JP5481325B2 - リチウムイオン二次電池及びその物性評価方法 - Google Patents
リチウムイオン二次電池及びその物性評価方法 Download PDFInfo
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- JP5481325B2 JP5481325B2 JP2010199274A JP2010199274A JP5481325B2 JP 5481325 B2 JP5481325 B2 JP 5481325B2 JP 2010199274 A JP2010199274 A JP 2010199274A JP 2010199274 A JP2010199274 A JP 2010199274A JP 5481325 B2 JP5481325 B2 JP 5481325B2
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- positive electrode
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- battery
- electrode active
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 25
- 230000000704 physical effect Effects 0.000 title claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 42
- 239000011800 void material Substances 0.000 claims description 32
- 239000011163 secondary particle Substances 0.000 claims description 25
- 239000011164 primary particle Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 description 32
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- -1 nickel metal hydride Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002482 conductive additive Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910014397 LiNi1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910005800 NiMnCo Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910021437 lithium-transition metal 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
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
Images
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Description
Pin=Emax・(Emax−Eocv)/Rdcr・・・(式2)
Pout:最大出力(W)
Pin:最大入力(W)
Emin:使用下限電圧(V)
Emax:使用上限電圧(V)
Eocv:開回路電圧(V)
Rdcr:内部抵抗(Ω)
(1)一次粒子が集合して二次粒子を形成している正極活物質において、該二次粒子の断面に露出している空隙部分及び一次粒子部分の面積の合計のうち、該空隙部分の割合が25%以上100%未満であり、かつ、該空隙部分のボックスカウント法におけるボックス次元が1.7以上2.0未満である正極活物質を用いたリチウムイオン二次電池。
(2)正極活物質が、一般式Li1+xNiyMnzCo1−y−zO(4+x)/2(ここで、−0.20≦x≦0.20かつ0.30≦y≦0.50かつ0.30≦z≦0.50)で示される前記(1)に記載のリチウムイオン二次電池。
(3)一次粒子が集合して二次粒子を形成している正極活物質において、該二次粒子の断面に露出している空隙部分及び一次粒子部分の面積の合計のうちの該空隙部分の割合、及び該空隙部分のボックスカウント法におけるボックス次元を求め、該空隙部分の割合及び該ボックス次元を正極活物質の物性の指標とする、リチウムイオン二次電池用の正極活物質の物性評価方法。
(18650型電池の作製と性能測定)
正極電極板の作製には、空隙部分の割合及びボックス次元の値が各々異なる、下記の表1に示される6種類の正極活物質(組成式LiNi1/3Co1/3Mn1/3O2)を用いた。
(正極活物質の断面測定)
上記のように作製した、6種類の正極活物質を用いた正極電極板の各々から、一部を切り取り樹脂に埋包し、研磨を行うことで電極の合材層に含まれる正極活物質の断面を得た。上記のように、走査型電子顕微鏡の反射電子像から正極活物質粒子の断面画像を得て、さらに二値化画像を得た。活物質1の反射電子像及び二値化画像を図4に例示する。得られた二値化画像から、空隙部分の割合及びボックス次元を求めた結果を表1に示す。
2 正極合材層
3 正極リード
11 負極集電体
12 負極合材層
13 負極リード
21 セパレータ
31 インシュレータ
41 電池缶
51 正極端子
Claims (3)
- 一次粒子が集合して二次粒子を形成している正極活物質において、該二次粒子の、D50%粒子径に対応する径を示す断面に露出している空隙部分及び一次粒子部分の面積の合計のうち、該空隙部分の割合が25%以上100%未満であり、かつ、該空隙部分のボックスカウント法におけるボックス次元が1.7以上2.0未満である正極活物質を用いたリチウムイオン二次電池。
- 正極活物質が、一般式Li1+xNiyMnzCo1−y−zO(4+x)/2(ここで、−0.20≦x≦0.20かつ0.30≦y≦0.50かつ0.30≦z≦0.50)で示される請求項1に記載のリチウムイオン二次電池。
- 一次粒子が集合して二次粒子を形成している正極活物質において、該二次粒子の断面に露出している空隙部分及び一次粒子部分の面積の合計のうちの該空隙部分の割合、及び該空隙部分のボックスカウント法におけるボックス次元を求め、該空隙部分の割合及び該ボックス次元を正極活物質の物性の指標とする、リチウムイオン二次電池用の正極活物質の物性評価方法。
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JP6500001B2 (ja) | 2016-08-31 | 2019-04-10 | 住友化学株式会社 | リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池 |
JP6472822B2 (ja) | 2017-03-03 | 2019-02-20 | 住友化学株式会社 | 非水電解液二次電池用セパレータ |
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JP4740415B2 (ja) * | 2007-05-25 | 2011-08-03 | 株式会社日立製作所 | 電気自動車或いはハイブリッド自動車用リチウム二次電池 |
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