JP2018092936A - セラミックリチウムイオン固体電解質の反応焼結 - Google Patents
セラミックリチウムイオン固体電解質の反応焼結 Download PDFInfo
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Abstract
【解決手段】固体、高密度、気密性のリチウムイオン電解質膜を形成する方法は、非晶質、ガラス質または低溶融温度固体反応体を、耐火性酸化物反応体と混合し、混合物を形成する工程と、混合物をキャストして、グリーンボディを形成する工程と、グリーンボディを焼結して、固体膜を形成する工程とを含んでなる。得られた電解質膜は、リチウムイオン電池に組み込むことができる。
【選択図】図1
Description
焼結を促進する1つのアプローチは、過剰量のリチウムを添加することであり、これによって、低融点リン酸リチウム液相の形成を生じることができる。しかしながら、このアプローチは、最終的な膜から水性環境に浸出する残留リン酸リチウム相を生じ得、機械的な弱さおよび/または膜破損をももたらし得る。実施形態に従って、焼結の間に液相を形成する低融点反応体を使用して、水に安定な膜を形成することができるが、低融点反応体は、焼結の間に消費される。
組成Li1+xAlxTi2−x(PO4)3を有するリチウムイオンセラミック電解質が形成される。この材料はアルミニウムがドーピングされて、10−4S/cmより高い高リチウムイオン伝導率を有することが示された。
実施例2に記載されるLAPガラスを、0.5マイクロメートル未満のd50まで粉砕されたGeO2を含有するミルバッチと混合した。テープキャストグリーンテープは、実施例2で使用されるものと同様の方法で調製された。このテープを、乾燥させ、切断し、剥離し、そして2時間900℃で焼結して、膜試料を製造した。試料を直径1インチ(2.54cm)のディスクに切断し、SEM、XRDおよびインピーダンス分光法によって特徴決定した。得られた膜は、高密度、気密性であり、そして1マイクロメートル未満の平均粒度を有する。XRDによって、ほぼ純粋なLi1.4Al0.4Ge1.6(PO4)3が示される。インピーダンス分光法によって、1.8×10−4S/cmの伝導率が示される。
実施例2に記載されるLAPガラスを、0.5マイクロメートル未満のd50まで粉砕されたSnO2を含有するミルバッチと混合した。テープキャストグリーンテープは、実施例2で使用されるものと同様の方法で調製された。このテープを、乾燥させ、切断し、剥離し、そして2時間900℃で焼結して、膜試料を製造した。試料を直径1インチ(2.54cm)のディスクに切断し、SEM、XRDおよびインピーダンス分光法によって特徴決定した。得られた膜は、高密度、気密性であり、そして1マイクロメートル未満の平均粒度を有する。XRDによって、ほぼ純粋なLi1.4Al0.4Sn1.6(PO4)3が示される。インピーダンス分光法によって、2.1×10−4S/cmの伝導率が示される。
ガラスのガラス転移温度を増加させることによって、出発LAPガラスの吸湿状を低下させるため、そして粉砕時間を低下させるため、出発LAPガラスは、最終的なNASICON材料に所望の遷移金属のフラクションを含むことによって変性されてもよい。下記の表で、様々な「LAP+M」溶融物に関して0.5マイクロメートル未満のd50を達成するために必要とされる吸湿性挙動および粉砕時間が比較される。表1に、ID桁の名称「a」は、Al置換、すなわち、Li1+aAlaM2−a(PO4)3の量を表す。Li2O、Al2O3、P2O5、TiO2およびGeO2組成は、モル%で報告される。溶融温度Tmはセ氏度で記載される。表の第9桁は、ガラスが吸湿性であったかどうか示す。第10桁に、粉砕時間が時間で記載される。試料5〜8に関して見られるように、TiO2および/またはGeO2の添加によって、吸湿性挙動を低下させることができ、粉砕時間を短縮することができる。
さらなる実施形態において、気密性LATP膜は、非晶質リン酸チタン(TP)および/またはリン酸アルミニウムチタン(ATP)材料から反応焼結を通して製造することができる。フレームスプレー熱分解(FSP)法を使用して、非晶質TPおよびATP ナノ粉末を生成した。FSPプロセスにおいて、Ti−イソプロポキシド、Alトリ−sec−ブトキシド、AlCl3、トリメチルホスフェートなどのTi、AlおよびP前駆体を、エタノール、イソプロパノール、2−メトキシエタノールなどの有機溶媒に溶解する。ある種の前駆体の高い揮発性のために、溶液の前駆体濃度は、燃焼の間に前駆体材料の損失を最小化するために、少なくとも30%(例えば少なくとも40%)であることができる。実施例プロセスでは、スプレーされた液滴を燃焼させるために、CH4/O2フレームによって取り囲まれるノズルを通して溶液がスプレーされる。フレーム中、前駆体材料は反応して、ナノ粉末生成物を形成する。
Claims (6)
- 固体リチウムイオン電解質膜を形成する方法であって、
非晶質、ガラス質、または、リン酸リチウムガラス、リン酸ゲルマニウムガラス、リン酸リチウムアルミニウムガラスおよび結晶化リン酸リチウムアルミニウムセラミックからなる群から選択された低溶融温度固体反応体を、耐火性酸化物反応体と組み合わせて、混合物を形成する工程と、
前記混合物をキャストして、グリーンボディを形成する工程と、
前記グリーンボディを焼結して、固体膜を形成する工程であって、その焼結の間に、前記低溶融温度固体反応体が前記耐火性酸化物反応体と反応して前記固体膜を形成する工程と、
を含んでなることを特徴とする方法。 - 前記低溶融温度固体反応体は、前記反応の間に実質的に消費されることを特徴とする、請求項1に記載の方法。
