JP2013016481A - 負極活物質、それを含む電極、それを採用したリチウム電池及びその製造方法 - Google Patents
負極活物質、それを含む電極、それを採用したリチウム電池及びその製造方法 Download PDFInfo
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- JP2013016481A JP2013016481A JP2012142806A JP2012142806A JP2013016481A JP 2013016481 A JP2013016481 A JP 2013016481A JP 2012142806 A JP2012142806 A JP 2012142806A JP 2012142806 A JP2012142806 A JP 2012142806A JP 2013016481 A JP2013016481 A JP 2013016481A
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- Prior art keywords
- negative electrode
- active material
- electrode active
- porous
- manganese oxide
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 163
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- 239000002244 precipitate Substances 0.000 description 1
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Abstract
【解決手段】規則的な多孔性マンガン酸化物を含み、該マンガン酸化物の気孔が二重サイズ分布を有する負極活物質、それを含む電極、それを採用したリチウム電池及び該負極活物質の製造方法である。
【選択図】図1A
Description
MnxOy
前記化学式1で、1≦x≦3、1≦y≦4、2≦x+y≦7、0<y/x<2である。
MnxOy
前記化学式1で、1≦x≦3、1≦y≦4、2≦x+y≦7、0<y/x<2である。
MnOz
前記化学式2で、1≦z<2である。
O2;LiNiVO4;Li(3−f)J2(PO4)3(0≦f≦2);Li(3−f)Fe2(PO4)3(0≦f≦2);LiFePO4の化学式のうちいずれか一つで表現される化合物を使用することができる。
実施例1(Mn2O3の合成)
Mn(NO3)2・6H2Oを加熱して溶かした溶融物を、多孔性SiO2に注入した。前記SiO2 100重量部に対し、Mn2O3 40重量部の比率になるように、Mn(NO3)2・6H2O溶融物を、多孔性SiO2に注入した。次に、前記Mn(NO3)2・6H2Oが注入された多孔性SiO2を大気雰囲気で、550℃で3時間焼成させ、SiO2−Mn2O3複合体を得た。前記複合体を2M NaOH水溶液に投入し、1時間反応させる過程を2回反復し、SiO2テンプレートを除去した後で濾過し、多孔性Mn2O3を得た。
100℃で水熱合成された多孔性SiO2の代わりに、140℃で水熱合成された多孔性SiO2を使用したことを除いては、実施例1と同じ方法で、多孔性Mn2O3を製造した。
140℃で水熱合成された多孔性SiO2の代わりに、150℃で水熱合成された多孔性SiO2を使用したことを除いては、実施例1と同じ方法で、多孔性Mn2O3を製造した。
150℃で水熱合成された多孔性SiO2の代わりに、160℃で水熱合成された多孔性SiO2を使用したことを除いては、実施例1と同じ方法で、多孔性Mn2O3を製造した。
Mn(NO3)2・6H2Oを加熱して溶かした溶融物を、多孔性SiO2に注入した。前記SiO2 100重量部に対し、Mn2O3 40重量部の比率になるように、Mn(NO3)2・6H2O溶融物をSiO2に注入した。次に、前記Mn(NO3)2・6H2Oが注入された多孔性SiO2を大気雰囲気で550℃で3時間焼成させ、SiO2−Mn2O3複合体を得た。得られたSiO2−Mn2O3複合体を、混合ガス(H2:N2=1:1、体積比)を使用した還元雰囲気で300℃で3時間熱処理し、SiO2−Mn3O4複合体を得た。前記複合体を2M NaOH水溶液に投入し、1時間反応させる過程を2回反復し、SiO2テンプレートを除去した後で濾過し、多孔性Mn3O4を得た。
Mn(NO3)2・6H2Oを加熱して溶かした溶融物を、多孔性SiO2に注入した。前記SiO2 100重量部に対し、Mn2O3 40重量部の比率になるように、Mn(NO3)2・6H2O溶融物をSiO2に注入した。次に、前記Mn(NO3)2・6H2Oが注入された多孔性SiO2を、大気雰囲気で550℃で3時間焼成させ、SiO2−Mn2O3複合体を得た。得られたSiO2−Mn2O3複合体を、混合ガス(H2:N2=1:1、体積比)を使用した還元雰囲気で300℃で3時間熱処理し、SiO2−Mn3O4複合体を得た。前記複合体を2M NaOH水溶液に投入し、1時間反応させる過程を2回反復してSiO2テンプレートを除去した後で濾過し、多孔性Mn3O4を得た。多孔性Mn3O4を、H2ガスを利用した還元雰囲気で、400℃で2時間熱処理し、多孔性MnOを得た。
気孔のないバルク(bulk)Mn2O3をそのまま入手して使用した。
