JPWO2005112152A1 - リチウム二次電池正極用のリチウム含有複合酸化物の製造方法 - Google Patents
リチウム二次電池正極用のリチウム含有複合酸化物の製造方法 Download PDFInfo
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- JPWO2005112152A1 JPWO2005112152A1 JP2006513570A JP2006513570A JPWO2005112152A1 JP WO2005112152 A1 JPWO2005112152 A1 JP WO2005112152A1 JP 2006513570 A JP2006513570 A JP 2006513570A JP 2006513570 A JP2006513570 A JP 2006513570A JP WO2005112152 A1 JPWO2005112152 A1 JP WO2005112152A1
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- Prior art keywords
- lithium
- carboxylic acid
- source
- powder
- positive electrode
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000000843 powder Substances 0.000 claims abstract description 72
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 230000020169 heat generation Effects 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 27
- 239000007774 positive electrode material Substances 0.000 abstract description 18
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000005973 Carvone Substances 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- -1 LiCoO 2 Chemical class 0.000 description 18
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 17
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 17
- 239000002002 slurry Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 150000002641 lithium Chemical class 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 6
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- 239000012736 aqueous medium Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
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- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
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- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
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- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 238000012360 testing method 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
- 230000007704 transition Effects 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
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Abstract
Description
(1)一般式LipNxMyOzFa(但し、Nは、Co、Mn及びNiからなる群から選ばれる少なくとも1種の元素であり、MはN以外の遷移金属元素、Sn、Zn、Al及びアルカリ土類金属元素からなる群から選ばれる少なくとも1種の元素である。0.9≦p≦1.1、0.97≦x<1.00、0<y≦0.03、1.9≦z≦2.1、x+y=1、0≦a≦0.02)で表され、リチウム源、N元素源、必要に応じて、M元素源及びフッ素源を含む混合物を酸素含有雰囲気において、700〜1050℃で焼成するリチウム含有複合酸化物の製造方法であって、分子内にカルボン酸基又はカルボン酸基と水酸基を合計で2つ以上有しかつ必要に応じてM元素を有するカルボン酸若しくはその塩の水溶液を、平均粒径(D50)が2〜20μmのN元素源粉末に含浸し乾燥した粉末をN元素源として使用することを特徴とするリチウム二次電池正極用リチウム含有複合酸化物の製造方法。