- 前記耐火性酸化物反応体が、酸化チタン、酸化スズおよび酸化ゲルマニウムからなる群から選択されることを特徴とする、請求項1または2に記載の方法。
- 前記低溶融温度固体反応体の平均粒径が0.5マイクロメートル未満であり、そして前記耐火性酸化物反応体の平均粒径が0.5マイクロメートル未満であることを特徴とする、請求項1〜3のいずれか一項に記載の方法。
- 焼結温度が1100℃未満であ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方法。
- 前記膜の密度が、その理論的な密度の少なくとも95%であ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方法。
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Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9308511B2 (en) | 2009-10-14 | 2016-04-12 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Fabricating porous materials using thixotropic gels |
US9242900B2 (en) | 2009-12-01 | 2016-01-26 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Porous geopolymer materials |
KR102060844B1 (ko) | 2011-09-21 | 2019-12-30 | 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 | 지오폴리머 수지 재료, 지오폴리머 재료, 및 그에 의해 제조된 재료 |
WO2013109622A1 (en) * | 2012-01-16 | 2013-07-25 | Ceramatec, Inc | Lithium-ion-conducting materials |
JP5969799B2 (ja) * | 2012-04-11 | 2016-08-17 | 株式会社コベルコ科研 | Li含有燐酸化合物焼結体およびスパッタリングターゲット、並びにその製造方法 |
US8821771B2 (en) * | 2012-09-26 | 2014-09-02 | Corning Incorporated | Flame spray pyrolysis method for forming nanoscale lithium metal phosphate powders |
US9876247B2 (en) | 2012-11-15 | 2018-01-23 | Corning Incorporated | Solid ceramic electrolytes |
US10170759B2 (en) | 2013-06-21 | 2019-01-01 | Arizona Board Of Regents On Behalf Of Arizona State University | Metal oxides from acidic solutions |
KR101683949B1 (ko) * | 2013-11-14 | 2016-12-07 | 주식회사 엘지화학 | 화염분무열분해법을 이용한 리튬 이차전지용 고체 전해질 나노 입자의 제조 방법 |
US10926241B2 (en) | 2014-06-12 | 2021-02-23 | Arizona Board Of Regents On Behalf Of Arizona State University | Carbon dioxide adsorbents |
US9673483B2 (en) | 2015-01-19 | 2017-06-06 | Corning Incorporated | Reactive sintering of ceramic lithium ion electrolyte membranes |
CN105304938B (zh) * | 2015-09-29 | 2017-10-17 | 山东玉皇新能源科技有限公司 | 固体电解质磷酸钛铝锂的电化学制备方法 |
WO2017195232A1 (ja) * | 2016-05-10 | 2017-11-16 | 株式会社住田光学ガラス | Ltpまたはlatp結晶粒子の製造方法 |
WO2018136695A1 (en) | 2017-01-20 | 2018-07-26 | Seo Dong Kyun | Aluminosilicate nanorods |
DE102018102387B3 (de) * | 2018-02-02 | 2019-06-27 | Schott Ag | Glaskeramik mit ionenleitender Restglasphase und Verfahren zu ihrer Herstellung |
CN108383517B (zh) * | 2018-03-30 | 2020-12-22 | 华南理工大学 | 一种低温烧结Li-Mg-P-O固体电解质陶瓷及其制备方法 |
JP7054658B2 (ja) * | 2018-07-31 | 2022-04-14 | 太平洋セメント株式会社 | 二次電池の固体電解質用latp結晶粒子の製造方法 |
