JP4481007B2 - アルカリ電池 - Google Patents
アルカリ電池 Download PDFInfo
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- JP4481007B2 JP4481007B2 JP2003546417A JP2003546417A JP4481007B2 JP 4481007 B2 JP4481007 B2 JP 4481007B2 JP 2003546417 A JP2003546417 A JP 2003546417A JP 2003546417 A JP2003546417 A JP 2003546417A JP 4481007 B2 JP4481007 B2 JP 4481007B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
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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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/023—Gel electrode
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Description
1.蒸留水または脱イオン水中で前駆体スピネル粉末を攪拌してそのスラリーを形成し、約10℃から50℃、好ましくは約15℃から30℃に調整する工程と;
2.このスラリーに、たとえば硫酸、硝酸、塩酸、過塩素酸、トルエンスルホン酸、あるいはトリフルオロメチルスルホン酸のような酸の水溶液を添加して、スラリーのpHが典型的には約2より低く、約1より低く、あるいは約0.7より低く、ただし約0.5より高い値に安定し、pHがこの値で少なくとも0.75時間保持するまで、スラリー温度を一定に維持するように、ある速度で一定に攪拌する工程(任意選択的に攪拌をさらに24時間まで続けることもできる)と;
3.こうしてできた固体生成物を、たとえば吸引ろ過、圧力ろ過、あるいは遠心分離などで上澄み液から分離させ、洗浄液が中性pH(例、約6から7)になるまで、一定量の蒸留水または脱イオン水にて洗浄する工程と;
4.固体生成物を、4から24時間、30℃から120℃、あるいは50℃から90℃、または60℃から70℃で、真空乾燥する工程とを含むことができる。
式1
2LiMn+3Mn + O4 + 4H+ → 3λ-Mn+4O2 + Mn+2 + 2Li+ + 2H2O
式2
Li1+xMn2-xO4 → Li3x[Mn4+ 1.5+0.5xLix]O3+3x → H3x[Mn4+ 1.5+0.5xLix]O3+3x
ただし0.02<x<0.33
乾燥λ-MnO2粉末のサンプルを次のようにして調製した。
EMD(Kerr-McGeeのTronaD)粉末を、天然黒鉛(Nacionale de GrafiteのMP-0702X)と、38%KOH電解液とに、60:35:5の重量比で、乳鉢と乳棒とを用いて手作業で配合した。こうしてできた約0.5gのカソード混合材料を、635型アルカリボタン電池のカソード缶底部のカソードディスク内に、圧縮加工した。そして、実施例1と同様にして、ボタン電池組み立てを行った。組み立てたばかりの電池の開回路電圧が測定され表2に示されている。この電池は、比較例C1a、C1b、およびC1cにおいて、3mA、6mA、および30mAの定電流放電が行われ、これらは放電レートC/30、C/15、およびC/3に相当する。このような電池のそれぞれの上記定電流放電で得られる、終止電圧1Vおよび0.8Vまでの重量比放電容量もまた、表2に示されている。このボタン電池の、C/30レートおよびC/15レートの放電で得られる、終止電圧0.8Vまでの重量比放電容量は、282mAh/gおよび266mAh/gであった。さらにC/3レートの放電の場合、このボタン電池で得られる、0.8Vの終止電圧までの重量比放電容量は、215mAh/gとかなり低かった。
乾燥λ-MnO2粉末のサンプルを、実施例1と同様に、ただしスピネルBの代わりにスピネルA(Kerr-McGee Grade LMO-210)から調製した。このλ-MnO2粉末を、天然黒鉛(Nacionale de GrafiteのMP-0702X)と、38%KOH電解液とに、60:35:5の重量比で、乳鉢と乳棒とを用いて手動で、もしくは高速実験用のミキサーミル(例、Waringミキサー)を用いて機械的に、配合した。
実施例1と同様にして、乾燥λ-MnO2粉末のサンプルを調製した。このλ-MnO2粉末を、天然黒鉛(Nacionale de GrafiteのMP-0702X)と、38%KOH電解液とに、87:8:5の重量比で、高速実験用のミキサーミル(例、Waringミキサー)を用いて配合した。
実施例1と同様にして、乾燥λ-MnO2粉末のサンプルを調製した。このλ-MnO2粉末を、天然黒鉛(Nacionale de GrafiteのMP-0702X)と膨張黒鉛(TimcalのEBNB-90)とを1:1の重量比で含有する混和剤と、38%KOH電解液とに、すべての成分がそれぞれ87:4:4:5の重量比で、高速実験用のミキサーミル(例、Waringミキサー)を用いて配合した。
EMD(Kerr-McGeeのTronaD)粉末を、天然黒鉛(Nacionale de GrafiteのMP-0702X)と膨張黒鉛(TimcalのEBNB-90)とを1:1の重量比で含有する混和剤と、38%KOH電解液とに、すべての成分がそれぞれ87:4:4:5の重量比で、高速実験用のミキサーミル(例、Waringミキサー)を用いて配合した。
Claims (11)
- マンガン酸リチウムスピネルB前駆体から調製されたラムダ-二酸化マンガンを含有するカソード活物質を含むカソードと;
亜鉛を含むアノードと;
アノードとカソードとの間のセパレーターと;
アノードとカソードとに接触するアルカリ電解液とを備えるアルカリ電池であって:
前記カソード活物質が、20mA/gのカソード活物質比電流値の放電レートで、0.8Vの終止電圧まで、290mAh/gより大きな特定放電容量を有し、
前記ラムダ-二酸化マンガンが8m 2 /gより大きいB.E.T.比表面積を有する
ことを特徴とするアルカリ電池。 - 前記カソード活物質が、20mA/gのカソード活物質比電流値の放電レートで、0.8Vの終止電圧まで、300mAh/gより大きな特定放電容量を有することを特徴とする請求項1記載の電池。
- 前記カソード活物質が、20mA/gのカソード活物質比電流値の放電レートで、0.8Vの終止電圧まで、310mAh/gより大きな特定放電容量を有することを特徴とする請求項1乃至2のいずれか一項に記載の電池。
- ラムダ-二酸化マンガンがグラムあたり0.05から0.15立方センチメートルの全細孔容積を有することを特徴とする請求項1乃至3のいずれか一項に記載の電池。
