JP5179070B2 - 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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- JP5179070B2 JP5179070B2 JP2007045690A JP2007045690A JP5179070B2 JP 5179070 B2 JP5179070 B2 JP 5179070B2 JP 2007045690 A JP2007045690 A JP 2007045690A JP 2007045690 A JP2007045690 A JP 2007045690A JP 5179070 B2 JP5179070 B2 JP 5179070B2
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- Prior art keywords
- negative electrode
- lithium
- active material
- mixture
- secondary battery
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- 229910052744 lithium Inorganic materials 0.000 title claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 30
- 239000000203 mixture Substances 0.000 claims description 41
- 239000007773 negative electrode material Substances 0.000 claims description 25
- -1 polyethylene Polymers 0.000 claims description 25
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- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
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- 238000000926 separation method Methods 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
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- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
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- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead 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
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
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- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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。]
「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 (1)
- リチウム二次電池であって、
負極と、正極と、分離膜と、リチウム塩非水系電解質とを備えてなり、
前記負極が、負極活物質として難黒鉛化炭素及び黒鉛の混合物(重量比=9:1)と、導電剤としてカーボンブラックと、結合剤としてポリフッ化ビニリデンと、低温出力特性向上用添加剤として負極合剤全体重量を基準に30重量%のLi 4 Ti 5 O 12 と、及び溶媒であるN−メチルピロリドンとを混合したスラリーを銅箔に塗布して形成されたものであり、
前記正極が、正極活物質としてLiMn 2 O 4 とLiNi 1/3 Mn 1/3 Co 1/3 O 2 の混合物(重量比=9:1)と、導電剤としてカーボンブラックと、及び結合剤としてポリフッ化ビニリデン(PVDF)とを、重量比85:10:5として、溶媒であるN−メチルピロリドンと混合したスラリーをアルミニウム箔に塗布して形成されたものであり、
前記分離膜が、多孔性ポリエチレンフィルムであり、
前記リチウム塩非水系電解質が、プロピレンカーボネートとジメチルカーボネート(体積比=70:30)と、1M濃度のLiPF 6 との混合物である、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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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) |
KR (1) | KR100881637B1 (ja) |
WO (1) | WO2007126257A1 (ja) |
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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 |
---|---|
KR20070106821A (ko) | 2007-11-06 |
JP2013058495A (ja) | 2013-03-28 |
WO2007126257A1 (en) | 2007-11-08 |
US7985504B2 (en) | 2011-07-26 |
JP5812971B2 (ja) | 2015-11-17 |
JP2007299728A (ja) | 2007-11-15 |
US20110244321A1 (en) | 2011-10-06 |
US8110308B2 (en) | 2012-02-07 |
US20120100426A1 (en) | 2012-04-26 |
KR100881637B1 (ko) | 2009-02-04 |
US20100015524A1 (en) | 2010-01-21 |
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