JP2023532683A - リチウム二次電池用正極およびこれを含むリチウム二次電池 - Google Patents
リチウム二次電池用正極およびこれを含むリチウム二次電池 Download PDFInfo
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- JP2023532683A JP2023532683A JP2022580497A JP2022580497A JP2023532683A JP 2023532683 A JP2023532683 A JP 2023532683A JP 2022580497 A JP2022580497 A JP 2022580497A JP 2022580497 A JP2022580497 A JP 2022580497A JP 2023532683 A JP2023532683 A JP 2023532683A
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- positive electrode
- lithium secondary
- secondary battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000654 additive Substances 0.000 claims abstract description 63
- 230000000996 additive effect Effects 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- 239000011230 binding agent Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000004020 conductor Substances 0.000 claims description 24
- 239000011267 electrode slurry Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- -1 super P Substances 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 18
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 239000002210 silicon-based material Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
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- 229910052772 Samarium Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
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- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
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- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
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- 238000007599 discharging Methods 0.000 abstract description 13
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- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
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- 239000010439 graphite Substances 0.000 description 7
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- 239000007784 solid electrolyte Substances 0.000 description 6
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
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- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
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- 229910012348 LiSiO4—LiI—LiOH Inorganic materials 0.000 description 1
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- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- 229910021385 hard carbon Inorganic materials 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
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- 150000002461 imidazolidines Chemical class 0.000 description 1
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- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides 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
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
Description
本発明は、一実施形態において、
正極集電体と、
前記正極集電体上に位置し、正極活物質、下記化学式1で示す正極添加剤、導電材およびバインダーを含む正極合材層と、を具備し、
下記の式1が1.55以下を満たす、リチウム二次電池用正極を提供する:
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5であり;
RLCZO/R0
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。
Lix[NiyCozMnwM2 v]Ou
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。
製造されたプレ分散液、正極活物質およびバインダーを混合して、正極スラリーを製造する段階と、
正極集電体上に前記正極スラリーを塗布して、正極合材層を製造する段階と、を含み、
製造された正極は、下記の式1が1.55以下を満たす、リチウム二次電池用正極の製造方法を提供する:
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5であり;
RLCZO/R0
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。
上述した本発明による正極と、負極と、前記正極と負極の間に位置する分離膜と、を含むリチウム二次電池を提供する。
本発明は、一実施形態において、
正極集電体と
前記正極集電体上に位置し、正極活物質、正極添加剤、導電材およびバインダーを含む正極合材層と、を備えるリチウム二次電池用正極を提供する。
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5である。
RLCZO/R0
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。
Lix[NiyCozMnwM2 v]Ou
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。
また、本発明は、一実施形態において、
