JP2010509719A - 再充電可能な電気化学電池 - Google Patents
再充電可能な電気化学電池 Download PDFInfo
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Abstract
Description
− 電池充電中の電気的エネルギーから化学的エネルギーへの変換と放電時の化学的エネルギーから電気的エネルギーへの逆変換との両方が、両方の電極におけるそれぞれの電極の活性物質と電子伝導性の集電子(基板)との間で生じる電極反応(酸化還元反応)に基づいている。電極反応に由来する電流は、外部電気回路を流れるように作られている。電池内部の負極の活性金属と正極の活性物質とが電子伝導的に接触すると短絡が形成され、電池内の電極間で電子の直接的な移転が起こる。この種の短絡が起きた結果、荷電が損失し、すなわち充電中の効率が低下し、貯蔵された電気的エネルギーが自己放電により失われる。
− 短絡によって強電流が生じ、これにより過度の発熱が生じる。その結果「熱散逸」とそれに関連した安全性の問題が起こりうる。
a)電池の初期充電の前:
− SO2のみが溶媒である電解液の場合:導電性塩1モルあたりSO2が少なくとも0.5モル。
− 追加成分としてSO2を含む混合電解液の場合:導電性塩1モルあたりSO2が少なくとも0.1モル、好ましくは少なくとも0.5モル、特に好ましくは少なくとも1.0モル。
b)孔内セパレータ層形成後の電池の定常作動中:導電性塩1モルあたりSO2が少なくとも0.1モル。
− 多孔質正極層の内部表面(好ましくはさらに外部表面)に十分に薄い層の形状で適用することが可能でなければならない。
− 材料は化学的に安定でなければならない。すなわち電池に存在するその他の成分に対して、また電界中で、不活性でなければならない。
− 多孔質正極層の形成に用いる前に、構造形成粒子をコーティングする。
− ガス流を用いるコーティング法(例えば、物理的気相成長法、化学的気相成長法、プラズマまたは高電流放電)。層に液体を通すことを含む方法も好適である。
− 原子が多孔質正極層に浸透してその内部表面を被覆する、気相からコーティングを行う方法、特にスパッタリング。
− 電子絶縁かつリチウムイオン透過性の層による、負極基板のコーティング;
− 電子絶縁かつリチウムイオン透過性の層による、多孔質正極層の外部表面のコーティング;および
− 後の活性金属(特にリチウム)の浸透に干渉しない、非常に薄くて多孔質の電子絶縁層材料、例えばガラス繊維布の導入。
− 電極層の成分、すなわち94%コバルト酸リチウム、4%結合剤(PTFE)、および2%カーボンブラックを乾燥状態で混合した。
− 混合物はイソプロパノールに吸収され、溶媒容量が約20〜30重量%のペーストとなった。
− ペーストを攪拌して均質化し、ニッケル発泡体製の集電子に貼り付けた。
− 次いで、孔隙率35%となるまで乾燥工程と加圧工程を行い、370℃で1時間加熱して熱処理を行った。
Claims (30)
- 負極(5)と、電解液と、正極(4)と、電池の充電中に前記負極(5)において起こる電極反応に由来する活性金属(24)の貯蔵部とを備えた再充電可能な電気化学電池であって、
前記電池は、前記正極の活性物質(17)を含む多孔質構造(13)にして、前記負極における前記電極反応に由来する前記活性金属(24)の少なくとも一部が、前記正極(4)の活性物質(17)を含む前記多孔質構造(13)の細孔(14)内に浸透して内部に貯蔵されるように、前記負極(5)の電子伝導性基板(12)近傍に配置される多孔質構造(13)を備え、
前記活性金属(24)は、少なくとも一部が、前記正極の活性物質(17)を含む前記多孔質構造(13)の細孔(14)内に金属状で沈着して貯蔵されることを特徴とする電池。 - 前記多孔質構造(13)における前記正極(4)の活性物質(17)の重量割合が、少なくとも50%、好ましくは少なくとも80%である請求項1に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)の孔隙率が、20〜80%、好ましくは25〜75%、特に好ましくは25〜50%である請求項1または2に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)の細孔(14)の平均径が、500μm以下、好ましくは100μm以下、より好ましくは10μm以下である請求項1〜3のいずれか1項に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)は、互いに結合した固形粒子(16)を含む請求項1〜4のいずれか1項に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)の前記固形粒子(16)は、結合剤(19)によって互いに結合しており、前記結合剤(19)の体積分率は、前記多孔質構造(13)の全実体積の50%以下、好ましくは30%以下、より好ましくは20%以下、最も好ましくは10%以下である請求項5に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)は、その構造形成材料中に、電子伝導性の伝導性向上材料(18)、好ましくは炭素または金属由来の粒子材料を含む請求項1〜6のいずれか1項に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)が層状に形成され、層状に形成された前記正極の電子伝導性基板(12)に連結されている請求項1〜7のいずれか1項に記載の電池。
- 前記正極の基板が、開放細孔層として、特に金属発泡体層として提供され、前記正極の活性物質を含む前記多孔質構造の前記構造形成材料は、少なくとも一部が、前記開放細孔基板に浸透する請求項8に記載の電池。
- 前記電池の作動状態において、前記正極の活性物質(17)を含む前記多孔質構造(13)の内部表面が、孔内セパレータ層(25)で被覆された請求項1〜9のいずれか1項に記載の電池。
- 前記孔内セパレータ層(25)の少なくとも一部は、その場で形成される請求項10に記載の電池。