(2)カルボン酸が、炭素数が2〜8のカルボン酸である上記(1)に記載の製造方法。
(3)カルボン酸が、クエン酸、乳酸、蓚酸及び酒石酸からなる群から選ばれる少なくとも1種である上記(1)又は(2)に記載の製造方法。
(4)カルボン酸若しくはその塩の水溶液が、pH2〜12である上記(1)〜(3)のいずれか1項に記載の製造方法。
(5)カルボン酸のM元素塩の水溶液をN元素源粉末に含浸させ、乾燥により水分を除去した後、リチウム源粉末、及び必要に応じて、フッ素源を乾式混合し、その混合粉末を酸素含有雰囲気において850〜1050℃で焼成する上記(1)〜(4)のいずれか1項に記載の製造方法。
(6)カルボン酸のM元素塩の水溶液を、リチウム源粉末、及び必要に応じてフッ素源の共存下で、N元素源粉末に含浸させ、次いで乾燥により水分を除去した後の混合粉末を酸素含有雰囲気において850〜1050℃で焼成する上記(1)〜(4)のいずれか1項に記載の製造方法。
(7)M元素が、Ti、Zr、Hf、Nb、Ta、Mg、Sn、Zn及びAlからなる群から選ばれる少なくとも1種である上記(1)〜(6)のいずれか1項に記載の製造方法。
(8)M元素が、少なくともAlとMgからなり、Al/Mgが原子比で1/3〜3/1であり、かつ0.005≦y≦0.025である上記(1)〜(7)のいずれか1項に記載の製造方法。
(9)M元素がMgとM2(M2は少なくともTi、Zr、Ta及びNbからなる群から選ばれる少なくとも1種の元素)とからなり、M2/Mgが原子比で1/40〜2/1であり、かつ0.005≦y≦0.025である上記(1)〜(7)のいずれか1項に記載の製造方法。
(10)リチウム含有複合酸化物粉末の、CuKαを線源とするX線回折によって測定される、2θ=66.5±1°付近の(110)面の回折ピークの積分幅が0.08〜1.40°、表面積が0.2〜0.6m2/g、発熱開始温度が160℃以上である上記(1)〜(9)のいずれか1項に記載の製造方法。
(11)上記(1)〜(10)のいずれか1項に記載の製造方法により製造されたリチウム含有複合酸化物を含むリチウム二次電池用正極。
(12)上記(11)に記載された正極を使用したリチウム二次電池。
(A)カルボン酸のM元素塩の水溶液をN元素源粉末に含浸させ、乾燥により水分を除去した後、リチウム源粉末、及び必要に応じて、フッ素源を乾式混合し、その混合粉末を酸素含有雰囲気において850〜1050℃で焼成する。
(B)カルボン酸のM元素塩の水溶液を、リチウム源粉末、及び必要に応じてフッ素源の共存下で、N元素源粉末に含浸させ、次いで乾燥により水分を除去した後の混合粉末を酸素含有雰囲気において850〜1050℃で焼成する。
[例1]
硫酸コバルト水溶液と水酸化アンモニウムの混合液と苛性ソーダ水溶液を連続的に混合して、連続的に水酸化コバルトスラリーを既知の方法により合成し、凝集、ろ過及び乾燥工程を経て水酸化コバルト粉体を得た。得られた水酸化コバルトは、CuKα線を使用した粉末X線回折において、2θ=19±1°付近の(001)面の回折ピークの積分幅は0.27°であり、2θ=38°±1付近の(101)面の回折ピークの積分幅は0.23°であり、走査型電子顕微鏡観察の結果、微粒子が凝集して、略球状の二次粒子から形成されていることが判った。走査型電子顕微鏡観察の画像解析から求めた体積基準の粒度分布解析の結果、平均粒径D50が17.5μm、D10が7.1μm、D90が26.4μmであった。水酸化コバルトのコバルト含量は61.5%であった。
上記水酸化コバルト194.71gと、比表面積が1.2m2/gの炭酸リチウム粉末76.18gとを混合した。
炭酸マグネシウム0.99gと、市販のクエン酸アルミニウム2.43gとクエン酸2.51gを純水174.56gに加えて溶解せしめ、pH2.9のマグネシウムとルミニウムが均一に溶解したクエン酸塩の水溶液を得た。上記水溶液を、例1と同様に混合して得た、水酸化コバルト194.60gと炭酸リチウム76.14gとの混合物に加え、スラリー状にした。スラリー中の固形分濃度は60重量%であった。
例2と同様に調製したクエン酸塩の水溶液に水酸化コバルト粉末を混合し、スラリーを得た。得られたスラリーを100℃、10時間乾燥して水分を除去し、アルミニウムとマグネシウムが水酸化コバルト粉末に均一に含浸された水酸化コバルト粉末を得た。得られた水酸化コバルト粉末に所定量の炭酸リチウム粉末74.62gとフッ化リチウム粉末1.07gを秤量混合した後、例1と同じ条件で焼成し、LiCo0.990Mg0.005Al0.005O1.995F0.005を得た。
例1において、水溶液を加えない他は例1と同様な方法で、水酸化コバルト195.8gと炭酸リチウム75.85gを混合し、焼成してLiCoO2で表されるリチウム含有複合酸化物を得た。焼成物を解砕し得られた1次粒子が凝集してなるリチウム含有複合酸化物粉末の粒度分布をレーザー散乱式粒度分布測定装置を用いて水溶媒中にて測定した結果、平均粒径D50が17.3μm、D10が7.8μm、D90が26.2μmであり、BET法により求めた比表面積が0.30m2/gの塊状のリチウム含有複合酸化物粉末を得た。このリチウム含有複合酸化物粉末について、X線回折装置(理学電機社製RINT 2100型)を用いてX線回折スペクトルを得た。CuKα線を使用した粉末X線回折において、2θ=66.5±1°付近の(110)面の回折ピークの積分幅は0.110°であった。この粉末のプレス密度は3.00g/cm3であった。2θ=66.5±1°付近の(110)面の回折ピークの積分幅は0.115°であった。