CN108987799B (zh) * | 2018-08-09 | 2021-07-20 | 河南科技学院 | 一种全固态电池固态电解质及其制备方法和应用 |
US11819806B1 (en) * | 2018-10-15 | 2023-11-21 | Ampcera Inc. | Methods for manufacturing a solid state ionic conductive membrane on a macro porous support scaffold |
CN110137564B (zh) * | 2019-04-09 | 2021-08-10 | 中国科学院合肥物质科学研究院 | 一种用于锂离子电池的多孔型固态电解质制备方法 |
WO2020206552A1 (fr) * | 2019-04-11 | 2020-10-15 | HYDRO-QUéBEC | Électrolytes céramiques, leurs procédés de préparation et les cellules électrochimiques les comprenant |
RU2744884C1 (ru) * | 2020-10-21 | 2021-03-16 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Способ получения сложного литиевого танталата стронция и лантана |
CN113178615A (zh) * | 2021-03-30 | 2021-07-27 | 深圳市新创材料科技有限公司 | 一种latp固态电解质的制备方法 |
CN113422108A (zh) * | 2021-06-22 | 2021-09-21 | 万年县阿尔伯特新能源研究有限公司 | 一种新型lgsp固态电解质及制备方法 |
CN113666642B (zh) * | 2021-08-19 | 2023-08-04 | 蜂巢能源科技有限公司 | 一种全固态电池用电解质膜及其制备方法和应用 |
CN114784275B (zh) * | 2022-04-13 | 2023-11-14 | 中国计量大学 | 一种阳极材料及其制备方法、锂电池阳极及其制备方法、锂电池 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002151142A (ja) * | 2000-11-15 | 2002-05-24 | Toyota Central Res & Dev Lab Inc | リチウムイオン伝導体およびその製造方法 |
JP2008091328A (ja) * | 2006-09-04 | 2008-04-17 | Sumitomo Electric Ind Ltd | リチウム二次電池およびその製造方法 |
JP2009080970A (ja) * | 2007-09-25 | 2009-04-16 | Ohara Inc | リチウムイオン伝導性固体電解質およびその製造方法 |
JP2009187911A (ja) * | 2008-02-08 | 2009-08-20 | Ohara Inc | 固体電池およびその電極の製造方法 |
JP2009193894A (ja) * | 2008-02-15 | 2009-08-27 | Ohara Inc | グリーンシート積層体の製造方法 |
JP2011150817A (ja) * | 2010-01-19 | 2011-08-04 | Ohara Inc | 全固体電池 |
Family Cites Families (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4113928A (en) * | 1976-02-17 | 1978-09-12 | University Of Utah | Method of preparing dense, high strength, and electrically conductive ceramics containing β"-alumina |
US4985317A (en) | 1988-11-30 | 1991-01-15 | Japan Synthetic Rubber Co., Ltd. | Lithium ion-conductive solid electrolyte containing lithium titanium phosphate |
JPH0329206A (ja) * | 1989-03-09 | 1991-02-07 | Japan Synthetic Rubber Co Ltd | リチウムイオン導電性固体電解質およびその製法 |
US5094577A (en) | 1990-06-29 | 1992-03-10 | The Eastern Company | Mine roof expansion anchor |
JP3029206B2 (ja) | 1990-07-17 | 2000-04-04 | 富士通株式会社 | 半導体装置の配線方法 |
US5094677A (en) | 1991-03-04 | 1992-03-10 | Corning Incorporated | Preparation of pollucite ceramics |
EP0838441B1 (en) | 1996-10-28 | 2003-04-09 | Kabushiki Kaisha Ohara | Lithium ion conductive glass-ceramics and electric cells and gas sensors using the same |
