JP6811032B2 - リチウムイオン二次電池用正極 - Google Patents
リチウムイオン二次電池用正極 Download PDFInfo
- Publication number
- JP6811032B2 JP6811032B2 JP2016104870A JP2016104870A JP6811032B2 JP 6811032 B2 JP6811032 B2 JP 6811032B2 JP 2016104870 A JP2016104870 A JP 2016104870A JP 2016104870 A JP2016104870 A JP 2016104870A JP 6811032 B2 JP6811032 B2 JP 6811032B2
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- Japan
- Prior art keywords
- lithium
- positive electrode
- nickel
- composite oxide
- ion secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 55
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 119
- 239000002131 composite material Substances 0.000 claims description 104
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 69
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 239000007774 positive electrode material Substances 0.000 claims description 47
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010248 power generation Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
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- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-L methanedisulfonate Chemical compound [O-]S(=O)(=O)CS([O-])(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-L 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical class CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
正極活物質として、リチウム・ニッケル系複合酸化物(LNO)、スピネル型リチウム・マンガン複合酸化物(LMO)およびリチウム・ニッケル・アルミニウム複合酸化物(NCA)を用意した。表1に記載するように配合した正極活物質混合物と、導電助剤としてBET比表面積62m2/gのカーボンブラック(CB)(TIMCAL製、SC65)と、バインダ樹脂としてPVDF(クレハ製、#7200)とを、固形分質量比で正極活物質:CB:PVDFが96:3:3の割合となるように混合し、溶媒であるNMPに添加した。さらに、この混合物に有機系水分捕捉剤として無水シュウ酸(分子量90)を、上記混合物からNMPを除いた固形分100質量部に対して0.03質量部添加した上で遊星方式の分散混合を30分間実施することで、これらの材料を均一に分散させてスラリーを作製した。得られたスラリーを、正極集電体となる厚み20μmのアルミニウム箔上に乾燥後重量が片面あたり16.0±0.3mg/cm2となるように塗布した。次いで、125℃にて10分間、電極を加熱し、NMPを蒸発させることにより正極活物質層を形成した。さらに、正極を3.5N/cm2でプレスして、正極集電体の片面上に正極活物質層を塗布した正極を作製した。
負極として金属リチウムを用いた。リチウム金属に対する各正極の電位を確認するためである。
ポリプロピレンからなる厚さ20μmのセパレータを使用した。
エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ジエチルカーボネート(DEC)を、25:5:70(体積比)で混合した混合非水溶媒に電解質塩としての六フッ化リン酸リチウム(LiPF6)を濃度が0.9mol/Lとなるように溶解させ、次いで、添加剤としてMMDSを1.2重量%となるように溶解させた。これらの非水混合溶媒を電解液として各々用いた。