気孔のないバルク(bulk)Mn3O4をそのまま入手して使用した。
気孔のないバルク(bulk)MnOをそのまま入手して使用した。
100mL蒸溜水に、5mmolニトリロトリ酢酸(nitrilotriacetate acid)及び5mmol Mn(CH3COO)2を溶かした。この溶液を、オートクレーブ(autoclave)を利用して、180℃で6時間水熱処理した。このような方法で、得られた白色の沈殿物を、円心分離を介して分離した後、80℃で8時間乾燥させた。前記乾燥物に対する600℃での3時間の熱処理を介して、不規則な気孔を有する多孔性Mn2O3を合成した。
実施例7
前記実施例1で製造された多孔性Mn2O3粉末70mg、炭素導電剤(Super−P、Timcal Inc.)15mg、及びバインダ(ポリアミド/イミド、PAI)15mgを、15mLのN−メチルピロリドン(NMP)と共にメノウ乳鉢(agate mortar)で混合してスラリを製造した。前記スラリを、ドクターブレードを使用して銅集電体上に、約50μm厚に塗布し、常温で2時間乾燥した後、真空、200℃の条件で2時間さらに乾燥させて負極板を製造した。
前記実施例1で製造されたマンガン酸化物の代わりに、前記実施例2ないし6で製造されたマンガン酸化物を使用したことを除いては、前記実施例7と同じ方法で製造した。
前記実施例1で製造されたマンガン酸化物の代わりに、前記比較例1ないし4で製造されたマンガン酸化物を使用したことを除いては、前記実施例7と同じ方法で製造した。
前記実施例1で製造されたMn2O3粉末に対し、X線回折(X−ray diffraction)実験を行い、その結果を図1Aに示し、低角X線回折実験を行い、その結果を図1Bに示した。
前記実施例1で製造されたMn2O3粉末に対し、窒素吸着実験を行った。
前記実施例1で製造された負極活物質粉末に対して電子透過顕微鏡(TEM)実験を行い、その結果を図7Aないし図7Bに示した。
前記実施例7ないし12及び比較例5ないし8で製造されたリチウム電池に対し、負極活物質1g当たり100mAの電流で、電圧が0.001V(vs.Li)に至るまで充電し、また同じ電流で、電圧が3V(vs.Li)に至るまで放電した。次に、同じ電流と電圧との区間で、充電及び放電を50回反復した。
容量維持率[%]=[50回目のサイクル放電容量/1回目のサイクル放電容量]×100(ただし、比較例8は、30回目のサイクル放電容量を使用)
初期充放電効率[%]=[1回目のサイクル放電容量/1回目のサイクル充電容量]×100
2 負極
3 正極
4 セパレータ
5 電池ケース
6 キャップ・アセンブリ
Claims (29)
- 規則的な多孔性マンガン酸化物を含み、
前記マンガン酸化物が、下記化学式1で表示される負極活物質:
[化1]
MnxOy
前記化学式1で、1≦x≦3、1≦y≦4、2≦x+y≦7、0<y/x<2である。 - 前記マンガン酸化物の気孔が、二重サイズ分布を有することを特徴とする請求項1に記載の負極活物質。
- 前記気孔が、1nmないし5nm範囲の第1ピーク、及び10nmないし20nm範囲の第2ピークを含むことを特徴とする請求項1に記載の負極活物質。
- 前記気孔が、2nmないし5nm範囲の第1ピーク、及び16ないし20nm範囲の第2ピークを含むことを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の低角X線回折スペクトルで、(110)面に係わるピークが、Bragg2θ角0.6±0.2°で示されることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の低角X線回折スペクトルで、(110)面に係わるピークと、(221)面に係わるピークとの強度比I(110)/I(221)が、0.1以上であることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の低角X線回折スペクトルで、(110)面に係わるピークと、(221)面に係わるピークとの強度比I(110)/I(221)が、0.1ないし10であることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の骨格厚が、5nm以上であることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の骨格厚が、5nmないし20nmであることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の結晶サイズが、5nm以上であることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の結晶サイズが、5nmないし30nmであることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の気孔体積が、0.1cm3/gないし2cm3/gであることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の気孔体積が、0.5m2/gないし1cm3/gであることを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の気孔が互いに連結され、チャネルを形成することを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物の気孔が、1nmないし20nmの直径を有し、気孔間の壁を形成する骨格が、5nmないし20nmの厚みを有することを特徴とする請求項1に記載の負極活物質。
