JP6320771B2 - 複合正極活物質及びその製造方法、該複合正極活物質を採用した正極とリチウム電池 - Google Patents
複合正極活物質及びその製造方法、該複合正極活物質を採用した正極とリチウム電池 Download PDFInfo
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- JP6320771B2 JP6320771B2 JP2014016582A JP2014016582A JP6320771B2 JP 6320771 B2 JP6320771 B2 JP 6320771B2 JP 2014016582 A JP2014016582 A JP 2014016582A JP 2014016582 A JP2014016582 A JP 2014016582A JP 6320771 B2 JP6320771 B2 JP 6320771B2
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- 238000005805 hydroxylation reaction Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- 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
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
xLi2−yM”yMO3−(1−x)LiM’O2
xLi2−yM”yMO3−x’LiM’O2−x”Li1+dM'''2−dO4
xLi2−yM”yMnO3−(1−x)LiNiaCobMncO2
xLi2MO3−(1−x)LiM’O2
xLi2MO3−(1−x)LiM’O2
xLi2−yM”yMO3−(1−x)LiM’O2
xLi2−yM”yMO3−x’LiM’O2−x”Li1+dM’’’2−dO4
xLi2MO3−(1−x)LiM’O2
xLi2−yM”yMnO3−(1−x)LiNiaCobMncO2
xLi2−yM”yMO3−x’LiM’O2−x”Li1+dM’’’2−dO4
xLi2MO3−(1−x)LiM’O2
xLi2MnO3−(1−x)LiNiaCobMncO2
xLi2MO3−x’LiM’O2−x”Li1+dM’’’2−dO4
Li[LixMey]O2+d
Li[LixNiaCobMnc]O2+d
1)OLO(over−lithiated oxide)活物質の酸処理
OLO活物質として、0.55Li2MnO3−0.45LiNi0.5Co0.2Mn0.3O2組成の物質を用いる。前記OLO活物質10gをHNO3 0.2M水溶液500mLに添加して5分間撹拌した後、真空フィルタリングで溶液を除去して80℃で乾燥させ、酸処理されたOLO活物質を得た。
酸処理された前記OLO活物質10gをAl硝酸塩0.4wt%水溶液500mLに投入し、50℃で24時間撹拌した。撹拌後、前記水溶液を真空フィルタリングで除去して80℃で乾燥させた後、空気中で300℃で5時間熱処理を行った。熱処理を完了してAl陽イオンでドーピングされたOLO活物質を得た。
前記ドーピング処理されたOLO活物質の充放電特性及び電圧効果を確認するために、下記のようにコインハーフセルを製作した。
Al硝酸塩の代わりに、Ga硝酸塩を0.3wt%含む水溶液を用いて、Ga陽イオンでドーピングされたOLO活物質を製造して使用したことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
Al硝酸塩の代わりに、Ni硝酸塩を0.4wt%含む水溶液を用いて、Ni陽イオンでドーピングされたOLO活物質を製造して使用したことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
Al硝酸塩の代わりに、Cr硝酸塩を0.5wt%含む水溶液を用いて、Cr陽イオンでドーピングされたOLO活物質を製造して使用したことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
Al硝酸塩の代わりに、MgNO3を1wt%を含む水溶液を用いて、Mg陽イオンでドーピングされたOLO活物質を製造して活用したことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
Al硝酸塩の代わりに、MgNO3を10wt%を含む水溶液を用いて、Mg陽イオンでドーピングされたOLO活物質を製造して使用したことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
前記OLO活物質にフッ素が遷移金属対比6モル%添加された正極活物質を使って、前記実施例1と同じ過程の酸処理及びAl陽イオンドーピング処理を行った。