- 前記孔内セパレータ層(25)は、前記電解液の成分を反応物の1つとして用いる反応によって形成される請求項11に記載の電池。
- 前記孔内セパレータ層(25)の少なくとも一部は、前記電池セル(3)の初期充電前に前記正極の活性物質を含む前記多孔質構造(13)の前記内部表面をコーティングすることによって形成される請求項10〜12のいずれか1項に記載の電池。
- 前記孔内セパレータ層(25)は、イオン伝導性ガラス、イオン伝導性セラミック材料またはイオン伝導性プラスチック材料から形成される請求項13に記載の電池。
- 前記負極(5)の前記活性金属(24)は、アルカリ金属、アルカリ土類金属、周期系の第2亜族の金属からなる群より選択される請求項1〜14のいずれか1項に記載の電池。
- 前記負極(5)の前記活性金属(24)は、リチウム、ナトリウム、カルシウム、亜鉛またはアルミニウムである請求項15に記載の電池。
- 前記負極(5)の前記基板(12)の少なくとも一部は、前記負極の活性金属を貯蔵するのに好適な材料から形成される請求項1〜16のいずれか1項に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)の細孔(14)は、前記負極の活性金属を貯蔵するのに好適な材料(23)を含有する請求項1〜17のいずれか1項に記載の電池。
- 前記活性金属を貯蔵するのに好適な材料は、グラファイト、層間化合物、前記負極の活性金属と合金を形成するのに好適な金属からなる群より選ばれる請求項17又は18に記載の電池。
- 前記正極の活性物質(17)を含む前記多孔質構造(13)は、前記負極(5)の基板との間に空洞を形成しないように前記基板に密に接触して配置され、多孔質構造(13)の内部で、前記電池充電中の前記負極における前記電極反応に由来する活性金属(24)が、金属状で蓄積することが可能である請求項1〜19のいずれか1項に記載の電池。
- 前記負極(5)の基板と前記正極の活性物質を含む多孔質構造との境界に、電子伝導を防ぎかつ前記電池充電中の前記負極における前記電極反応に由来する前記活性金属の流れを可能とする装置を含む請求項1〜20のいずれか1項に記載の電池。
- 前記正極(4)の前記活性物質(17)は、金属化合物、好ましくは金属酸化物を含む請求項1〜21のいずれか1項に記載の電池。
- 前記正極(4)の前記活性物質(17)は、遷移金属M、特に原子番号22〜28の元素の、金属酸化物を含む請求項22に記載の電池。
- 前記正極(4)の前記活性物質(17)は、層間化合物を含む請求項1〜23のいずれか1項に記載の電池。
- 前記電解液(21)は、二酸化硫黄を含む請求項1〜24のいずれか1項に記載の電池。
- 前記電池セル(3)における前記電解液(21)の体積が、前記正極の活性物質(17)を含む多孔質構造(13)の自由細孔容積の2倍以下、好ましくは前記自由細孔容積以下に相当する請求項1〜25のいずれか1項に記載の電池。
- 前記電解液は、アルカリ金属、特にリチウムの、ハロゲン化物、シュウ酸塩、ホウ酸塩、リン酸塩、ヒ酸塩および没食子酸塩からなる群より選択される導電性塩を含む請求項1〜26のいずれか1項に記載の電池。
- 前記電解液は、前記導電性塩に加えて、更なる塩、特にハロゲン化アルカリ、好ましくはフッ化アルカリおよび特に好ましくはフッ化リチウムを含む請求項1〜27のいずれか1項に記載の電池。
- 前記電池の前記エネルギー密度は、750Wh/lを超える、好ましくは1000Wh/lを超える、より好ましくは1250Wh/lを超える、さらにより好ましくは1500Wh/lを超える請求項1〜28のいずれか1項に記載の電池。
- ベルトロー−ロス製品(BRP)が前記電池の実際の爆発性の実質的に正確な測定値となるように、前記電池の前記成分が巨視的に均一に分散している請求項1〜29のいずれか1項に記載の電池。
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EP06023611A EP1923934A1 (de) | 2006-11-14 | 2006-11-14 | Wiederaufladbare elektrochemische Batteriezelle |
PCT/EP2007/009744 WO2008058685A1 (de) | 2006-11-14 | 2007-11-10 | Wiederaufladbare elektrochemische batteriezelle |
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JP2014527695A (ja) * | 2011-08-12 | 2014-10-16 | アレヴォ・リサーチ・アー・ゲーAlevo Research Ag | 再充電可能電気化学セル及びその製造方法 |
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JP2012531010A (ja) * | 2009-06-30 | 2012-12-06 | エルジー・ケム・リミテッド | 多孔性コーティング層を備える電極の製造方法、その方法によって形成された電極、及びそれを備える電気化学素子 |
JP2012099225A (ja) * | 2010-10-29 | 2012-05-24 | Ohara Inc | 全固体リチウムイオン二次電池およびその製造方法 |
JP2014527695A (ja) * | 2011-08-12 | 2014-10-16 | アレヴォ・リサーチ・アー・ゲーAlevo Research Ag | 再充電可能電気化学セル及びその製造方法 |
US11145857B2 (en) | 2012-04-11 | 2021-10-12 | Ionic Materials, Inc. | High capacity polymer cathode and high energy density rechargeable cell comprising the cathode |
US11319411B2 (en) | 2012-04-11 | 2022-05-03 | Ionic Materials, Inc. | Solid ionically conducting polymer material |
