JP5812971B2 - 低温出力特性が改善されたリチウム二次電池 - Google Patents
低温出力特性が改善されたリチウム二次電池 Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
LixMyOz (1)
Lix’My’Sz’ (2)
[上記式中、
Mはそれぞれ独立的にTi、Sn、Cu、Pb、Sb、Zn、Fe、In、AlまたはZrを表し、
x、y、z、x’、y’及びz’は、Mの酸化数(oxidation number)によって決定されるものである。]
本発明の好ましい態様
〔1〕 炭素系負極活物質を含むリチウム二次電池用負極合剤であって、
下記式(1)で表されるリチウム金属酸化物及び下記の式(2)で表されるリチウム金属硫化物からなる群より選ばれた1または2以上の化合物を、前記負極合剤全体重量を基準に1〜50重量%含んでなる、負極合剤を提案する。
LixMyOz (1)
Lix’My’Sz’ (2)
[上記式中、
Mはそれぞれ独立的にTi、Sn、Cu、Pb、Sb、Zn、Fe、In、AlまたはZrを表し、
x、y、z、x’、y’及びz’は、Mの酸化数によって決定されるものである。]
〔2〕前記炭素系活物質が、結晶質炭素と非晶質炭素の混合物である、〔1〕に記載の負極合剤である。
〔3〕前記混合物が、難黒鉛化炭素と黒鉛の混合物である、〔2〕に記載の負極合剤である。
〔4〕上記式(1)で表されるリチウム金属酸化物が、Li4Ti5O12、LiTi2O4またはこれらの混合物である、〔1〕に記載の負極合剤である。
〔5〕上記式(2)で表されるリチウム金属硫化物が、LiTiS2である、〔1〕に記載の負極合剤。
〔6〕前記化合物の含有量が、負極合剤全体重量を基準に5〜30重量%である、〔1〕に記載の負極合剤。
〔7〕前記負極合剤が、導電剤及び結着剤と、必要に応じて充填剤とをさらに含んでなる、〔1〕に記載の負極合剤。
〔8〕〔1〕〜〔7〕のいずれか一項に記載の負極合剤で製造された負極と、正極と、分離膜と、及びリチウム塩含有非水電解質とを備えてなる、リチウム二次電池が提案される。
〔9〕前記正極が、正極活物質として、リチウムマンガン酸化物及びリチウムニッケル−マンガン−コバルト複合酸化物の混合物を含んでなるものである、〔8〕に記載のリチウム二次電池である。
〔10〕前記電池が、優れた低温出力特性が要求される電気自動車またはハイブリッド電気自動車の電源として使用されるものである、〔8〕に記載のリチウム二次電池である。
「活物質」とは「活性物質」をも意味し、「負極合剤」は、「負極混合剤」又は「負極混合物」をも意味する。
LixMyOz (1)
Lix’My’Sz’ (2)
上記式中、Mはそれぞれ独立的にTi、Sn、Cu、Pb、Sb、Zn、Fe、In、AlまたはZrを表し;x、y、z、x’、y’及びz’は、Mの酸化数(oxidation number)によって決定される。
正極活物質としてLiMn2O4とLiNi1/3Mn1/3Co1/3O2の混合物(重量比=9:1)、導電剤としてスーパーP(Super P)、及び結合剤としてポリフッ化ビニリデン(PVDF)を、重量比85:10:5として溶媒(N−メチルピロリドン)に混合してスラリーを製造した。このスラリーをアルミニウム箔に均一に塗布し、130℃の対流式オーブンで乾燥したのちプレスして正極を製造した。
負極製造時に、Li4Ti5O12を30重量%添加した以外は、実施例1と同様にして電池を製造した。
負極製造時に、Li4Ti5O12の代わりにLiTiS2を同量添加した以外は、実施例1と同様にして電池を製造した。
負極製造時に、Li4Ti5O12の代わりにLiTi2O4を15重量%添加した以外は、実施例1と同様にして電池を製造した。
負極製造時に、Li4Ti5O12などの添加剤を添加せず、負極活物質、導電剤及び結着剤を90:5:5重量比とした以外は、実施例1と同様にして電池を製造した。
上記実施例1〜4と比較例1でそれぞれ製造された電池に対して、−30℃の条件で、SOC 50で10C-rateの電流でそれぞれ5初間放電して電圧降下(voltage drop)を測定した。その結果を、下記の表1に示す。
Claims (3)
- 改善された低温出力特性を付与してなる、リチウム二次電池であって、
炭素系負極活物質、導電剤及び結着剤を含むリチウム二次電池用負極合剤で製造された負極と、
正極と、
分離膜と、及び
リチウム塩含有非水電解質とを備えてなり、
前記負極合剤が、Li4Ti5O12、LiTi2O4及びLiTiS2からなる群より選ばれた1または2以上の化合物を、前記負極合剤全体重量を基準に5〜30重量%含んでなり、
前記炭素系負極活物質が、難黒鉛化炭素と黒鉛の混合物(重量比9:1)であり、
前記正極が、正極活物質として、リチウムマンガン酸化物及びリチウムニッケル−マンガン−コバルト複合酸化物の混合物(重量比9:1)を含んでなるものである、リチウム二次電池。 - 前記負極合剤が、充填剤をさらに含んでなる、請求項1に記載のリチウム二次電池。
- 電気自動車又はハイブリッド電気自動車の電源として使用される、請求項1に記載のリチウム二次電池。
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KR1020060039137A KR100881637B1 (ko) | 2006-05-01 | 2006-05-01 | 저온 출력 특성이 개선된 리튬 이차전지 |
KR10-2006-0039137 | 2006-05-01 |
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JP2007045690A Division JP5179070B2 (ja) | 2006-05-01 | 2007-02-26 | 低温出力特性が改善されたリチウム二次電池 |
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JP2013058495A JP2013058495A (ja) | 2013-03-28 |
JP5812971B2 true JP5812971B2 (ja) | 2015-11-17 |
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JP2012254394A Active JP5812971B2 (ja) | 2006-05-01 | 2012-11-20 | 低温出力特性が改善されたリチウム二次電池 |
