balance that passed the nail penetration test was obtained. Furthermore, in Example 5 in which Mn as the M component and Mg as the N component were additionally added, the respective characteristics were further improved.
In comparison with the example in which the L component effective for reducing the mass increase rate is added, the comparative examples 1, 2, and 8 in which the L component is not added and the comparative example 9 in which the washing step is omitted are Shows a very large value, and when Comparative Examples 1, 2, 8 and 9 are used as the positive electrode material, there is a concern that gelation may occur in the manufacturing process of the positive electrode or swelling in the battery.
Measurement results of press density in Examples 1, 3, 4, 5, 17 in which the number-based particle size distribution D 90 -D 10 is 5.0 μm or more and in Comparative Examples 3, 4, 9 in which it is less than 5.0 μm. Compared with each other, the difference is remarkable, and even if the discharge capacity per mass is high, it is difficult to improve the capacity per volume, and Examples 1, 3, 4, 5, and 17 have excellent capacity characteristics. Can be said.
The composite oxides of Comparative Examples 1, 2, and 8 are positive electrode materials that do not contain an L component element, have low thermal stability, and have a problem in battery safety obtained when the nail penetration test fails.
実施例１、３、１１，２０，２２は、二次粒子の分布が十分広い。実施例３，４，８，９，１８はプレス密度が高い。実施例６，７，１１，１２，１３は、質量増加率が低い。実施例５，７〜１０は初回放電容量が高い。実施例１，５〜１１、１６，２２は初回充放電効率が高い。実施例８，１１，１３，１５〜１７，２０はレート特性が高い。 In Examples 1, 3, 11, 20, and 22, the distribution of secondary particles is sufficiently wide. Examples 3, 4, 8, 9, and 18 have high press densities. Examples 6, 7, 11, 12, and 13 have low mass increase rates. Examples 5, 7 to 10 have high initial discharge capacity. Examples 1, 5 to 11, 16, and 22 have high initial charge/discharge efficiency. The rate characteristics are high in Examples 8, 11, 13, 15 to 17, and 20.
本発明のリチウム二次電池用正極材料を用いる正極は、安全性が高く容量が大きく、レート特性に優れ、特定雰囲気下での質量増加率が小さい。かかる正極を使用したリチウム二次電池は、情報関連機器、通信機器、車輌などにおける小型、軽量でかつ高エネルギー密度の電源として広く使用される。本発明のリチウム二次電池用正極材料を用いて製造される二次電池は、筒形（円筒形や角筒形）の外装缶を使用した筒形電池や、扁平形（平面視で円形や角形の扁平形）の外装缶を使用した扁平形電池、ラミネートフィルムを外装体としたソフトパッケージ電池についても同様に適用することができる。 A positive electrode using the positive electrode material for a lithium secondary battery of the present invention has high safety, a large capacity, excellent rate characteristics, and a small mass increase rate in a specific atmosphere. A lithium secondary battery using such a positive electrode is widely used as a small and lightweight power source with high energy density in information-related devices, communication devices, vehicles and the like. The secondary battery manufactured using the positive electrode material for a lithium secondary battery of the present invention includes a tubular battery using a tubular (cylindrical or rectangular tubular) outer can, a flat battery (circular in plan view, or The same can be applied to a flat battery using an outer can of a rectangular flat shape and a soft package battery using a laminate film as an outer package.
Claims (9)
但し、
Ｍ：ＭｎおよびＣｏから選ばれる１種又は２種の元素、
Ｎ：Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれる１種又は２種以上の元素、
Ｌ：Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれる１種又は２種以上の元素であり、
ａ／（ｂ＋ｃ＋ｄ） ： ０．８０〜１．３０
ｂ／（ｂ＋ｃ＋ｄ） ： ０．３０〜０．９５
ｃ／（ｂ＋ｃ＋ｄ） ： ０．０５〜０．６０
ｄ／（ｂ＋ｃ＋ｄ） ： ０．００５〜０．１０
ｅ／（ｂ＋ｃ＋ｄ） ： ０．０００５〜０．０１０
ｂ＋ｃ＋ｄ＝１、
ｘ ： １．５〜２．５
であり、前記複合酸化物の二次粒子において、レーザー回折散乱式測定方法によって求めた、個数基準の積算値９０％での粒径Ｄ９０と個数基準の積算値１０％での粒径Ｄ１０との差が５．０μｍ以上であり、大気雰囲気、２５℃、湿度６０％の環境下において、２４０時間後の質量変化が０．６０質量％以下である。 A positive electrode material for a lithium secondary battery, which is a composite oxide having an overall composition represented by Li a Ni b M c N d L e O x :
However,
M: one or two elements selected from Mn and Co,
N: one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe,
L: one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba,
a/(b+c+d): 0.80 to 1.30
b/(b+c+d): 0.30 to 0.95
c/(b+c+d): 0.05-0.60
d/(b+c+d): 0.005-0.10
e/(b+c+d): 0.0005 to 0.010
b+c+d=1,
x: 1.5 to 2.5
, And the said at secondary particles of composite oxide was determined by a laser diffraction scattering measuring method, the particle diameter D 10 of an integration value of 10% of the particle diameter D 90 and the number-based on the integrated value 90% based on the number Is 5.0 μm or more, and the change in mass after 240 hours is 0.60% by mass or less under an atmosphere of air, 25° C., and a humidity of 60%.
但し、
Ｍ：ＭｎおよびＣｏから選ばれる１種又は２種の元素、
Ｎ：Ｍｇ、Ａｌ、Ｔｉ、ＣｒおよびＦｅからなる群から選ばれる１種又は２種以上の元素、
Ｌ：Ｂ、Ｃ、Ｎａ、Ｓｉ、Ｐ、Ｓ、Ｋ、ＣａおよびＢａからなる群から選ばれる１種又は２種以上の元素であり、
ａ／（ｂ＋ｃ＋ｄ） ： ０．８０〜１．３０
ｂ／（ｂ＋ｃ＋ｄ） ： ０．３０〜０．９５
ｃ／（ｂ＋ｃ＋ｄ） ： ０．０５〜０．６０
ｄ／（ｂ＋ｃ＋ｄ） ： ０．００５〜０．１０
ｅ／（ｂ＋ｃ＋ｄ） ： ０．０００５〜０．０１０
ｂ＋ｃ＋ｄ＝１、
ｘ ： １．５〜２．５
であり、
原料元素または原料元素を含む化合物を混合し、７００〜９５０℃で焼成した後、水洗、脱水および乾燥して、大気雰囲気、２５℃、湿度６０％の環境下において、２４０時間後の質量変化が０．６０質量％以下である。 A positive electrode material for a lithium secondary battery, which is a composite oxide whose overall composition is represented by Li a Ni b M c N d L e O x :
However,
M: one or two elements selected from Mn and Co,
N: one or more elements selected from the group consisting of Mg, Al, Ti, Cr and Fe,
L: one or more elements selected from the group consisting of B, C, Na, Si, P, S, K, Ca and Ba,
a/(b+c+d): 0.80 to 1.30
b/(b+c+d): 0.30 to 0.95
c/(b+c+d): 0.05-0.60
d/(b+c+d): 0.005-0.10
e/(b+c+d): 0.0005 to 0.010
b+c+d=1,
x: 1.5 to 2.5
And
After mixing the raw material elements or the compounds containing the raw material elements and baking at 700 to 950° C., washing with water, dehydration and drying, the mass change after 240 hours under the atmosphere of air atmosphere, 25° C., and humidity of 60% changes. It is 0.60 mass% or less.
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