- 前記多孔性マンガン酸化物が、MnO、Mn2O3及びMn3O4からなる群から選択された一つ以上であることを特徴とする請求項1に記載の負極活物質。
- 請求項1ないし請求項16のうち、いずれか1項に記載の負極活物質を含む負極。
- 請求項17に記載の負極を採用したリチウム電池。
- 負極活物質単位重量当たり放電容量が、800mAh/g以上であることを特徴とする請求項18に記載のリチウム電池。
- 前記リチウム電池が、充放電実験の最初の充電サイクルで得られる電圧(V)による充電容量(Q)の変化率(dQ)が、リチウム対比で、2.2ないし3Vの電圧範囲でピークを示すことを特徴とする請求項18に記載のリチウム電池。
- 請求項17に記載の負極を採用したキャパシタ。
- 多孔性化合物にマンガン前駆体を含む液体を含浸させる段階と、
前記液体が含浸された多孔性化合物を焼成させる段階と、
前記焼成の結果物をエッチング液でエッチングする段階と、を含む負極活物質の製造方法。 - 前記多孔性化合物が、シリカ(SiO2)、Al2O3、ZnO、MgO、及びそれらの混合物からなる群から選択される一つ以上であることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記マンガン前駆体が、Mn(NO3)2・6H2O、Mn(CH3COO)2・4H2O及びMnCl2・4H2Oからなる群から選択される一つ以上であることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記液体が、前記マンガン前駆体の溶融物または前記マンガン前駆体を溶媒に溶解させた溶液であることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記焼成段階の焼成温度が、300℃ないし700℃であることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記焼成が、酸化性雰囲気または還元性雰囲気で行われることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記還元性雰囲気が、窒素、アルゴン、ヘリウム及び水素からなる群から選択された一つ以上のガス雰囲気であることを特徴とする請求項22に記載の負極活物質の製造方法。
- 前記エッチング液が、フッ酸(HF)、NaOH及びHF−NH4Fからなる群から選択される一つ以上であることを特徴とする請求項22に記載の負極活物質の製造方法。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017135095A (ja) * | 2015-11-02 | 2017-08-03 | アイメック・ヴェーゼットウェーImec Vzw | リチウムマンガン酸化物層を形成するための方法 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9413004B2 (en) | 2013-03-26 | 2016-08-09 | Toyota Motor Engineering & Manufacturing North America, Inc. | Magnesium battery having a cathode containing manganese dioxide nanoparticles as active material |
US9590240B2 (en) | 2013-05-14 | 2017-03-07 | Nano And Advanced Materials Institute Limited | Metal/non-metal co-doped lithium titanate spheres with hierarchical micro/nano architectures for high rate lithium ion batteries |
WO2014200442A1 (en) * | 2013-06-14 | 2014-12-18 | Nanyang Technological University | Method of preparing a metal oxyhydroxide nanostructured material |
PL404381A1 (pl) * | 2013-06-19 | 2014-12-22 | Instytut Elektrotechniki | Sposób wytwarzania tlenkowego materiału elektrodowego, tlenkowy materiał elektrodowy i zastosowanie tlenkowego materiału elektrodowego |
KR102155694B1 (ko) * | 2013-08-30 | 2020-09-14 | 삼성전자주식회사 | 전극 활물질, 그 제조방법, 이를 포함한 전극 및 상기 전극을 포함한 리튬 전지 |
KR102124053B1 (ko) | 2013-09-17 | 2020-06-17 | 삼성전자주식회사 | 고분자, 이를 포함하는 리튬 전지용 전극 및 이를 구비한 리튬 전지 |