0.55Li2MnO3−0.45LiNi0.5Co0.2Mn0.3O2組成のOLO活物質を、酸処理または金属陽イオンドーピング処理なしにそのまま用いて、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
酸処理効果を確認するために、0.55Li2MnO3−0.45LiNi0.5Co0.2Mn0.3O2組成のOLO活物質を、金属陽イオンのドーピング処理をせずに酸処理過程のみ行ったことを除いては、前記実施例1と同じ過程を行ってコインハーフセルを製作した。
前記実施例1でOLO活物質の酸処理効果を確認するために、下記のように充放電を行い、その結果を図4に示した。
前記実施例1、比較例1及び比較例2のコインセルの前記と同じ条件での充放電結果を、図7に示した。
前記比較例1の0.55Li2MnO3−0.45LiNi0.5Co0.2Mn0.3O2組成のOLO活物質と、実施例1の酸処理及び陽イオンドーピングされたOLO活物質とのTEM分析結果を、それぞれ図8及び図9に示した。
前記比較例1及び実施例1〜4のコインセルについて、下記のように初期効率、容量及びレート特性を測定し、その結果を下記の表1に示した。
前記比較例1〜2及び実施例1〜3及び5のコインセルについて、0.05C充電/0.05C放電で初期化成を行い、0.5C充電/0.5C放電を40回繰り返しつつ各サイクルでの平均電圧を測定し、その結果を図10に示した。
前記比較例1及び実施例1〜3のコインセルについて40サイクル寿命前後のdQ/dVカーブを、それぞれ図11ないし図14に示した。dQ/dVカーブは、電圧(V、横軸)に対して充放電容量を前記電圧で微分した値(dQ/dV、縦軸)を示したものである。
金属陽イオン添加量による効果を確認するために、何の処理もしていない比較例1と、Mg塩をそれぞれ1wt%及び10wt%使った実施例5及び6とのコインセルについて、初期効率、容量及びレート特性を前記評価例4と同じ方法で測定し、その結果を下記の表2に示した。
フッ素を含むOLO活物質の酸処理及び金属陽イオンドーピング処理の効果を確認するために、比較例1のOLO活物質と実施例7のフッ素含有OLO活物質とをそれぞれ正極として使い、グラファイトを負極として使った18650フルセルに対して1Cレートに当たる電流値を印加し、4.55V充電(cc mode)、2.5V放電(cc mode)条件で300回充放電を行った。100、200サイクルのピークは、容量確認のために0.2C基準電流を流して発生した。各サイクルにおける平均電圧を測定し、その結果を図15に示した。
22 負極
23 正極
24 セパレータ
25 電池容器
26 封込み部材
Claims (19)
- 過リチウム化された(overlithiated)リチウム遷移金属酸化物を含む複合正極活物質であり、前記過リチウム化されたリチウム遷移金属酸化物は、下記の化学式1または化学式3で表示される化合物を含む複合正極活物質:
[化1]
xLi2−yM”yMO3−(1−x)LiM’O2
前記式で、
Mは、平均酸化数+4を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M’は、平均酸化数+3を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M”は、前記Mとは相異なり、2周期ないし7周期元素から選択される少なくとも一つの金属陽イオンであり、
0<x<0.6であり、0<y<0.1である;
[化3]
xLi2−yM”yMO3 −x’LiM’O2 −x”Li1+dM’’’2−dO4
前記式で、
Mは、平均酸化数+4を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M’は、平均酸化数+3を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M’’’は、平均酸化数+3及び+4の組み合わせからなる、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M”は、前記M、M’及びM’’’とは異なって2周期ないし7周期元素から選択される少なくとも一つの金属陽イオンであり、
x+x’+x”=1;0<x<0.6、0<x’<1、0<x”<1;0<y<0.1;0≦d≦0.33である。 - 前記化学式1または化学式3で、M”は、Li2−yM”yMO3のLiイオン層にドーピングされる請求項1に記載の複合正極活物質。
- 前記過リチウム化されたリチウム遷移金属酸化物は、フッ素をさらに含む請求項1または2に記載の複合正極活物質。
- 前記Mは、Mn、Ti、Zr、Sn、及びMoのうち少なくとも一つの金属である請求項1から3の何れか1項に記載の複合正極活物質。