US11251455B2 (en) | 2012-04-11 | 2022-02-15 | Ionic Materials, Inc. | Solid ionically conducting polymer material |
US11611104B2 (en) | 2012-04-11 | 2023-03-21 | Ionic Materials, Inc. | Solid electrolyte high energy battery |
US11152657B2 (en) | 2012-04-11 | 2021-10-19 | Ionic Materials, Inc. | Alkaline metal-air battery cathode |
US11749833B2 (en) | 2012-04-11 | 2023-09-05 | Ionic Materials, Inc. | Solid state bipolar battery |
US11949105B2 (en) | 2012-04-11 | 2024-04-02 | Ionic Materials, Inc. | Electrochemical cell having solid ionically conducting polymer material |
JP2016532279A (ja) * | 2013-09-27 | 2016-10-13 | リップ, クリスチアネRipp, Christiane | 再充電可能な電気化学セル |
JP2019216125A (ja) * | 2013-09-27 | 2019-12-19 | インノリス・アセッツ・アー・ゲーInnolith Assets Ag | 再充電可能な電気化学セル |
JP2015076401A (ja) * | 2013-10-08 | 2015-04-20 | コリア エレクトロニクス テクノロジ インスティチュート | ナトリウム−金属塩化物系二次電池及びその製造方法 |
JP2015076400A (ja) * | 2013-10-08 | 2015-04-20 | コリア エレクトロニクス テクノロジ インスティチュート | ナトリウム−二酸化硫黄系二次電池及びその製造方法 |
US10811688B2 (en) | 2013-12-03 | 2020-10-20 | Ionic Materials, Inc. | Solid, ionically conducting polymer material, and methods and applications for same |
JP2016062890A (ja) * | 2014-09-16 | 2016-04-25 | コリア エレクトロニクス テクノロジ インスティチュート | 金属塩化物とアルカリ金属塩化物を含有する陽極及びそれを含むアルカリ金属イオン二次電池 |
US11114655B2 (en) | 2015-04-01 | 2021-09-07 | Ionic Materials, Inc. | Alkaline battery cathode with solid polymer electrolyte |
US11145899B2 (en) | 2015-06-04 | 2021-10-12 | Ionic Materials, Inc. | Lithium metal battery with solid polymer electrolyte |
US11605819B2 (en) | 2015-06-08 | 2023-03-14 | Ionic Materials, Inc. | Battery having aluminum anode and solid polymer electrolyte |
US11342559B2 (en) | 2015-06-08 | 2022-05-24 | Ionic Materials, Inc. | Battery with polyvalent metal anode |
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CA2669551A1 (en) | 2008-05-22 |
US20100062341A1 (en) | 2010-03-11 |
AU2007321466A1 (en) | 2008-05-22 |
IL198445A (en) | 2015-02-26 |
WO2008058685A1 (de) | 2008-05-22 |
BRPI0718646B1 (pt) | 2018-12-11 |
AU2007321466B2 (en) | 2011-11-03 |
HK1140313A1 (en) | 2010-10-08 |
RU2009117719A (ru) | 2010-11-20 |
IL198445A0 (en) | 2010-02-17 |
EP1923934A1 (de) | 2008-05-21 |
MX2009003977A (es) | 2009-06-23 |
BRPI0718646A2 (pt) | 2013-11-19 |
CA2669551C (en) | 2016-01-12 |
US8906556B2 (en) | 2014-12-09 |
ES2574564T3 (es) | 2016-06-20 |
KR20090088405A (ko) | 2009-08-19 |
EP2089924A1 (de) | 2009-08-19 |
CN101622738A (zh) | 2010-01-06 |
JP5356240B2 (ja) | 2013-12-04 |
CN101622738B (zh) | 2013-09-18 |
ZA200904054B (en) | 2010-04-28 |
RU2438212C2 (ru) | 2011-12-27 |
EP2089924B1 (de) | 2016-04-13 |
KR101639238B1 (ko) | 2016-07-13 |
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