JP4843918B2 - 複合酸化物材料及びリチウム二次電池用正極活物質 - Google Patents
複合酸化物材料及びリチウム二次電池用正極活物質 Download PDFInfo
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- JP4843918B2 JP4843918B2 JP2004247221A JP2004247221A JP4843918B2 JP 4843918 B2 JP4843918 B2 JP 4843918B2 JP 2004247221 A JP2004247221 A JP 2004247221A JP 2004247221 A JP2004247221 A JP 2004247221A JP 4843918 B2 JP4843918 B2 JP 4843918B2
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- 239000007774 positive electrode material Substances 0.000 title claims description 51
- 239000000463 material Substances 0.000 title claims description 42
- 229910052744 lithium Inorganic materials 0.000 title claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 28
- 239000002131 composite material Substances 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000002194 amorphous carbon material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 22
- 239000011572 manganese Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000011149 active material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000009783 overcharge test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000010334 sieve classification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Description
原料としてLi2CO3,MnO2,CoCO3,Al(OH)3、Ni(NO3)2,SiOを用いて正極活物質を合成した。金属元素の組成を種々変えて、原料粉末を混合した後に、高純度アルミナ容器に入れて950℃−20時間の第1焼成と、1050℃で20時間の第2焼成をした。作製した正極活物質の活物質名と、活物質組成を表1に示す。上記の焼成はいずれも空気中で行った。得られた正極活物質を粉砕分級し、いずれの場合でも平均粒径D50=9〜11ミクロンとなるようにした。上記材料のX線回折装置で回折パターンを測定したところ、六方晶層状構造が得られたものと、MnO2,Al2O3,SiO2の不純物層が混在したもの、スピネル相が生成したものに分かれた。図1に示す三角相図に、目的とする六方晶層状構造が得られた組成を●で示した(図1中符号hが実施例1であり、a〜g、iおよびjは参考例)。組成比を表すa,b,cの値がa+b+c=1,9b≦5a+2.7,0<a<1,0<b<1,0<c<1を満足する範囲で所定の結晶構造を有する正極活物質が得られていることが分かった。
本比較例では実施例1と同様の方法により、表2に示す組成の正極活物質を作製した。図2中符号kからmで、相図に上記の組成を示した。得られた正極活物質を、X線回折法により調べたところ活物質名(k),(l),(m)は結晶性が悪く、2θ値で60度付近,80度付近に見られるピークの半値幅が増大しているのが認められた。活物質(n)は、Liの他はNi,Mn,Coのみから構成されるものであり、本発明に関るものではなく、上記活物質(n)を比較例として検討した。
本発明実施例1(h)の複合酸化物材料を、以下に述べる作製方法により作製した。炭酸リチウム、水酸化ニッケル、二酸化マンガン、酸化ゲルマニウム、四酸化三コバルト、水酸化アルミを原料として、金属元素が所定の組成比となるように混合し、870℃で10時間、空気中で第1焼成を行った。焼成は箱型焼成炉を用いて、原料粉末を高純度のアルミナ容器に入れて行った。第1焼成後の材料を、ボールミルで粉砕した後に1000℃で10時間の第2焼成をして複合酸化物材料を得た。この、Cu−kα線(30kV−200mA、DS=0.5、SS=0.5、 RS=0.15)を用いてX線回折パターン測定した結果を、図6に示す。回折パターンは層状構造の六方晶系を示しており、2θ値の角度で、18.7度、36.9度、48.3度、59.1度、63.2度、65.0度、67.9度、77.2度に特徴的な強い回折ピークが認められた。これらの回折ピークをkα線とkβ線の分離を行った後にカーブフィットして求められた半値幅は、いずれの角度においても0.12度から0.25度の間にあり、結晶性が良好であることを示していた。
Claims (7)
- Li及びNiを少なくとも含有する層状構造を有する複合酸化物材料であって、前記Li及びNiの他にMn以外の4価の元素とCo以外の3価の元素を有し、化学式LixNia(MnyM1−y)b(CozM′1−z)cO2(0<x<1.2,0<y<1,0<z<1,a+b+c=1,9b≦5a+2.7,0<a<1,0<b<1,0<c<1、M:Ge、M′:Al)で表され、Cu−kα線を用いたX線回折測定において、2θ値で20以上80度以下の角度に現れる回折ピークの半値幅が、いずれも0.12度から0.25度の範囲であることを特徴とする複合酸化物材料。
- Li及びNiを少なくとも含有する層状リチウム二次電池用正極材料であって、前記Li及びNiの他にMn以外の4価の元素とCo以外の3価の元素を有し、化学式LixNia(MnyM1−y)b(CozM′1−z)cO2(0<x<1.2,0<y<1,0<z<1,a+b+c=1,9b≦5a+2.7,0<a<1,0<b<1,0<c<1、M:Ge、M′:Al)で表され、Cu−kα線を用いたX線回折測定において、2θ値で20以上80度以下の角度に現れる回折ピークの半値幅が、いずれも0.12度から0.25度の範囲であることを特徴とするリチウム電池用正極活物質。
- Li複合酸化物を少なくとも含有する正極と、負極に黒鉛又は非晶質炭素材料を含有する非水リチウム二次電池であって、前記正極に含有されるLi複合酸化物は前記請求項2に記載の正極活物質であることを特徴とする非水リチウム二次電池。
- 請求項2に記載のリチウム電池用正極活物質を製造する方法であって、所定の金属組成比に混合された原料を、空気雰囲気中において800℃から950℃の温度で第1の焼成を行い、その後に空気雰囲気中で1000℃から1100℃の温度で第2の焼成を行うことを特徴とするリチウム電池用正極活物質の製造方法。
- 請求項1に記載の複合酸化物材料を製造する方法であって、所定の金属組成比に混合された原料を、空気雰囲気中において800℃から950℃の温度で第1の焼成を行い、その後に空気雰囲気中で1000℃から1100℃の温度で第2の焼成を行うことを特徴とする複合酸化物材料の製造方法。
- 所定の金属組成比に混合された原料を、空気雰囲気中において800℃から950℃の温度で第1の焼成を行い、その後に空気雰囲気中で1000℃から1100℃の温度で第2の焼成を行うことにより製造される、請求項1に記載の複合酸化物材料。
- 所定の金属組成比に混合された原料を、空気雰囲気中において800℃から950℃の温度で第1の焼成を行い、その後に空気雰囲気中で1000℃から1100℃の温度で第2の焼成を行うことにより製造される、請求項2に記載のリチウム電池用正極活物質。
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JP5917027B2 (ja) | 2010-06-30 | 2016-05-11 | 株式会社半導体エネルギー研究所 | 電極用材料の作製方法 |
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