JP2021527919A - リチウム二次電池用正極活物質及びリチウム二次電池 - Google Patents
リチウム二次電池用正極活物質及びリチウム二次電池 Download PDFInfo
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- JP2021527919A JP2021527919A JP2020566218A JP2020566218A JP2021527919A JP 2021527919 A JP2021527919 A JP 2021527919A JP 2020566218 A JP2020566218 A JP 2020566218A JP 2020566218 A JP2020566218 A JP 2020566218A JP 2021527919 A JP2021527919 A JP 2021527919A
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- Prior art keywords
- lithium
- transition metal
- positive electrode
- metal oxide
- lithium secondary
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 150
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 53
- 239000010410 layer Substances 0.000 claims abstract description 84
- 239000002131 composite material Substances 0.000 claims abstract description 80
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 73
- 239000011229 interlayer Substances 0.000 claims abstract description 66
- 230000008859 change Effects 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 230000007704 transition Effects 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
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- 239000004020 conductor Substances 0.000 description 14
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- 239000010936 titanium Substances 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
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- 239000010949 copper Substances 0.000 description 6
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000005469 synchrotron radiation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本出願は、2018年6月20日に出願された韓国特許出願第10−2018−0071056号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
[化学式1]
Lix[NiaCobMncMd]O2
前記化学式1中、前記Mは、Zr、W、Al、Ti、Mg及びCoよりなる群から選択される1種以上の元素であり、0.9≦x≦1.2、0.50≦a≦0.75、0<b<0.4、0<c<0.4、0<d<0.2である。
本発明による正極は、正極活物質層を含み、前記正極活物質層は、正極活物質として、層状構造を有し且つ遷移金属全体のうちニッケルの含有量が50atm%から75atm%であるリチウム複合遷移金属酸化物を含む。
[化学式1]
Lix[NiaCobMncMd]O2
前記化学式1中、前記Mは、遷移金属サイトに置換されたドーピング元素であって、正極活物質の構造安定性を向上させる役割を担う。前記Mは、例えば、Zr、W、Al、Ti、Mg及びCoよりなる群から選択される1種以上の元素であってよい。好ましくは、前記Mは、Zr、W、Al、Ti、Mg及びCoよりなる群から選択される2種以上の元素を含むものであってよい。さらに好ましくは、前記Mは、Zr及びCoを含むものであってよい。
式(1):SOC58%から86%充電区間におけるリチウム‐酸素層の層間距離の変化率(%)={(SOC58%におけるリチウム‐酸素層の層間距離 − SOC86%におけるリチウム‐酸素層の層間距離)/SOC58%におけるリチウム‐酸素層の層間距離}×100
式(2):SOC58%から86%充電区間における遷移金属‐酸素層の層間距離の変化率(%)={(SOC58%における遷移金属‐酸素層の層間距離 − SOC86%における遷移金属‐酸素層の層間距離)/SOC58%における遷移金属‐酸素層の層間距離}×100
負極は、通常、リチウム二次電池で分離膜として用いられるものであれば、特に制限なく使用可能であり、例えば、負極集電体及び前記負極集電体上に位置する負極活物質層を含むものであってよい。
前記分離膜は、負極と正極の間に介在され、正極及び負極を分離してリチウムイオンの移動通路を提供するものであって、通常、リチウム二次電池で分離膜として用いられるものであれば特に制限なく使用可能であり、特に電解質のイオン移動に対して低抵抗でありながら電解液含湿能に優れたものが好ましい。具体的には、多孔性高分子フィルム、例えば、エチレン単独重合体、プロピレン単独重合体、エチレン/ブテン共重合体、エチレン/ヘキセン共重合体及びエチレン/メタクリレート共重合体などのようなポリオレフィン系高分子で製造した多孔性高分子フィルムまたはこれらの2層以上の積層構造体が用いられてよい。また、通常の多孔性不織布、例えば、高融点のガラス繊維、ポリエチレンテレフタレート繊維などからなる不織布が用いられてもよい。また、耐熱性または機械的強度の確保のために、セラミックス成分または高分子物質が含まれたコーティングされた分離膜が用いられてもよく、選択的に単層または多層構造で用いられてよい。
前記電解質としては、リチウム二次電池に使用可能な有機系液体電解質、無機系液体電解質、固体高分子電解質、ゲル型高分子電解質、固体無機電解質、溶融型無機電解質などが用いられてよく、特に限定されない。
