JP3991966B2 - 負極および電池 - Google Patents
負極および電池 Download PDFInfo
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- JP3991966B2 JP3991966B2 JP2003317400A JP2003317400A JP3991966B2 JP 3991966 B2 JP3991966 B2 JP 3991966B2 JP 2003317400 A JP2003317400 A JP 2003317400A JP 2003317400 A JP2003317400 A JP 2003317400A JP 3991966 B2 JP3991966 B2 JP 3991966B2
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- 229910052744 lithium Inorganic materials 0.000 claims description 155
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 154
- 239000007773 negative electrode material Substances 0.000 claims description 97
- 238000000034 method Methods 0.000 claims description 73
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 20
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- 239000000126 substance Substances 0.000 claims description 16
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- 230000000052 comparative effect Effects 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 17
- 239000007774 positive electrode material Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 6
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910004706 CaSi2 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910019974 CrSi Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910005329 FeSi 2 Inorganic materials 0.000 description 1
- 229910006115 GeF Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
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- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
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- 229910017996 MIO 2 Inorganic materials 0.000 description 1
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- 229910016006 MoSi Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
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- 150000002291 germanium compounds Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
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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
Description
また、負極活物質層が、ケイ素またはゲルマニウムの単体,合金および化合物からなる群のうちの少なくとも1種を含むようにしたので、高容量を得ることができると共に、リチウムを予め吸蔵させたことによる容量の損失を小さくすることができる。更に、リチウムを吸蔵させることにより、負極活物質層に存在するダングリングボンドや、または水素あるいは酸素などの不純物を低減させることができ、サイクル特性などの電池特性を向上させることができる。
まず、厚み15μmの銅箔よりなる負極集電体11の上にスパッタリング法によりケイ素よりなる負極活物質層12を形成した。次いで、負極活物質層12の上に真空蒸着法により金属リチウムを堆積させた。金属リチウムを堆積させる際の雰囲気は1×10-3Pa未満とし、堆積速度は5nm/sよりも大きくした。なお、堆積させる金属リチウムの量、すなわち負極活物質層12に予め吸蔵させるリチウムの量は、実施例1−1〜1−7で負極活物質層12の有するリチウム吸蔵容量の0.5%、1%、5%、10%、20%、30%、40%と順に変化させた。また、負極活物質層12の厚みは、負極活物質層12の持つ容量から予め吸蔵させるリチウムの容量を差し引いた容量が一定となるようにした。すなわち負極活物質層12の厚みは、実施例1−1では5.03μm、実施例1−2では5.05μm、実施例1−3では5.26μm、実施例1−4では5.56μm、実施例1−5では6.25μm、実施例1−6では7.14μm、実施例1−7では8.33μmとした。この負極活物質層12の厚みはSEM(Scanning Electron Microscope;走査型電子顕微鏡)により確認した。
負極活物質層12をスパッタリング法でゲルマニウムにより形成したことを除き、他は実施例1−1〜1−7と同様にして実施例2−1〜2−7の負極10を作製し、同様にして二次電池を作製した。また、実施例2−1〜2−7に対する比較例2−1〜2−3として、負極に予め吸蔵させるリチウムの量を表2に示したように変えたことを除き、他は実施例2−1〜2−7と同様にして負極を作製し、二次電池を作製した。但し、比較例2−3については、比較例1−3と同様に、リチウムを吸蔵させたことによる負極の変形が大きく、電池を作製することができなかった。作製した実施例2−1〜2−7および比較例2−1,2−2の二次電池についても、実施例1−1〜1−7と同様にして、充放電試験を行い、50サイクル目の容量維持率を求めた。その結果を表2に示す。