- ラムダ-二酸化マンガンを含有するカソード活物質を含む正極を提供する工程と;
この正極と亜鉛極とを備える電池を形成する工程とを含むアルカリ電池の製造法であって:
前記ラムダ-二酸化マンガンは、
化学式、Li1+xMn2-xO4、ただしxは−0.02から+0.02を有するとともに1から10m 2 /gのB.E.T.比表面積を有するスピネルBの化合物と水とを接触させる工程と;
この水と化合物とに、水が1またはそれより小さいpHを有するまで、酸を添加する工程と;
この水と酸とから固体を分離させる工程と;
この固体を120℃またはそれより低い温度で乾燥させて、ラムダ-二酸化マンガンを得る工程とによって調整される
ことを特徴とする製造方法。 - 前記固体が約100℃より低い温度で乾燥される
ことを特徴とする請求項5記載の方法。 - 前記固体が50℃から70℃の温度で乾燥される
ことを特徴とする請求項6記載の方法。 - 前記xが−0.005から+0.005である
ことを特徴とする請求項5乃至7のいずれか一項に記載の方法。 - 化合物と水とを接触させる前記工程が、スラリー形成を含む
ことを特徴とする請求項5乃至8のいずれか一項に記載の方法。 - 前記スラリーが50℃より低い温度で維持されることを特徴とする請求項9記載の方法。
- 酸濃度が1から8モル濃度であることを特徴とする請求項5乃至10のいずれか一項に記載の方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/988,297 US6783893B2 (en) | 2001-11-19 | 2001-11-19 | Alkaline battery |
PCT/US2002/036938 WO2003044879A2 (en) | 2001-11-19 | 2002-11-15 | Zinc-alkaline battery containing lambda-mn02 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005510037A JP2005510037A (ja) | 2005-04-14 |
JP4481007B2 true JP4481007B2 (ja) | 2010-06-16 |
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Application Number | Title | Priority Date | Filing Date |
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JP2003546417A Expired - Lifetime JP4481007B2 (ja) | 2001-11-19 | 2002-11-15 | アルカリ電池 |
Country Status (10)
Country | Link |
---|---|
US (2) | US6783893B2 (ja) |
EP (1) | EP1446848B1 (ja) |
JP (1) | JP4481007B2 (ja) |
CN (1) | CN1331255C (ja) |
AR (1) | AR037382A1 (ja) |
AT (1) | ATE340415T1 (ja) |
AU (1) | AU2002366160A1 (ja) |
BR (1) | BR0214052B1 (ja) |
DE (1) | DE60214880T2 (ja) |
WO (1) | WO2003044879A2 (ja) |
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US7045252B2 (en) * | 2002-08-08 | 2006-05-16 | The Gillette Company | Alkaline battery including lambda-manganese dioxide |
TW200520292A (en) | 2003-08-08 | 2005-06-16 | Rovcal Inc | High capacity alkaline cell |
AR047875A1 (es) | 2004-06-04 | 2006-03-01 | Rovcal Inc | Celdas alcalinas que presentan alta capacidad |
US20060046135A1 (en) * | 2004-08-27 | 2006-03-02 | Weiwei Huang | Alkaline battery with MnO2/NiOOH active material |
US8231988B2 (en) * | 2005-02-09 | 2012-07-31 | University Of Iowa Research Foundation | Batteries and battery components with magnetically modified manganese dioxide |
US7771873B2 (en) * | 2005-07-12 | 2010-08-10 | Panasonic Corporation | Alkaline battery |
US20070218339A1 (en) * | 2006-03-14 | 2007-09-20 | More Energy Ltd. | Leak-proof liquid fuel cell |
JP5235060B2 (ja) * | 2007-08-10 | 2013-07-10 | 日立マクセル株式会社 | アルカリ電池用正極およびアルカリ電池 |
JP5431452B2 (ja) * | 2008-04-07 | 2014-03-05 | カーネギー メロン ユニバーシティ | ナトリウムイオンを用いた水性電解質系電気化学的二次エネルギー貯蔵装置 |
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US8303840B2 (en) * | 2010-03-12 | 2012-11-06 | The Gillette Company | Acid-treated manganese dioxide and methods of making thereof |
US20110223477A1 (en) * | 2010-03-12 | 2011-09-15 | Nelson Jennifer A | Alkaline battery including lambda-manganese dioxide and method of making thereof |
US8298706B2 (en) | 2010-03-12 | 2012-10-30 | The Gillette Company | Primary alkaline battery |
