JP5705549B2 - 薄膜電池および他のデバイスのための薄膜カプセル化 - Google Patents

薄膜電池および他のデバイスのための薄膜カプセル化 Download PDF

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JP5705549B2
JP5705549B2 JP2010542365A JP2010542365A JP5705549B2 JP 5705549 B2 JP5705549 B2 JP 5705549B2 JP 2010542365 A JP2010542365 A JP 2010542365A JP 2010542365 A JP2010542365 A JP 2010542365A JP 5705549 B2 JP5705549 B2 JP 5705549B2
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ベルント ヨット． ノイデッカー，
ベルント ヨット． ノイデッカー，
ショーン ダブリュー． スナイダー，
ショーン ダブリュー． スナイダー，
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インフィニット パワー ソリューションズ， インコーポレイテッド
インフィニット パワー ソリューションズ， インコーポレイテッド
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Description

（関連出願）
本出願は、３５Ｕ．Ｓ．Ｃ．§１１９の下において、２００８年１月１１日に出願された、米国仮特許出願第６１／０２０，５０６号の利益を主張し、該仮出願は、その全体が本明細書に参考として援用される。
（発明の分野）
本発明の分野は、電池を含む固体の薄膜の二次電気化学デバイスおよび一次電気化学デバイスを堆積、カプセル化および製作するデバイス、組成物、および方法である。
（発明の背景）
薄膜電池（ＴＦＢ）は、典型的には、数年間の寿命にわたって周囲の化学反応物質（例えば、Ｏ２、Ｈ２Ｏ、Ｎ２、ＣＯ２など）に対して電池を保護する高性能密閉カプセル化を必要とし得る。カプセル化に対する品質要求は、薄膜電池、アノード（金属リチウム、リチウムイオン［例えば、炭素または窒化スズ］、または「Ｌｉフリー」アノード［＝ＴＦＢの動作中に金属リチウムがメッキされる集電器］）において最も感受性のある構成要素の材料選択と無関係であり得る。なぜなら、これらのアノードのどれもが、相当量の反応物質の長期間蓄積されたＴＦＢへの透過後に動作を停止し得るからである。例えば１０年間の予想貯蔵期間に、カプセル化は、好ましくは１０−３ｇ／ｍ２日未満の水蒸気透過率（ＷＶＴＲ）を示すべきであり、一方、酸素透過率（ＯＴＲ）は、好ましくは５×１０−４ｇ／ｍ２日より小さくあるべきである。これらの推定量は、アノードにおけるＬｉＯＨまたはＬｉ２Ｏのいずれかに対するリチウム金属またはリチウムイオンの１．６×１０−４の完全な反応に基づく。さらにこれらの推定量は、実際的な率を表し、ＭＯＣＯＮ法によるカプセル化を通って垂直にのみ測定される典型的な透過率の他に、カプセル化ＴＦＢシール領域に沿った反応物質の進入（透過）を含む。
しかしながら、現在の非薄膜カプセル化は、概して標準ＴＦＢの全厚のほぼ５０％以上を担う。所与の厚さ内における最大のエネルギーの供給が重大である用途のためにＴＦＢを電池スタックの中に接合する場合、非エネルギー提供カプセル化におけるスタック体積の５０％を無駄にする余裕はない場合がある。
従って、保護性能を損なうことなく、カプセル化厚さを最小限に減少させるニーズが存在する。
（発明の概要）