IL230509A (en) * | 2014-01-16 | 2016-02-29 | Elbit Systems Land & C4I Ltd | Super-capacitor configuration with peptide-coated graphene electrodes |
KR101981609B1 (ko) * | 2015-09-24 | 2019-05-24 | 주식회사 엘지화학 | 리튬 이차전지용 음극활물질 및 그 제조방법 |
CN105895950A (zh) * | 2016-01-22 | 2016-08-24 | 西北工业大学 | 全锰系锂离子电池及其制备方法 |
CN105702923B (zh) * | 2016-01-29 | 2018-08-10 | 中国科学院宁波材料技术与工程研究所 | 一种氧化锰/碳/碳纳米管纳米杂化材料及其制备方法和应用 |
CN108236959A (zh) * | 2016-12-26 | 2018-07-03 | 天津喜蕊科技有限公司 | 一种暖气片底部的镍金甲醛消除涂层的制备方法 |
US10615412B2 (en) * | 2018-01-30 | 2020-04-07 | Octopus Technologies Inc. | Manganese oxide composition and method for preparing manganese oxide composition |
KR102417774B1 (ko) | 2018-04-20 | 2022-07-05 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 및 이를 포함하는 리튬 이차 전지 |
KR102417773B1 (ko) * | 2018-04-27 | 2022-07-05 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 및 이를 포함하는 리튬 이차 전지 |
US11443902B2 (en) | 2018-10-04 | 2022-09-13 | Pacesetter, Inc. | Hybrid anode and electrolytic capacitor |
KR102245764B1 (ko) * | 2019-09-20 | 2021-04-28 | 포항공과대학교 산학협력단 | 다공성 산화망간 나노입자 및 이의 제조방법 |
KR102393189B1 (ko) * | 2020-02-27 | 2022-05-02 | 코칩 주식회사 | 리튬이 배제된 메조 다공성 금속 산화물을 적용한 의사 커패시터 및 그 제조 방법 |
KR20220168220A (ko) | 2021-06-15 | 2022-12-23 | 성균관대학교산학협력단 | 나노 구조 음극 활물질, 이의 제조방법 및 이를 이용한 리튬 이차전지 |
KR20220168634A (ko) | 2021-06-16 | 2022-12-26 | 성균관대학교산학협력단 | 삼상 구조 음극 활물질, 이의 제조방법 및 이를 이용한 리튬 이차전지 |
CN114614013B (zh) * | 2022-03-21 | 2023-12-22 | 柳州鹏辉能源科技有限公司 | 锂离子电池复合添加剂、正极浆料及其制备方法、正极极片和用电设备 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000100430A (ja) * | 1998-09-18 | 2000-04-07 | Canon Inc | 多孔質構造の金属酸化物、電極構造体、二次電池及びこれらの製造方法 |
JP2004534357A (ja) * | 2001-06-08 | 2004-11-11 | エヴァレディー バッテリー カンパニー インコーポレイテッド | 最適化されたアルカリ電気化学電池 |
WO2009106837A1 (en) * | 2008-02-29 | 2009-09-03 | Nanotecture Ltd | Mesoporous particulate materials |
JP2009289728A (ja) * | 2007-12-28 | 2009-12-10 | Panasonic Corp | アルカリ電池 |
JP2010114086A (ja) * | 2008-11-10 | 2010-05-20 | Samsung Electronics Co Ltd | アノード活物質、これを含むアノード、これを採用したリチウム電池及びその製造方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3635694A (en) * | 1969-07-07 | 1972-01-18 | Bethlehem Steel Corp | Method of manufacturing manganese oxide pellets |
KR970004614B1 (ko) * | 1993-12-03 | 1997-03-29 | 엘지전자 주식회사 | 자기헤드용 비자성 세라믹기판재료 |
JPH07288140A (ja) * | 1994-04-15 | 1995-10-31 | Nippon Telegr & Teleph Corp <Ntt> | リチウム二次電池 |