本発明のリチウム二次電池の外形は特に制限がないが、缶を用いた円筒状、角形、パウチ(pouch)型またはコイン(coin)型などからなってよい。
Ni0.6Co0.2Mn0.2(OH)2とLi2CO3H2O及びZrO2、CoOH2を乾式混合し、860℃で10時間の間焼成し、Zr及びCoがドーピングされたリチウム複合遷移金属酸化物の粉末を製造した。製造されたリチウム複合遷移金属酸化物の粉末は、D50が12μmであるユニモーダル粒度分布を有した。
製造例1により製造されたリチウム複合遷移金属酸化物とB4C、W(OH)2を混合した後、350℃で10時間の間熱処理し、前記リチウム複合遷移金属酸化物の表面にB及びWを含むコーティング層を形成した。製造されたリチウム複合遷移金属酸化物の粉末は、D50が12μmであるユニモーダル粒度分布を有した。
Ni0.6Co0.2Mn0.2(OH)2とLi2CO3H2O及びZrO2を乾式混合し、860℃で10時間の間焼成し、Zrがドーピングされたリチウム複合遷移金属酸化物の粉末を製造した。
Ni0.5Co0.2Mn0.3(OH)2とLi2CO3H2O及びZrO2を乾式混合し、860℃で10時間の間焼成し、Zrがドーピングされたリチウム複合遷移金属酸化物の粉末を製造した。
前記製造例1〜4により製造されたそれぞれのリチウム複合遷移金属酸化物と、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中で重量比96:2:2の比率で混合して正極合剤を製造し、これをアルミニウム集電体の片面に塗布した後、130℃で乾燥し、圧延して正極を製造した。
正極活物質として製造例1により製造されたリチウム複合遷移金属酸化物、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中で重量比96:2:2の比率で混合して正極合剤を製造し、これをアルミニウム集電体の片面に塗布した後、130℃で乾燥し、圧延して正極を製造した。
正極活物質として製造例2により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−1と同一の方法でリチウム二次電池を製造した。
正極活物質として製造例3により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−1と同一の方法でリチウム二次電池を製造した。
正極活物質として製造例4により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−1と同一の方法でリチウム二次電池を製造した。
実施例1−1、実施例2−1、比較例1−1及び比較例2−1のリチウム二次電池の容量特性を次のような方法で測定した。リチウムイオンの挿入と脱離の過程中の温度による変数を除去するため、前記実施例及び比較例のリチウム二次電池は、25℃の恒温チャンバ内で充放電サイクルを進行し、高電圧容量特性を評価するための充電、放電の条件は、基準容量200mAh/gで1番目の充電と放電時の電流値を0.2Cで計算した後、計算された電流値を充放電器によって印加してから4.4Vまで充電した時に計算される容量を充電容量、2.5Vで放電した時に計算される容量を放電容量として評価し、充電容量と放電容量の比を初期効率として定義した。測定の結果は、下記表3に示した。
正極活物質として製造例1により製造されたリチウム複合遷移金属酸化物、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中で重量比96:2:2の比率で混合して正極合剤を製造し、これをアルミニウム集電体の片面に塗布した後、乾燥、圧延して正極を製造した。
正極活物質として製造例2により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−2と同一の方法でリチウム二次電池(フルセル)を製造した。
正極活物質として製造例3により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−2と同一の方法でリチウム二次電池(フルセル)を製造した。
正極活物質として製造例4により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1−2と同一の方法でリチウム二次電池(フルセル)を製造した。
実施例1−2、実施例2−2、比較例1−2及び比較例2−2により製造されたリチウム二次電池の高電圧寿命特性を次のような方法で測定した。
Claims (8)
- 正極、負極、前記正極と前記負極の間に介在される分離膜、及び電解質を含むリチウム二次電池であって、
前記正極は、正極活物質として、層状構造を有し且つ遷移金属全体のうちニッケルの含有量が50atm%から75atm%であるリチウム複合遷移金属酸化物の粉末を含み、
前記リチウム複合遷移金属酸化物の粉末のSOC(充電状態)58%から86%充電区間におけるリチウム‐酸素層の層間距離の変化率が3%以下である、リチウム二次電池。 - 前記リチウム複合遷移金属酸化物の粉末のSOC58%から86%充電区間におけるリチウム‐酸素層の層間距離の変化率が2%以下である、請求項1に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物の粉末のSOC58%から86%充電区間における遷移金属‐酸素層の層間距離の変化率が6%以上である、請求項1または2に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物は、下記化学式1で表され、
[化学式1]
Lix[NiaCobMncMd]O2
前記化学式1で、
前記Mは、Zr、W、Al、Ti、Mg及びCoよりなる群から選択される1種以上の元素であり、
0.9≦x≦1.2、0.50≦a≦0.75、0<b<0.4、0<c<0.4、0<d<0.2である、請求項1から3のいずれか一項に記載のリチウム二次電池。 - 前記Mは、Zr、W、Al、Ti、Mg及びCoよりなる群から選択される2種以上の元素を含む、請求項4に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物は、その表面にAl、Ti、W、B、F、P、Mg、Ni、Co、Fe、Cr、V、Cu、Ca、Zn、Zr、Nb、Mo、Sr、Sb、Bi、Si、及びSよりなる群から選択された1種以上の元素よりなる群から選択された1種以上の元素を含むコーティング層を含む、請求項1から5のいずれか一項に記載のリチウム二次電池。
- 前記コーティング層は、B及びWを含む、請求項6に記載のリチウム二次電池。
- 層状構造を有し且つ遷移金属全体のうちニッケルの含有量が50atm%から75atm%であるリチウム複合遷移金属酸化物の粉末を含むリチウム二次電池用正極活物質であり、
前記リチウム複合遷移金属酸化物の粉末のSOC58%から86%充電区間におけるリチウム‐酸素層の層間距離の変化率が3%以下である正極活物質。
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