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JP (2) | JP5179070B2 (ja) |
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WO (1) | WO2007126257A1 (ja) |
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JP4752085B2 (ja) * | 2000-02-01 | 2011-08-17 | 株式会社豊田中央研究所 | リチウム二次電池用負極 |
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CA2327370A1 (fr) * | 2000-12-05 | 2002-06-05 | Hydro-Quebec | Nouvelle methode de fabrication de li4ti5o12 pur a partir du compose ternaire tix-liy-carbone: effet du carbone sur la synthese et la conductivite de l'electrode |
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FR2831715B1 (fr) * | 2001-10-25 | 2004-03-19 | Centre Nat Rech Scient | Oxyde de lithium et de vanadium, son utilisation comme matiere active d'electrode |
WO2003036752A1 (en) | 2001-10-26 | 2003-05-01 | Kabushiki Kaisha Toshiba | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
JP3698320B2 (ja) * | 2002-06-03 | 2005-09-21 | 日産自動車株式会社 | 組電池 |
JP2004063394A (ja) | 2002-07-31 | 2004-02-26 | Sanyo Electric Co Ltd | 非水電解質電池 |
JP2004139743A (ja) * | 2002-08-21 | 2004-05-13 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP4183472B2 (ja) * | 2002-10-10 | 2008-11-19 | 三洋電機株式会社 | 非水電解質二次電池 |
JP4612321B2 (ja) | 2003-04-04 | 2011-01-12 | 株式会社東芝 | 非水電解質二次電池 |
JP4207678B2 (ja) * | 2003-06-18 | 2009-01-14 | 日産自動車株式会社 | リチウムイオン電池型二次電池用電極の製造方法およびその装置並びにリチウムイオン電池型二次電池用電極 |
KR20050006540A (ko) * | 2003-07-09 | 2005-01-17 | 한국과학기술연구원 | 초극세 섬유상 다공성 고분자 분리막을 포함하는리튬이차전지 및 그 제조방법 |
JP5142452B2 (ja) * | 2003-09-29 | 2013-02-13 | 三洋電機株式会社 | 非水電解質二次電池の充放電制御方法 |
JP4554911B2 (ja) | 2003-11-07 | 2010-09-29 | パナソニック株式会社 | 非水電解質二次電池 |
JP4667071B2 (ja) | 2004-03-30 | 2011-04-06 | 三洋電機株式会社 | 非水電解質二次電池 |
JP4245532B2 (ja) * | 2004-08-30 | 2009-03-25 | 株式会社東芝 | 非水電解質二次電池 |
-
2006
- 2006-05-01 KR KR1020060039137A patent/KR100881637B1/ko active IP Right Grant
-
2007
- 2007-02-26 JP JP2007045690A patent/JP5179070B2/ja active Active
- 2007-04-27 WO PCT/KR2007/002069 patent/WO2007126257A1/en active Application Filing
- 2007-04-27 US US12/299,273 patent/US7985504B2/en active Active
-
2011
- 2011-06-20 US US13/164,431 patent/US8110308B2/en active Active
-
2012
- 2012-01-05 US US13/343,797 patent/US20120100426A1/en not_active Abandoned
- 2012-11-20 JP JP2012254394A patent/JP5812971B2/ja active Active
Also Published As
Publication number | Publication date |
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US7985504B2 (en) | 2011-07-26 |
JP2013058495A (ja) | 2013-03-28 |
KR20070106821A (ko) | 2007-11-06 |
US20120100426A1 (en) | 2012-04-26 |
US8110308B2 (en) | 2012-02-07 |
JP2007299728A (ja) | 2007-11-15 |
JP5179070B2 (ja) | 2013-04-10 |
US20100015524A1 (en) | 2010-01-21 |
US20110244321A1 (en) | 2011-10-06 |
KR100881637B1 (ko) | 2009-02-04 |
WO2007126257A1 (en) | 2007-11-08 |
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