JP6096216B2 - 出力特性が向上された混合正極活物質及びこれを含む正極、リチウム二次電池 - Google Patents
出力特性が向上された混合正極活物質及びこれを含む正極、リチウム二次電池 Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims description 90
- 229910052744 lithium Inorganic materials 0.000 title claims description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 56
- 239000011572 manganese Substances 0.000 claims description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000004020 conductor Substances 0.000 claims description 19
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 14
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006182 cathode active material Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims description 3
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000006231 channel black Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000006232 furnace black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000006233 lamp black Substances 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- BVPMZCWLVVIHKO-UHFFFAOYSA-N lithium cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Co+2].[Li+] BVPMZCWLVVIHKO-UHFFFAOYSA-N 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910015118 LiMO Inorganic materials 0.000 claims 1
- 239000006234 thermal black Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- -1 polyethylene, tetrafluoroethylene Polymers 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014089 LiMn1/3Ni1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011853 conductive carbon based material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
[化1]
aLi2MnO3・(1-a)LixMO2 (1)
[化2]
Li4-xMn5-2x-yCo3xMyO12 (2)
前記式(2)において、0<x<1.5(好ましくは、0.1≦x≦0.5)であり、0≦y<0.5(好ましくは、y=0)であり、Mは遷移金属元素の一つ、または2種以上の遷移金属元素が同時に適用されたものである。代表的な例としては、y=0であるLi4-xMn5-2xCo3xO12を挙げることができる。
下記式(1)で表される層状構造のリチウムマンガン酸化物(Mn-rich)に作動電圧範囲が、前記Mn-richより低い第2の正極活物質を混合した正極活物質に関するものである。
[化3]
aLi2MnO3・(1-a)LixMO2 (1)
前記式(1)において、0<a<1であり、0.9≦x≦1.2(好ましくは、x=1)であり、MはAl、Mg、Mn、Ni、Co、Cr、V及びFeからなる群から選択される何れかの元素、または2つ以上の元素が同時に適用されたものである。
[化4]
Li4-xMn5-2x-yCo3xMyO12 (2)
前記式(2)において、0<x<1.5(好ましくは、0.1≦x≦0.5)であり、0≦y<0.5(好ましくは、y=0)であり、Mは遷移金属元素の一つ、または2種以上の遷移金属元素が同時に適用されたものである。
(正極の製造)
正極活物質として、0.5Li2MnO3・0.5LiMn1/3Ni1/3Co1/3O2((Mn-rich、85重量%)とLi3.7Mn4.4Co0.9O12 (15重量%)からなる混合物90重量%を導電材であるデンカブラック6重量%、バインダーであるPVDF4重量%と共にNMPに添加してスラリーを作った。これを正極集電体であるアルミニウム(Al)フォイルの上にコーティングして圧延及び乾燥してリチウム二次電池用正極を製造した。
前記のように製造された正極と黒鉛系負極の間に多孔性のポリエチレンの分離膜を介在し、リチウム電解液を注入し、ポリマータイプリチウム二次電池を製造した。
前記ポリマータイプのリチウム二次電池を4.6Vにおいてフォーメーションした後、4.5Vと2Vの間で充放電しつつ、SOCによって抵抗を測定した(C-rate=1C)。
第2の正極活物質としてLi3.7Mn4.4Co0.9O12の代わりにLi4Mn5O12を使用したことを除いては、実施例と同一である。
正極活物質として0.5Li2MnO3・0.5LiMn1/3Ni1/3Co1/3O2(Mn-rich)のみを使用したことを除いては、実施例と同一である。
前記実施例及び比較例1、2によって製造されたフルセル(full cell)リチウム二次電池に対してSOCによる抵抗変化を測定し、図3に示した。
Claims (13)
- 下記式(1)で表されるリチウムマンガン酸化物と下記式(2)で表される第2の正極活物質を含み、前記第2の正極活物質は、混合正極活物質100重量部に対して10から30重量部に含まれる混合正極活物質:
[化1]
aLi2MnO3・(1-a)LiMO2 (1)
前記式(1)において、0<a<1であり、MはAl、Mg、Mn、Ni、Co、Cr、V及びFeからなる群から選択される何れかの元素、または2つ以上の元素が同時に適用されたものである。
[化2]
Li4-xMn5-2xCo3xO12 (2)
前記式(2)において、0.1≦x≦0.5である。 - 前記混合正極活物質には、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウムマンガン酸化物、リチウムコバルト−ニッケル酸化物、リチウムコバルト−マンガン酸化物、リチウムマンガン−ニッケル酸化物、リチウムコバルト−ニッケル−マンガン酸化物及びこれらに他元素らが置換またはドーピングされた酸化物からなる群から選択される1種以上のリチウム含有金属酸化物がさらに含まれていることを特徴とする請求項1に記載の混合正極活物質。
- 前記他元素は、Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、Ca、Zn、Zr、Nb、Mo、Sr、Sb、W及びBiからなる群から選択される1種以上であることを特徴とする請求項2に記載の混合正極活物質。
- 前記リチウム含有金属酸化物は、前記混合正極活物質100重量部に対して50重量部以内に含まれることを特徴とする請求項2または請求項3に記載の混合正極活物質。
- 請求項1から請求項4の何れか一項に記載の混合正極活物質を含む正極。
- 導電材及びバインダーをさらに含む請求項5に記載の正極。
- 前記導電材は、黒鉛及び導電性炭素からなる請求項6に記載の正極。
- 前記導電材は、前記混合正極活物質100重量部に対して0.5から15重量部含まれる請求項6または請求項7に記載の正極。
- 前記導電性炭素は、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーナスブラック、ランプブラック及びサーマルブラックからなる群から選択される少なくとも一つのカーボンブラック;結晶構造がグラフェンやグラファイトを含む物質からなる群から選択される少なくとも一つ;及びこれらが混合された物質;からなる群から選択される請求項7に記載の正極。
- 請求項5から請求項9のいずれか1項に記載の正極を含むことを特徴とするリチウム二次電池。
- 前記リチウム二次電池は、SOC10から40%区間における出力がSOC50%における出力対比20%以上であることを特徴とする請求項10に記載のリチウム二次電池。
- 前記リチウム二次電池は、シリーズ方式のPHEV(Plug-in Hybrid Electric Vehicle)に使用されることを特徴とする請求項10または11に記載のリチウム二次電池。
- 前記リチウム二次電池は、EV(Electric Vehicle)に使用されることを特徴とする請求項10から12の何れか一項に記載のリチウム二次電池。
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