リ電池正極および負極を直径1.2mmに打ち抜いた。ポリプロピレン多孔質セパレータの両面に上記負極板と正極板とを両活物質層がセパレータを隔てて重なるように配置したものをコインセル部材(宝仙、CR2320)に入れた。ここに電解液20μLを入れ、コイン電池蓋を閉め、周囲を封止してコイン型リチウムイオン二次電池を作製した。なお、チウムイオン二次電池の作製は、アルゴン雰囲気下のグローブボックス内で行った。
初回充放電は、雰囲気温度25℃で、0.01C電流にて、上限電圧4.3Vまで定電流定電圧(CC−CV)充電を行った。その後、3.0Vまで0.1C電流での定電流放電を行った。この充放電を2回行い、2回目の放電により求められる放電容量(電池電圧3.0Vまで0.1Cで放電したときの放電電気量)をコインセルの容量とした。次いで雰囲気温度25℃で、0.01C電流にて、上限電圧4.3Vまで定電流定電圧(CC−CV)充電を行った後、0℃で3.0Vまで5C放電(すなわち低温下での急速放電)を行った。このときの放電容量を急速放電容量とし、([急速放電容量]/[コインセル容量])×100を各コインセルの放電特性とした。また、比較例1(LNO1およびLNO2が共にNCA523である実験例)の放電特性値を100としたときの各コインセルの放電特性相対値を求めた。
101 負極集電体
102 負極活物質
103 導電助剤
104バインダ
10 リチウムイオン二次電池
11 負極集電体
12 正極集電体
13 負極活物質層
15 正極活物質層
17 セパレータ
25 負極リード
27 正極リード
29 外装体
31 電解液
Claims (7)
- 一般式Lix1Niy1Me(1.0−y1)O2(ここでMeは、Al、Mn、Na、Fe、Co、Cr、Cu、Zn、Ca、K、Mg、およびPbからなる群より選択される少なくとも1種以上の金属であり、1.0≦x1≦1.2であり、y1は1.0未満の正の数である。)で表される第1リチウム・ニッケル系複合酸化物と、
一般式Lix2Niy2Me(1.0−y2)O2(ここでMeは、Al、Mn、Na、Fe、Co、Cr、Cu、Zn、Ca、K、Mg、およびPbからなる群より選択される少なくとも1種以上の金属であり、1.0≦x2≦1.2であり、y2は1.0未満の正の数である。)で表される第2リチウム・ニッケル系複合酸化物と、
リチウム・マンガン系複合酸化物と、を含むリチウムイオン二次電池用正極活物質を、正極集電体に配置した、リチウムイオン二次電池用正極であって、
y1の値はy2の値よりも大きく、
該正極活物質成分の平均粒径が、該リチウム・マンガン系複合酸化物、該第1リチウム・ニッケル系複合酸化物Lix1Niy1Me(1.0−y1)O2、該第2リチウム・ニッケル系複合酸化物Lix2Niy2Me(1.0−y2)O2の順に大きく、
該正極活物質成分の混合比率が、該第1リチウム・ニッケル系複合酸化物Li x1 Ni y1 Me (1.0−y1) O 2 、該リチウム・マンガン系複合酸化物、該第2リチウム・ニッケル系複合酸化物Li x2 Ni y2 Me (1.0−y2) O 2 の順に高い、
前記リチウムイオン二次電池用正極。 - 該第2リチウム・ニッケル系複合酸化物Lix2Niy2Me(1.0−y2)O2のニッケル含有比率y2の値が0.5以下である、請求項1に記載のリチウムイオン二次電池用正極。
- 該第1リチウム・ニッケル系複合酸化物Lix1Niy1Me(1.0−y1)O2のニッケル含有比率y1の値が、0.5、0.6または0.8である、請求項1または2に記載のリチウムイオン二次電池用正極。
- 該第1リチウム・ニッケル系複合酸化物Lix1Niy1Me(1.0−y1)O2のニッケル含有比率y1の値が0.5である、請求項1〜3のいずれかに記載のリチウムイオン二次電池用正極。
- 該リチウム・マンガン系複合酸化物の平均粒径に対する、該第2リチウム・ニッケル系複合酸化物Lix2Niy2Me(1.0−y2)O2の平均粒径の比が、0.2〜0.4である、請求項1〜4のいずれかに記載のリチウムイオン二次電池用正極。
- 該第1リチウム・ニッケル系複合酸化物が、一般式Lix1Niy1CoZ1Mn(1.0−y1−z1)O2(ここで、1.0≦x1≦1.2、および、y1およびz1はy1+z1<1.0を満たす正の数である。)で表される第1リチウム・ニッケル・コバルト・マンガン複合酸化物であり、該第2リチウム・ニッケル系複合酸化物が、一般式Lix2Niy2CoZ2Mn(1.0−y2−z2)O2(ここで、1.0≦x2≦1.2、および、y2およびz2はy2+z2<1.0を満たす正の数である。)で表されるリチウム・ニッケル・コバルト・マンガン複合酸化物である、請求項1〜5のいずれかに記載のリチウムイオン二次電池用正極。
- 請求項1〜6のいずれかに記載のリチウムイオン二次電池用正極と、
負極と、
セパレータと、
電解液と、
を含む発電要素を、外装体内部に含むリチウムイオン二次電池。
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