JP5367777B2 - 正極活物質及びこれを備えるリチウム電池 - Google Patents
正極活物質及びこれを備えるリチウム電池 Download PDFInfo
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- JP5367777B2 JP5367777B2 JP2011174545A JP2011174545A JP5367777B2 JP 5367777 B2 JP5367777 B2 JP 5367777B2 JP 2011174545 A JP2011174545 A JP 2011174545A JP 2011174545 A JP2011174545 A JP 2011174545A JP 5367777 B2 JP5367777 B2 JP 5367777B2
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- active material
- positive electrode
- transition metal
- electrode active
- metal oxide
- Prior art date
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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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
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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
- H01M4/362—Composites
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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
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Description
MoO3遷移金属酸化物を1,000〜1,500℃で、H2/N2の還元雰囲気(5体積%H2、95体積%N2の混合ガス)下で10時間熱処理し、MoO2遷移金属酸化物を形成した。
LiCoO2の100重量部に、上記製造例1で得たMoO2遷移金属酸化物1重量部を混合して、正極活物質を製造した。この収得した正極活物質94重量%に、Super Pカーボンブラック3重量%及びPVDF3重量%を混合して、正極活物質スラリ組成物を製造した後、このスラリ組成物を、アルミニウムホイルの電流集電体に塗布した後、乾燥させて正極を製造した。そして、黒鉛粉末約3重量%と、バインダとしてPVDF3重量%とを、N−メチル−2−ピロリドンに添加して負極活物質スラリを形成し、負極集電体である銅箔に塗布して負極を製造した。この正極と負極との中間に、ポリプロピレンからなる分離膜を介在させ、エチレンカーボネート:ジエチルカーボネートを3:7の割合で混合して作った混合溶媒に、LiPF6が1.50モル/Lの濃度で溶解された非水電解質を注入して、コイン型リチウム電池を製造した。
LiCoO2の100重量部に、上記製造例1で得たMoO2遷移金属酸化物5重量部を混合することを除いては、実施例1と同じ方法でリチウム電池を製造した。
LiCoO2の100重量部に、上記製造例1で得たMoO2遷移金属酸化物10重量部を混合することを除いては、実施例1と同じ方法でリチウム電池を製造した。
1重量部のMoO2を100mlの水に溶かしてコーティング液を製造した。このコーティング液に、平均粒径が20μmである100重量部のLiCoO2正極活物質と、1重量部の酢酸とを投入して反応させてコーティングした。コーティングされたLiCoO2を室温で24時間乾燥させた後、400℃で10時間熱処理して正極活物質を製造したことを除いては、実施例1と同じ方法でリチウム電池を製造した。
LiCoO2とLi2NiO2との混合物(LiCoO2:Li2NiO2=70:30重量比)100重量部に、上記製造例1で得たMoO2遷移金属酸化物5重量部を混合することを除いては、実施例1と同じ方法でリチウム電池を製造した。
正極活物質として、遷移金属酸化物が含まれず、LiCoO2正極活物質だけを使用したことを除いては、上記実施例1と同じ方法でリチウム電池を製造した。
正極活物質として、遷移金属酸化物が含まれず、LiCoO2とLi2NiO2との混合正極活物質(LiCoO2:Li2NiO2=70:30重量比)だけを利用して正極を製造したことを除いては、上記実施例5と同じ方法でリチウム電池を製造した。
実施例1、2、3及び4で製造されたコイン型リチウム電池を4.4Vまで充電した後、充電された電池を解体して正極活物質を得た。そこから収得された正極活物質を、エチレンカーボネート:ジエチルカーボネートを3:7の割合で混合して作った混合溶媒にLiPF6が1.50モル/Lの濃度で溶解された非水電解質と共に、サンプリングした。このようにサンプリングされた正極活物質に対して、50℃から375℃まで、N2雰囲気下で10℃/minの昇温速度で設定された示差走査熱量計(DSC、TA Instruments社製)を利用して発熱量変化を測定した。
実施例5及び比較例2で製造された正極活物質に対し、4.4Vまで充電後、60℃で100時間保存して電池内で発生したガス発生量を測定した。その結果を表1に表した。
実施例1〜5、比較例1及び2によって製造されたリチウム電池を利用し、定電流160mA/1Cで、電圧が4.4Vになるまで充電し、その後定電圧4.4Vで、電流が1/20Cになるまで充電して充電容量を測定した。その後、定電流160mA/1Cで、電圧が4.4Vになるまで放電して放電容量を測定し、効率を求めた。その結果を表1に表した。
Claims (3)
- LiCoO 2 及びLi 2 NiO 2 のうち一つ以上のリチウム複合酸化物100重量部及び0.05ないし15重量部のMoO2を含む正極活物質であって、リチウム複合酸化物が下記工程を含む方法によりMoO 2 によってコーティングされて成る正極活物質:
1)MoO 2 の水溶液を調製する工程、
2)該水溶液中に該リチウム複合酸化物を投入して該リチウム複合酸化物をコーティングする工程、
3)工程2)で得られるリチウム複合酸化物を乾燥し、次いで熱処理する工程。 - MoO 2 は、前記リチウム複合酸化物100重量部に対して、0.1ないし10重量部で含まれる、請求項1に記載の正極活物質。
- 請求項1又は2記載の正極活物質を含む正極と、負極と、電解質と、を備えるリチウム電池。
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2011
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- 2011-07-15 US US13/184,294 patent/US9368786B2/en active Active
- 2011-07-20 EP EP20110174701 patent/EP2418719A3/en not_active Withdrawn
- 2011-08-04 CN CN2011102223388A patent/CN102376946A/zh active Pending
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JP2012043787A (ja) | 2012-03-01 |
US20120037846A1 (en) | 2012-02-16 |
KR101264337B1 (ko) | 2013-05-14 |
KR20120022554A (ko) | 2012-03-12 |
EP2418719A2 (en) | 2012-02-15 |
EP2418719A3 (en) | 2013-01-09 |
US9368786B2 (en) | 2016-06-14 |
CN102376946A (zh) | 2012-03-14 |
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