US5604057A (en) | 1995-11-27 | 1997-02-18 | General Motors Corporation | Secondary cell having a lithium intercolating manganese oxide |
US20030211394A1 (en) * | 2001-05-11 | 2003-11-13 | Nghia Tang | Zinc-based electrode for alkaline electrochemical cell |
GB2376342A (en) * | 2001-06-08 | 2002-12-11 | Ever Ready Ltd | Optimised alkaline electrochemical cells |
CN1328805C (zh) * | 2004-04-05 | 2007-07-25 | 中国科学院物理研究所 | 用于二次锂电池的负极活性材料和用途 |
KR100760530B1 (ko) | 2005-10-27 | 2007-10-04 | 한국기초과학지원연구원 | 음극산화알루미늄 템플릿을 이용한 산화망간 나노튜브 또는나노막대의 제조방법 |
JP2009164023A (ja) | 2008-01-09 | 2009-07-23 | Univ Of Tokyo | リチウムイオン二次電池用活物質、その製造方法及び前記活物質を使用したリチウムイオン二次電池 |
US8435676B2 (en) | 2008-01-09 | 2013-05-07 | Nanotek Instruments, Inc. | Mixed nano-filament electrode materials for lithium ion batteries |
GB2457951A (en) | 2008-02-29 | 2009-09-02 | Nanotecture Ltd | Mesoporous materials for electrodes |
US9105925B2 (en) * | 2008-11-10 | 2015-08-11 | Samsung Electronics Co., Ltd. | Anode active material comprising a porous transition metal oxide, anode comprising the anode active material, lithium battery comprising the anode, and method of preparing the anode active material |
WO2011019988A2 (en) * | 2009-08-14 | 2011-02-17 | The Regents Of The University Of Michigan | DIRECT THERMAL SPRAY SYNTHESIS OF Li ION BATTERY COMPONENTS |
-
2011
- 2011-06-30 KR KR1020110065135A patent/KR101840818B1/ko active IP Right Grant
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2012
- 2012-05-09 CN CN201210142632.2A patent/CN102856541B/zh active Active
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- 2012-06-26 JP JP2012142806A patent/JP6116144B2/ja active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000100430A (ja) * | 1998-09-18 | 2000-04-07 | Canon Inc | 多孔質構造の金属酸化物、電極構造体、二次電池及びこれらの製造方法 |
JP2004534357A (ja) * | 2001-06-08 | 2004-11-11 | エヴァレディー バッテリー カンパニー インコーポレイテッド | 最適化されたアルカリ電気化学電池 |
JP2009289728A (ja) * | 2007-12-28 | 2009-12-10 | Panasonic Corp | アルカリ電池 |
WO2009106837A1 (en) * | 2008-02-29 | 2009-09-03 | Nanotecture Ltd | Mesoporous particulate materials |
JP2010114086A (ja) * | 2008-11-10 | 2010-05-20 | Samsung Electronics Co Ltd | アノード活物質、これを含むアノード、これを採用したリチウム電池及びその製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017135095A (ja) * | 2015-11-02 | 2017-08-03 | アイメック・ヴェーゼットウェーImec Vzw | リチウムマンガン酸化物層を形成するための方法 |
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