下記の化学式1で示す正極添加剤、導電材およびバインダーを混合して、プレ分散液を製造する段階と、
製造されたプレ分散液、正極活物質およびバインダーを混合して、正極スラリーを製造する段階と、
正極集電体上に前記正極スラリーを塗布して、正極合材層を製造する段階と、を含み、
製造された正極は、下記の式1が1.55以下を満たす、リチウム二次電池用正極の製造方法を提供する:
LipCo(1-q)M1 qO4
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5であり、
RLCZO/R0
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。
しかも、本発明は、一実施形態において、
上述した本発明による正極と、負極と、前記正極と負極の間に介在される分離膜と、を含むリチウム二次電池を提供する。
ホモミキサー(homo mixer)にN-メチルピロリドンを注入し、正極スラリー固形分100重量部に対して正極添加剤としてLi6Co0.7Zn0.3O4 5重量部、導電材としてカーボンブラック2重量部、およびバインダーとしてPVdF 1重量部を秤量して投入した後、2,000rpmで30分間1次混合して、正極製造用プレ分散液を製造した。この際、プレ分散液の製造時における温度および湿度は、それぞれ20~25℃および3%に調節した。
実施例1において正極添加剤を使用しないことを除いて、実施例1と同じ方法で行うことによって、リチウム二次電池用正極を製造した。
ホモミキサー(homo mixer)にN-メチルピロリドンを注入し、正極スラリー固形分100重量部に対して正極活物質としてLiNi0.6Co0.2Mn0.2O2 91重量部、正極添加剤としてLi6Co0.7Zn0.3O4 5重量部、導電材としてカーボンブラック2重量部、およびバインダーとしてPVdF 2重量部を秤量して投入した後、2,000rpmで60分間混合して、リチウム二次電池用正極スラリーを製造した。この際、混合時における温度および湿度は、それぞれ20~25℃および3%に調節した。
ホモミキサー(homo mixer)にN-メチルピロリドンを注入し、正極スラリー固形分100重量部に対して正極添加剤としてLi6Co0.7Zn0.3O4 5重量部、およびバインダーとしてPVdF 1重量部を秤量して投入した後、2,000rpmで30分間1次混合して、正極製造用プレ分散液を製造した。この際、プレ分散液の製造時における温度および湿度は、それぞれ20~25℃および3%に調節した。
プレ分散液の製造時における温度および湿度を下記の表1に示されたように調節したことを除いて、実施例1と同じ方法で行うことによって、リチウム二次電池用正極を製造した。
負極活物質としての天然黒鉛およびケイ素(SiOx、ただし、1≦x≦2)粒子と、バインダーとしてのスチレンブタジエンゴム(SBR)を準備し、正極スラリーを製造する方式と同じ方式で負極スラリーを準備した。この際、負極合材層の製造時に使用される黒鉛は、天然黒鉛(平均粒度:0.01~0.5μm)であり、ケイ素(SiOx)粒子は、0.9~1.1μmの平均粒度を有するものを使用した。準備した負極スラリーを銅集電体の一面に塗布した後、100℃で乾燥し、圧延して、負極を製造した。この際、負極合材層の総厚さは150μmであり、製造された負極の総厚さは約250μmであった。
本発明によるリチウム二次電池用正極の性能を評価するために、下記のような実験を行った。
実施例1と比較例1~5で製造された正極を対象に、4ポイントプローブ(4-point probe)方式で電極の面抵抗を測定し、その結果を下記の表3および図1に示した。
実施例2と比較例6~10で製造されたリチウム二次電池を対象に、55℃で3.5Vおよび1.0Cの条件で初期充電(formation)を行い、前記初期充電を行うことで、正極で発生するガスを脱気して、初期充電時に発生する酸素ガスの含有量を分析した。次に、45℃でそれぞれ0.3Cの条件で50回充放電を繰り返し行うことによって、各充放電時に酸素ガスの含有量をさらに分析し、分析した結果は、下記の表3に示した。
実施例2と比較例6~10で製造されたリチウム二次電池を対象に、25℃の温度で0.1Cの充電電流で充電終止電圧4.2~4.25Vまで充電し、終止電圧で電流密度が0.01Cになるまで充電を行うことによって活性化させた。以後、0.1Cの放電電流で終止電圧2Vまで放電させ、単位質量当たりの初期充放電容量を測定した。
Claims (13)
- 正極集電体と、
前記正極集電体上に位置し、正極活物質、下記の化学式1で示す正極添加剤、導電材およびバインダーを含む正極合材層と、を具備し、
下記の式1が1.55以下を満たす、リチウム二次電池用正極:
[化学式1]
LipCo(1-q)M1 qO4
前記化学式1中、
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5であり;
[式1]
RLCZO/R0
式1中、
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。 - 式1が1.3以下を満たす、請求項1に記載のリチウム二次電池用正極。
- 正極添加剤は、空間群がP42/nmcである正方晶系構造(tetragonal structure)を有する、請求項1または2に記載のリチウム二次電池用正極。
- 正極添加剤の含有量は、正極合材層100重量部に対して0.1~10重量部である、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用正極。
- 正極活物質は、下記の化学式2で示すリチウム金属複合酸化物である、請求項1から4のいずれか一項に記載のリチウム二次電池用正極:
[化学式2]
Lix[NiyCozMnwM2 v]Ou
前記化学式2中、
M2は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
x、y、z、w、vおよびuは、それぞれ1.0≦x≦1.30、0.1≦y<0.95、0.01<z≦0.5、0.01<w≦0.5、0≦v≦0.2、1.5≦u≦4.5である。 - 導電材は、天然黒鉛、人造黒鉛、カーボンブラック、アセチレンブラック、デンカブラック、ケッチェンブラック、スーパーP、チャネルブラック、ファーネスブラック、ランプブラック、サーマルブラック、グラフェンおよびカーボンナノチューブからなる群から選ばれる1種以上を含む、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用正極。
- 導電材は、正極合材層100重量部に対して0.1~5重量部で含まれる、請求項6に記載のリチウム二次電池用正極。
- 下記の化学式1で示す正極添加剤、導電材およびバインダーを混合して、プレ分散液を製造する段階と、
製造されたプレ分散液、正極活物質およびバインダーを混合して、正極スラリーを製造する段階と、
正極集電体上に前記正極スラリーを塗布して、正極合材層を製造する段階と、を含み、
製造された正極は、下記の式1が1.55以下を満たす、リチウム二次電池用正極の製造方法:
[化学式1]
LipCo(1-q)M1 qO4
前記化学式1中、
M1は、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、およびMoからなる群から選ばれる1種以上の元素であり、
pおよびqは、それぞれ5≦p≦7および0≦q≦0.5であり;
[式1]
RLCZO/R0
式1中、
RLCZOは、正極合材層に化学式1で示す正極添加剤を含有する場合の電極面抵抗を示し、
R0は、正極合材層に化学式1で示す正極添加剤を含有しない場合の電極面抵抗を示す。 - 前記プレ分散液を製造する段階は、10%以下の相対湿度条件で行われる、請求項8に記載のリチウム二次電池用正極の製造方法。
- 請求項1から7のいずれか一項に記載の正極と、負極と、前記正極と負極の間に位置する分離膜と、を含むリチウム二次電池。
- 負極は、負極集電体と、前記負極集電体上に位置し、負極活物質を含有する負極合材層と、を備え、
前記負極活物質は、炭素物質およびシリコン物質を含有する、請求項10に記載のリチウム二次電池。 - シリコン物質は、ケイ素(Si)粒子および酸化ケイ素(SiOX、1≦X≦2)粒子のうち1種以上を含む、請求項11に記載のリチウム二次電池。
- シリコン物質は、負極合材層100重量部に対して1~20重量部で含まれる、請求項11または12に記載のリチウム二次電池。
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