JP4518791B2 - 常温作動可能な再充電バッテリセル - Google Patents
常温作動可能な再充電バッテリセル Download PDFInfo
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- JP4518791B2 JP4518791B2 JP2003506031A JP2003506031A JP4518791B2 JP 4518791 B2 JP4518791 B2 JP 4518791B2 JP 2003506031 A JP2003506031 A JP 2003506031A JP 2003506031 A JP2003506031 A JP 2003506031A JP 4518791 B2 JP4518791 B2 JP 4518791B2
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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- H—ELECTRICITY
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- 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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- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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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
- Y10T29/10—Battery-grid making
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Description
−活性材料の部分の、電極放電エレメントの一方に対する電気的または電気化学的接続が失われるのかもしれない。
−電極放電エレメントと活性材料との間の物理的接続状態が失われ、活性材料が放電エレメントから剥離落下するのかもしれない。
−粒子から成る多孔性材料は、それら粒子間に必要な電気接触を提供する粒子間のブリッジを有する。そのようなバッテリを使用する時、これらのブリッジ間の電気抵抗を増大させるような変化が生じて、最終的に、電気接続が完全に遮断されるのかもしれない。
−最後に、セルに二次的反応(特に、自己放電または過剰充電反応)が発生し、それによって、活性材料の不可逆的破壊、そして、最終的に、容量の低下および/または、電気抵抗の増大が起こるのかもしれない。
米国特許4,892,796号に記載の方法では、クロム箔はニッケルベースに対する不連続な層として付加され、したがって明白な相境界を形成する。これと対照的に、本発明に拠れば、クロムと他の金属、特にニッケルとの合金が表面層中に形成される製造方法が使用される。これは、好ましくは、クロム原子を放電エレメントの表面から内部に向けて拡散させることによって達成される。これによって、クロム拡散層が形成され、このクロム拡散層内ではクロムの濃度は表面から離間する方向に減少する。
図1は、未処理ニッケルの放電エレメントを使用した場合のサイクリックボルタモグラムを示し、
図2は、ロジウムを含有する表面層を備えた放電エレメントを使用した場合のサイクリックボルタモグラムを示し、
図3は、クロム拡散層を備える放電エレメントを使用した場合のサイクリックボルタモグラムを示し、
図4は、タングステンの放電エレメントを使用した場合のサイクリックボルタモグラムを示し、
図5は、従来技術に基づくセルの場合における、充電/放電サイクルの回数の関数としての、放電容量と内部抵抗との変化を示し、
図6は、本発明に基づくセルの場合における、充電/放電サイクルの回数の関数としての、放電容量と内部抵抗との変化を示し、
図7は、クロム電気メッキを備えた放電エレメントの表面の断面のEDX線スキャンを示し、
図8は、クロム拡散層を備える放電エレメントの表面の断面のEDX線スキャンを示す。
Claims (11)
- 常温で作動する再充電式のバッテリセルであって、
SO2をベースとした電解質系と、
陰電極と陽電極とを有し、
前記電極の一方が、不要な反応から放電エレメントを保護するための反応保護材を表面層に含む導電性の放電エレメントを有するものにおいて、
前記導電性放電エレメントの前記表面層が反応保護材として、
−クロムと他の金属との合金、および/または、
−ロジウム、タングステン、レニウム、プラチナ、イリジウムおよびオスミウムから成るグループから選択される保護金属の単体または同単体どうしの合金または化合物、および/または、
−ニッケルの炭化物、窒化物或いはリン化物、を含み、
これにより、4ボルトを超えるセル電圧での駆動が可能であることを特徴とするバッテリセル。 - 前記表面層は、反応保護層として、クロム濃度が表面から離間する方向で減少するクロム拡散層としてのクロムと他の金属との合金を含むことを特徴とする請求項1に記載のバッテリセル。
- 前記表面層は、前記クロム拡散層をカバーするクロム層を含むことを特徴とする請求項2に記載のバッテリセル。
- 前記表面層はクロムの酸化物を含むことを特徴とする請求項1〜3のいずれか一項に記載のバッテリセル。
- 前記表面層の少なくとも1つの成分は、気相からのデポジションによって付加されることを特徴とする請求項1〜4のいずれか一項に記載のバッテリセル。
- 前記表面層の少なくとも1つの成分はエレクトロデポジションによって付加されることを特徴とする請求項1〜5のいずれか一項に記載のバッテリセル。
- 前記放電エレメントは複合体電極の一構成要素であり、その複合電極の中で前記放電エレメントは、それに対して永久的に結合された活性材料のための基材として働くことを特徴とする請求項1〜6のいずれか一項に記載のバッテリセル。
- 前記電解質系はハロゲン化物イオンを含むことを特徴とする請求項1〜7のいずれか一項に記載のバッテリセル。