US6248691B1 (en) | 1998-02-10 | 2001-06-19 | Corning Incorporated | Method of making mesoporous carbon |
AU2002215336A1 (en) | 2000-11-07 | 2002-05-21 | Corning Incorporated | Pollucite-based ceramic with low cte |
US7763382B2 (en) * | 2002-07-26 | 2010-07-27 | A123 Systems, Inc. | Bipolar articles and related methods |
CN101040401A (zh) * | 2004-08-17 | 2007-09-19 | 株式会社小原 | 锂离子二次电池及其固体电解质 |
JP5122063B2 (ja) | 2004-08-17 | 2013-01-16 | 株式会社オハラ | リチウムイオン二次電池および固体電解質 |
CN100495801C (zh) * | 2004-12-13 | 2009-06-03 | 松下电器产业株式会社 | 包含活性材料层和固体电解质层的叠层体及使用这种叠层体的全固态锂二次电池 |
WO2006064774A1 (ja) | 2004-12-13 | 2006-06-22 | Matsushita Electric Industrial Co., Ltd. | 活物質層と固体電解質層とを含む積層体およびこれを用いた全固体リチウム二次電池 |
US7833469B2 (en) * | 2004-12-15 | 2010-11-16 | Coorstek, Inc. | Preparation of yttria-stabilized zirconia reaction sintered products |
WO2007004590A1 (ja) | 2005-07-01 | 2007-01-11 | National Institute For Materials Science | 全固体リチウム電池 |
US9580320B2 (en) | 2005-10-13 | 2017-02-28 | Ohara Inc. | Lithium ion conductive solid electrolyte and method for manufacturing the same |
JP2007134305A (ja) * | 2005-10-13 | 2007-05-31 | Ohara Inc | リチウムイオン伝導性固体電解質およびその製造方法 |
US7771880B2 (en) * | 2005-11-21 | 2010-08-10 | University Of Dayton | Solid composite electrolyte membrane and method of making |
RU2403653C2 (ru) | 2005-12-06 | 2010-11-10 | Эл Джи Кем, Лтд. | Органическо/неорганический композитный разделитель, имеющий градиент морфологии, способ его изготовления и содержащее его электрохимическое устройство |
WO2007075867A2 (en) * | 2005-12-19 | 2007-07-05 | Polyplus Battery Company | Composite solid electrolyte for protection of active metal anodes |
US20070231704A1 (en) | 2006-03-30 | 2007-10-04 | Ohara Inc. | Lithium ion conductive solid electrolyte and production process thereof |
US20090291365A1 (en) * | 2006-12-19 | 2009-11-26 | General Electric Company | Energy storage device and method |
JP2008171705A (ja) | 2007-01-12 | 2008-07-24 | Toyota Motor Corp | 燃料電池システム |
JP2008171706A (ja) | 2007-01-12 | 2008-07-24 | D D K Ltd | コネクタ及び該コネクタに使用される抜去部品 |
US9178255B2 (en) * | 2008-06-20 | 2015-11-03 | University Of Dayton | Lithium-air cells incorporating solid electrolytes having enhanced ionic transport and catalytic activity |
JP4921428B2 (ja) | 2008-06-30 | 2012-04-25 | 株式会社オハラ | リチウムイオン伝導性固体電解質グリーンシートの製造方法 |
JP5234933B2 (ja) | 2008-06-30 | 2013-07-10 | 株式会社オハラ | リチウムイオン伝導性固体電解質の製造方法 |
CN101786873B (zh) * | 2009-01-22 | 2013-03-13 | 中国科学院上海硅酸盐研究所 | 锂离子电池电解质陶瓷膜的制备方法 |