例1において、水溶液の代わりに、水酸化マグネシウム粉末を1.20g、水酸化コバルト194.71gと炭酸リチウム76.18gを乾式混合して焼成した他は、例1と同様に実施し、LiCo0.99Mg0.01O2を得た。このリチウム含有複合酸化物粉末のプレス密度は3.00g/cm3であった。
また、上記リチウム含有複合酸化物粉末を使用し、例1と同様にして、正極体を製造し、電池を組み立てて、その電池特性を測定した。その結果、正極電極層の初期重量容量密度は161mAh/g、30回サイクル後の容量維持率は95.1%、発熱開始温度161℃であった。
例2において、水酸化コバルト191.99gと炭酸リチウム粉末76.27gとの混合物、及び水溶液として、クエン酸アルミニウム4.86gと炭酸マグネシウム1.97gとクエン酸7.92gとを水59.04gに溶かしたクエン酸塩の水溶液にZr含量15.1重量%の炭酸ジルコンアンモニウム(NH4)2[Zr(CO3)2(OH)2]水溶液を6.21g添加したpH9.4のカルボン酸塩の水溶液を用いた他は、例2と同様に実施し、LiAl0.01Co0.975Mg0.01Zr0.005O2を得た。このリチウム含有複合酸化物粉末のプレス密度は3.08g/cm3であった。また、上記リチウム含有複合酸化物粉末を使用し、例1と同様にして、正極体を製造し、電池を組み立てて、その電池特性を測定した。その結果、正極電極層の初期重量容量密度は162mAh/g、30回サイクル後の容量維持率は99.2%、発熱開始温度は174℃であった。
市販の乳酸アルミニウム6.03gと炭酸マグネシウム1.97gとクエン酸10.77gとを水48.79gに溶かした溶液に、Zr含量15.1重量%の炭酸ジルコンアンモニウム(NH4)2[Zr(CO3)2(OH)2]水溶液を12.39g添加して得たpH9.5のクエン酸塩の水溶液を、例1の方法で得た水酸化コバルト190.61gに加え、スラリーを得た。得られたスラリーを、120℃で2時間、乾燥機にて脱水した後、例1で用いたと同様の炭酸リチウム76.12gと混合し、950℃で12時間焼成し、LiAl0.01Co0.97Mg0.01Zr0.01O2を得た。このリチウム含有複合酸化物粉末のプレス密度は3.08g/cm3であった。また、上記リチウム含有複合酸化物粉末を使用し、例1と同様にして、正極体を製造し、電池を組み立てて、その電池特性を測定した。その結果、正極電極層の初期重量容量密度は160mAh/g、30回サイクル後の容量維持率は99.1%、発熱開始温度は171℃であった。
Claims (12)
- 一般式LipNxMyOzFa(但し、Nは、Co、Mn及びNiからなる群から選ばれる少なくとも1種の元素であり、MはN以外の遷移金属元素、Sn、Zn、Al及びアルカリ土類金属元素からなる群から選ばれる少なくとも1種の元素である。0.9≦p≦1.1、0.97≦x<1.00、0<y≦0.03、1.9≦z≦2.1、x+y=1、0≦a≦0.02)で表され、リチウム源、N元素源、必要に応じて、M元素源及びフッ素源を含む混合物を酸素含有雰囲気において、700〜1050℃で焼成するリチウム含有複合酸化物の製造方法であって、分子内にカルボン酸基又はカルボン酸基と水酸基を合計で2つ以上有しかつ必要に応じてM元素を有するカルボン酸若しくはその塩の水溶液を、平均粒径(D50)が2〜20μmのN元素源粉末に含浸し乾燥した粉末を使用することを特徴とするリチウム二次電池正極用リチウム含有複合酸化物の製造方法。
- カルボン酸が、炭素数が2〜8のカルボン酸である請求項1に記載の製造方法。
- カルボン酸が、クエン酸、乳酸、蓚酸及び酒石酸からなる群から選ばれる少なくとも1種である請求項1又は2に記載の製造方法。
- カルボン酸若しくはその塩の水溶液が、pH2〜12である請求項1〜3のいずれか1項に記載の製造方法。
- カルボン酸のM元素塩の水溶液をN元素源粉末に含浸させ、乾燥により水分を除去した後、リチウム源粉末、及び必要に応じて、フッ素源を乾式混合し、その混合粉末を酸素含有雰囲気において850〜1050℃で焼成する請求項1〜4のいずれか1項に記載の製造方法。
- カルボン酸のM元素塩の水溶液を、リチウム源粉末、及び必要に応じてフッ素源の共存下で、N元素源粉末に含浸させ、次いで乾燥により水分を除去した後の混合粉末を酸素含有雰囲気において850〜1050℃で焼成する請求項1〜4のいずれか1項に記載の製造方法。
- M元素が、Ti、Zr、Hf、Nb、Ta、Mg、Sn、Zn及びAlからなる群から選ばれる少なくとも1種である請求項1〜6のいずれか1項に記載の製造方法。
- M元素が、少なくともAlとMgからなり、Al/Mgが原子比で1/3〜3/1であり、かつ0.005≦y≦0.025である請求項1〜7のいずれか1項に記載の製造方法。
- M元素がMgとM2(M2は少なくともTi、Zr、Ta及びNbからなる群から選ばれる少なくとも1種の元素)とからなり、M2/Mgが原子比で1/40〜2/1であり、かつ0.005≦y≦0.025である請求項1〜7のいずれか1項に記載の製造方法。
- リチウム含有複合酸化物粉末の、CuKαを線源とするX線回折によって測定される、2θ=66.5±1°付近の(110)面の回折ピークの積分幅が0.08〜1.40°、表面積が0.2〜0.6m2/g、発熱開始温度が160℃以上である請求項1〜9のいずれか1項に記載の製造方法。
- 請求項1〜10のいずれか1項に記載の製造方法により製造されたリチウム含有複合酸化物を含むリチウム二次電池用正極。
- 請求項11に記載された正極を使用したリチウム二次電池。
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