- 前記M’は、Ni、Co、Mn、Fe、Al、Mg、Zn、Cu、Cr、V及びNbのうち少なくとも一つの金属である請求項1から4の何れか1項に記載の複合正極活物質。
- 前記M”は、Mg、Al、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Sr、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、及びInのうち少なくとも一つの金属陽イオンである請求項1から5の何れか1項に記載の複合正極活物質。
- 前記M”は、Al、Mn、Cr、Zn、Ga、Mg、V、及びZrのうち少なくとも一つの金属陽イオンである請求項6に記載の複合正極活物質。
- 前記過リチウム化されたリチウム遷移金属酸化物は、下記の化学式2で表示される化合物を含む請求項1から7の何れか1項に記載の複合正極活物質:
[化2]
xLi2−yM”yMnO3−(1−x)LiNiaCobMncO2
前記式で、
0<x<0.6、0<y<0.1、0<a<1、0<b<1、0<c<1、a+b+c=1であり、M”は、Mnとは異なって2周期ないし7周期元素から選択される少なくとも一つの金属陽イオンである。 - 前記過リチウム化されたリチウム遷移金属酸化物は、平均粒径が10nmないし500μmの粒子である請求項1から8の何れか1項に記載の複合正極活物質。
- 請求項1ないし9のうちいずれか1項に記載の複合正極活物質を含む正極と、
前記正極に対向して配される負極と、
前記正極と負極との間に配される電解質と、
を含むリチウム電池。 - 過リチウム化されたリチウム遷移金属酸化物を含む複合正極活物質であり、前記過リチウム化されたリチウム遷移金属酸化物は、下記の化学式9で表示される化合物を含む複合正極活物質:
[化9]
xLi2MO3−(1−x)LiM’O2
前記式で、
Mは、平均酸化数+4を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M’は、平均酸化数+3を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
前記化学式9の化合物のLi 2 MO 3 のLiイオン層の一部yが、2周期ないし7周期元素から選択される少なくとも一つの金属陽イオンに入れ替わり、
0<x<0.6であり、0<y<0.1である。 - 過リチウム化された金属酸化物を酸処理する段階と、
酸処理された前記過リチウム化された金属酸化物を金属陽イオンでドーピング処理する段階と、を含み、
前記過リチウム化された金属酸化物は、下記の化学式4で表示される化合物を含む複合正極活物質の製造方法:
[化4]
xLi2MO3−(1−x)LiM’O2
前記式で、
Mは、平均酸化数+4を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
M’は、平均酸化数+3を持つ、4周期及び5周期遷移金属から選択される少なくとも一つの金属であり、
0<x<1である。 - 前記過リチウム化された金属酸化物は、フッ素をさらに含む請求項12に記載の複合正極活物質の製造方法。
- 前記過リチウム化された金属酸化物内に含有された全体遷移金属の総モル数に対して10モル%以下の割合でフッ素が含まれる請求項13に記載の複合正極活物質の製造方法。
- 前記酸処理された、過リチウム化された金属酸化物のドーピング処理段階は、ドーピング溶液の全体重量を基準として金属陽イオンの塩の含量が0.01ないし5.00重量%範囲であるドーピング溶液を用いて行われる請求項12から14の何れか1項に記載の複合正極活物質の製造方法。
- 前記ドーピング処理された金属酸化物を空気中で10ないし100℃範囲で熱処理する段階をさらに含む請求項12から15の何れか1項に記載の複合正極活物質の製造方法。
- 前記過リチウム化された金属酸化物の酸処理段階は、硝酸、硫酸、塩酸、クエン酸、フマル酸、マレイン酸、ホウ酸(H3BO3)及び燐酸のうち少なくとも一つの酸を含む酸性溶液を用いて行われる請求項12から16の何れか1項に記載の複合正極活物質の製造方法。
- 前記過リチウム化された金属酸化物の酸処理段階後、前記酸処理された、過リチウム化された金属酸化物のドーピング処理段階前に、酸処理された前記過リチウム化された金属酸化物を200ないし500℃範囲で乾燥させる段階をさらに含む請求項12から17の何れか1項に記載の複合正極活物質の製造方法。
- 前記ドーピング処理段階は、前記Mと異なる金属陽イオンであって、2周期ないし7周期元素から選択される少なくとも一つの金属陽イオンM”の塩を含むドーピング溶液を用いて行われる請求項12から18の何れか1項に記載の複合正極活物質の製造方法。
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