- 請求項1〜8のいずれか一項に記載のバッテリセルを製造する方法であって、少なくともその表面に、クロム、ロジウム、タングステン、レニウム、プラチナ、イリジウムおよびオスミウムから成るグループから選択される金属を含有する平坦な放電エレメント材を焼き戻しする工程を有することを特徴とする方法。
- 前記焼き戻しの温度と持続時間は、前記金属の原子が前記放電エレメントの表面から隣接材料内に拡散し、これによって、前記金属の濃度が表面から離間する方向で減少するような拡散層が形成されるべく選択されることを特徴とする請求項9に記載の方法。
- 前記焼き戻し工程は不活性または還元性のガス雰囲気中で行われることを特徴とする請求項9または10に記載の方法。
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DE10128970A DE10128970A1 (de) | 2001-06-15 | 2001-06-15 | Bei Normaltemperatur betreibbare, wiederaufladbare Batteriezelle |
PCT/DE2002/002112 WO2002103827A2 (de) | 2001-06-15 | 2002-06-10 | Bei normaltemperatur betreibbare, wiederaufladbare batteriezelle |
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JP2004536427A JP2004536427A (ja) | 2004-12-02 |
JP2004536427A5 JP2004536427A5 (ja) | 2006-01-05 |
JP4518791B2 true JP4518791B2 (ja) | 2010-08-04 |
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US (1) | US7244530B2 (ja) |
EP (1) | EP1415359A2 (ja) |
JP (1) | JP4518791B2 (ja) |
AU (1) | AU2002316775A1 (ja) |
DE (2) | DE10128970A1 (ja) |
WO (1) | WO2002103827A2 (ja) |
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DE4241276A1 (de) * | 1992-12-08 | 1994-06-09 | Hambitzer Guenther Dr Rer Nat | Verfahren zum Herstellen einer Elektrode für elektrochemische Zellen, Elektrode und wiederaufladbares Element auf Basis einer solchen Elektrode |
US5928483A (en) * | 1997-11-12 | 1999-07-27 | The United States Of America As Represented By The Secretary Of The Navy | Electrochemical cell having a beryllium compound coated electrode |
ES2233416T3 (es) * | 1999-06-18 | 2005-06-16 | Hambitzer, Gunther, Dr. | Celdas electroquimicas recargables. |
DE10110716A1 (de) | 2001-03-07 | 2002-09-12 | Fortu Bat Batterien Gmbh | Wiederaufladbare nichtwässrige Batteriezelle |
-
2001
- 2001-06-15 DE DE10128970A patent/DE10128970A1/de not_active Withdrawn
-
2002
- 2002-06-10 EP EP02745133A patent/EP1415359A2/de not_active Withdrawn
- 2002-06-10 JP JP2003506031A patent/JP4518791B2/ja not_active Expired - Fee Related
- 2002-06-10 DE DE10292678T patent/DE10292678D2/de not_active Withdrawn - After Issue
- 2002-06-10 AU AU2002316775A patent/AU2002316775A1/en not_active Abandoned
- 2002-06-10 US US10/480,489 patent/US7244530B2/en not_active Expired - Fee Related
- 2002-06-10 WO PCT/DE2002/002112 patent/WO2002103827A2/de active Application Filing
Also Published As
Publication number | Publication date |
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US7244530B2 (en) | 2007-07-17 |
WO2002103827A3 (de) | 2004-02-19 |
WO2002103827A2 (de) | 2002-12-27 |
EP1415359A2 (de) | 2004-05-06 |
DE10128970A1 (de) | 2002-12-19 |
JP2004536427A (ja) | 2004-12-02 |
DE10292678D2 (de) | 2004-04-29 |
AU2002316775A1 (en) | 2003-01-02 |
US20040157129A1 (en) | 2004-08-12 |
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