JP5387051B2 (ja) | 2009-02-27 | 2014-01-15 | 日本ゼオン株式会社 | 全固体二次電池用積層体および全固体二次電池 |
JP2011003500A (ja) | 2009-06-22 | 2011-01-06 | Samsung Electronics Co Ltd | 全固体型リチウム二次電池 |
CA2770906A1 (en) * | 2009-08-14 | 2011-02-17 | The Regents Of The University Of Michigan | Direct thermal spray synthesis of li ion battery components |
US8263515B2 (en) * | 2009-08-29 | 2012-09-11 | Fatih Dogan | Nanostructured dielectric materials for high energy density multi layer ceramic capacitors |
KR20120004209A (ko) * | 2010-07-06 | 2012-01-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지 |
US20120135289A1 (en) | 2010-11-29 | 2012-05-31 | Ippei Noda | Polyolefin microporous membrane and separator for lithium ion battery |
EP2469623A1 (en) | 2010-12-24 | 2012-06-27 | Takemoto Yushi Kabushiki Kaisha | Polyolefin microporous membrane and separator for lithium ion battery |
-
2011
- 2011-11-29 US US13/306,011 patent/US10411288B2/en active Active
-
2012
- 2012-11-28 TW TW101144527A patent/TWI559599B/zh not_active IP Right Cessation
- 2012-11-29 JP JP2014544865A patent/JP2015506063A/ja active Pending
- 2012-11-29 WO PCT/US2012/066968 patent/WO2013082231A1/en active Application Filing
- 2012-11-29 CN CN201280067770.7A patent/CN104221183A/zh active Pending
- 2012-11-29 EP EP12799439.0A patent/EP2786440B1/en not_active Not-in-force
- 2012-11-29 KR KR1020147017973A patent/KR102218052B1/ko active IP Right Grant
- 2012-11-29 CN CN201910476750.9A patent/CN110127598A/zh active Pending
-
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- 2017-12-27 JP JP2017250681A patent/JP6748058B2/ja active Active
-
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- 2019-07-26 US US16/523,327 patent/US20190348706A1/en not_active Abandoned
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-
2022
- 2022-06-20 US US17/844,471 patent/US20220320576A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002151142A (ja) * | 2000-11-15 | 2002-05-24 | Toyota Central Res & Dev Lab Inc | リチウムイオン伝導体およびその製造方法 |
JP2008091328A (ja) * | 2006-09-04 | 2008-04-17 | Sumitomo Electric Ind Ltd | リチウム二次電池およびその製造方法 |
JP2009080970A (ja) * | 2007-09-25 | 2009-04-16 | Ohara Inc | リチウムイオン伝導性固体電解質およびその製造方法 |
JP2009187911A (ja) * | 2008-02-08 | 2009-08-20 | Ohara Inc | 固体電池およびその電極の製造方法 |
JP2009193894A (ja) * | 2008-02-15 | 2009-08-27 | Ohara Inc | グリーンシート積層体の製造方法 |
JP2011150817A (ja) * | 2010-01-19 | 2011-08-04 | Ohara Inc | 全固体電池 |
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