US8652672B2 (en) | 2012-03-15 | 2014-02-18 | Aquion Energy, Inc. | Large format electrochemical energy storage device housing and module |
US9028564B2 (en) | 2012-03-21 | 2015-05-12 | The Gillette Company | Methods of making metal-doped nickel oxide active materials |
US8703336B2 (en) | 2012-03-21 | 2014-04-22 | The Gillette Company | Metal-doped nickel oxide active materials |
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CN102867961A (zh) * | 2012-09-14 | 2013-01-09 | 黄宣斐 | 一次性碱性电池的电极材料 |
CN102856529A (zh) * | 2012-09-14 | 2013-01-02 | 黄宣斐 | 一次性碱性电池的电极材料 |
CN103401030B (zh) * | 2013-07-09 | 2016-05-04 | 哈尔滨工程大学 | 一种水系可充镁或锌离子电容电池 |
US9793542B2 (en) | 2014-03-28 | 2017-10-17 | Duracell U.S. Operations, Inc. | Beta-delithiated layered nickel oxide electrochemically active cathode material and a battery including said material |
US10804536B2 (en) | 2017-02-13 | 2020-10-13 | Energizer Brands, Llc | Substituted lambda manganese dioxides in an alkaline electrochemical cell |
WO2018208860A1 (en) | 2017-05-09 | 2018-11-15 | Duracell U.S. Operations, Inc. | Battery including beta-delithiated layered nickel oxide electrochemically active cathode meterial |
US10547059B2 (en) | 2018-02-21 | 2020-01-28 | Duracell U.S. Operations, Inc. | Sulfate and sulfonate based surfactants for alkaline battery anode |
CN112889167A (zh) * | 2018-06-14 | 2021-06-01 | 纽约城市大学研究基金会 | 高电压离子介导的液流/液流辅助二氧化锰-锌电池 |
EP4093703A1 (en) | 2020-01-23 | 2022-11-30 | Duracell U.S. Operations, Inc. | Oxidative delithiation of alkali nickel oxide |
CN114388831B (zh) * | 2021-11-30 | 2024-03-01 | 福建南平南孚电池有限公司 | 一种碱性锌锰电池 |
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2001
- 2001-11-19 US US09/988,297 patent/US6783893B2/en not_active Expired - Lifetime
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- 2002-11-14 AR ARP020104376A patent/AR037382A1/es unknown
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- 2002-11-15 EP EP02803652A patent/EP1446848B1/en not_active Expired - Lifetime
- 2002-11-15 AT AT02803652T patent/ATE340415T1/de not_active IP Right Cessation
- 2002-11-15 WO PCT/US2002/036938 patent/WO2003044879A2/en active IP Right Grant
- 2002-11-15 JP JP2003546417A patent/JP4481007B2/ja not_active Expired - Lifetime
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Also Published As
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WO2003044879A2 (en) | 2003-05-30 |
BR0214052A (pt) | 2004-10-13 |
WO2003044879A3 (en) | 2003-07-10 |
DE60214880T2 (de) | 2007-05-24 |
CN1331255C (zh) | 2007-08-08 |
US6932846B2 (en) | 2005-08-23 |
AU2002366160A1 (en) | 2003-06-10 |
DE60214880D1 (de) | 2006-11-02 |
EP1446848A2 (en) | 2004-08-18 |
US20040175616A1 (en) | 2004-09-09 |
ATE340415T1 (de) | 2006-10-15 |
US6783893B2 (en) | 2004-08-31 |
EP1446848B1 (en) | 2006-09-20 |
AR037382A1 (es) | 2004-11-03 |
AU2002366160A8 (en) | 2003-06-10 |
US20030099881A1 (en) | 2003-05-29 |
CN1618138A (zh) | 2005-05-18 |
BR0214052B1 (pt) | 2011-05-31 |
JP2005510037A (ja) | 2005-04-14 |
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