負極活物質層12の厚みを0.60μmまたは0.45μm、予め吸蔵させるリチウムの量を負極活物質層12の有するリチウム吸蔵容量の1%としたことを除き、実施例1−1〜1−7と同様にして負極10を作製し、二次電池を作製した。その際、実施例3−1では予め吸蔵させるリチウムの量を単位面積当たりの金属リチウムの厚みに換算して0.026μmとし、実施例3−2では単位面積当たりの金属リチウムの厚みに換算して0.019μmとした。また、実施例3−1,3−2に対する比較例3−1として、負極活物質層12の厚みを0.45μmとし、リチウムを予め吸蔵させないことを除き、実施例3−1,3−2と同様にして負極を作製し、二次電池を作製した。作製した実施例3−1,3−2および比較例3−1の二次電池についても、実施例1−1〜1−7と同様にして、充放電試験を行い、50サイクル目の容量維持率を求めた。その結果を表3に示す。
Claims (4)
- 負極集電体と、この負極集電体に設けられ、負極集電体との界面の少なくとも一部において負極集電体と合金化している負極活物質層とを有し、
前記負極活物質層は、ケイ素(Si)またはゲルマニウム(Ge)の単体,合金および化合物からなる群のうちの少なくとも1種を含み、
負極容量の5%以上40%以下のリチウムを吸蔵している
ことを特徴とする負極。 - 負極集電体と、この負極集電体に気相法,液相法および焼結法からなる群のうちの少なくとも1つの方法により形成された負極活物質層とを有し、
前記負極活物質層は、ケイ素(Si)またはゲルマニウム(Ge)の単体,合金および化合物からなる群のうちの少なくとも1種を含み、
負極容量の5%以上40%以下のリチウムを吸蔵している
ことを特徴とする負極。 - 正極および負極と共に電解質を備えた電池であって、
前記負極は、負極集電体と、この負極集電体に設けられ、負極集電体との界面の少なくとも一部において負極集電体と合金化している負極活物質層とを有し、
前記負極活物質層は、ケイ素(Si)またはゲルマニウム(Ge)の単体,合金および化合物からなる群のうちの少なくとも1種を含み、初回充放電前に負極容量の5%以上40%以下のリチウムを吸蔵している
ことを特徴とする電池。 - 正極および負極と共に電解質を備えた電池であって、
前記負極は、負極集電体と、この負極集電体に気相法,液相法および焼結法からなる群のうちの少なくとも1つの方法により形成された負極活物質層とを有し、
前記負極活物質層は、ケイ素(Si)またはゲルマニウム(Ge)の単体,合金および化合物からなる群のうちの少なくとも1種を含み、初回充放電前に負極容量の5%以上40%以下のリチウムを吸蔵している
ことを特徴とする電池。
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KR1020040071503A KR20050026348A (ko) | 2003-09-09 | 2004-09-08 | 음극 및 배터리 |
CNB2004100768703A CN100474664C (zh) | 2003-09-09 | 2004-09-08 | 阳极及电池 |
US10/935,827 US20050079421A1 (en) | 2003-09-09 | 2004-09-08 | Anode and battery |
US15/000,639 US20160133941A1 (en) | 2003-09-09 | 2016-01-19 | Anode and battery |
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JP4602478B2 (ja) * | 2008-08-04 | 2010-12-22 | パナソニック株式会社 | リチウム二次電池の製造方法およびリチウム二次電池 |
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JP2006324020A (ja) * | 2005-05-17 | 2006-11-30 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池の製造方法 |
JP5076305B2 (ja) * | 2005-11-01 | 2012-11-21 | パナソニック株式会社 | リチウム二次電池用負極の製造方法およびリチウム二次電池の製造方法 |
JP4883391B2 (ja) * | 2005-12-16 | 2012-02-22 | 住友電気工業株式会社 | リチウム二次電池用電極の製造方法 |
JP5238195B2 (ja) * | 2006-07-24 | 2013-07-17 | パナソニック株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
JP5181585B2 (ja) * | 2006-09-12 | 2013-04-10 | パナソニック株式会社 | リチウム二次電池用負極の製造法 |
EP2113960B1 (en) | 2006-11-16 | 2011-07-13 | Panasonic Corporation | Electricity storage device |
JP2008234850A (ja) * | 2007-03-16 | 2008-10-02 | Matsushita Electric Ind Co Ltd | 電気化学素子とその電極の製造方法、製造装置 |
US20090317726A1 (en) | 2008-04-08 | 2009-12-24 | Sony Corporation | Anode and secondary battery |
JP6219273B2 (ja) * | 2012-05-22 | 2017-10-25 | 三洋電機株式会社 | リチウム二次電池用負極、リチウム二次電池、及びリチウム二次電池用負極の製造方法 |
JP6218413B2 (ja) | 2013-03-29 | 2017-10-25 | 株式会社Subaru | プレドープ剤、これを用いた蓄電デバイス及びその製造方法 |
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JPWO2010016217A1 (ja) * | 2008-08-04 | 2012-01-19 | パナソニック株式会社 | リチウム二次電池の製造方法およびリチウム二次電池 |
US8603196B2 (en) | 2008-08-04 | 2013-12-10 | Panasonic Corporation | Lithium secondary battery manufacturing method comprising forming lithium metal layer and lithium secondary battery |
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