本発明は、例えば、薄膜電池などのデバイスのための高性能薄膜カプセル化に関し、該薄膜カプセル化は、その高温安定性を実質的に増加させながら、以前よりはるかに薄いカプセル化デバイスが製作されることを可能にする。説明されるアプローチは、多層の薄膜カプセル化に基づくものであり、該多層の薄膜カプセル化の構成するサブユニットは、例えば、酸素および水分によって実質的に浸透不可能である、交互になった金属ゲッタ／金属窒化物拡散ブロッカ副層を備えている。
一実施形態において、カプセル化デバイスは、約０．５μｍより大きく、約２００μｍより小さい厚さのカソードを有する薄膜電池である。電解質は、例えば厚さが約５μｍより小さくあり得る。アノードは、厚さが例えば約０．１μｍより大きく、約３０μｍより小さくあり得る。また、カプセル化層は、交互になった金属の副層およびセラミックのブロッキング副層を有し得、これらの副層の厚さは、各々少なくとも約５００オングストロームである。さらに、交互になった金属およびセラミックのブロッキング副層は、例えば、少なくとも２つのブロッキング副層および２つの金属の副層を備えている。最後に、少なくとも１つの実施形態において、あらゆる金属の副層およびあらゆるセラミックの副層の組み合わせた全厚は、約５μｍより小さくあり得る。
別の実施形態において、カプセル化デバイスは、電池であり、前のパラグラフにおいて説明された電池型および薄膜カプセル化を用い、複数のセルを積み重ねる。５個のセル積み重ねの全厚は、好ましくは概して約０．５ｍｍより小さくあり得る。
図１は、本発明の実施形態に従う電気化学デバイスをカプセル化するために用いられる多層の薄膜の断面を示す。
（詳細な説明）
図１は、本発明の一実施形態に従う電気化学デバイスをカプセル化するために用いられる多層の薄膜の断面を示す。薄いカプセル化材料は、例えば、交互にある非結晶質またはガラス状の酸化物または窒化物のセラミックブロッキング副層１２０を有する複数の強固な金属ゲッタ副層を含み得る。強固な金属ゲッタ副層１１０は、例えば、水分および酸素からデバイスを保護するために用いられ得る。強固な金属副層は、例えばＺｒ、Ｙ、Ｔｉ、Ｃｒ、Ａｌ、またはこれらの任意の合金から構成され得る。非結晶質またはガラス状のセラミックブロッキング副層１２０は、例えば、ＺｒＯ２、ＺｒＮ、ＺｒＣ、ＺｒＢ２、ＺｒＳｉ、Ｙ２Ｏ３、ＹＮ、ＹＣ、ＹＢ６、ＹＳｉ、ＴｉＯ２、ＴｉＮ、ＴｉＣ、ＴｉＢ２、ＴｉＳｉ、Ｃｒ２Ｏ３、ＣｒＮ、Ｃｒ３Ｃ２、ＣｒＢ２、ＣｒＳｉ、Ａｌ２Ｏ３、ＡｌＮ、Ａｌ４Ｃ３、ＡｌＢ２、Ａｌ４Ｓｉ３、またはこれらの任意の多元素の化合物などの、ゲッタ副層において用いられる１つの金属または複数の金属の酸化物、窒化物、炭化物、ケイ化物、またはホウ化物であり得る。これらのかなりの共有結合で結合された材料の非結晶質またはガラス状の副層は、典型的には、構成原子の塊を通る水分または酸素を非常に限定して拡散させるかまたは拡散させないことを可能にしながら、構成原子の高密度で充填された配置である。その結果、この多層の薄膜は、例えば、膜の容積を通り膜の界面に沿う水分または酸素のどの拡散も効果的にふさぎ得、また下にある空気感受性金属のアノードを保護し得る。さらに副層は、酸素および水分の浸透を防ぐのに十分な結合した厚さを有し得る。
特定の利用可能な材料の中で、金属の層（シート、フォイル、または薄膜）は、特に金属が環境感受性本体の周りに密閉してシールされ得るとき、酸素および水分に対して最も効果的な保護を提供し得る。具体的には、薄膜のデバイスの保護のために、金属の薄膜のカプセル化を適用することが最も好ましく、該金属の薄膜のカプセル化は、基板を有し、きつく密閉する方法でデバイスの隣の表面に沿った基板にカプセル化を取り付けるデバイスの上にテント様の構造を作る。
ＴＦＢのために特に設計された最適化のカプセル化アプローチは、粒子構造をほとんど示さないかまたは全く示さない、交互になった非結晶質またはガラス状の無機の酸化物および／または窒化物および／または炭化物、および／またはケイ化物、および／またはホウ化物の副層を有する複数の薄い金属の副層によって形成される多層構造から成る。特に、特定の「粒子のない」窒化物、炭化物、ケイ化物、およびホウ化物は、非常に高密度の材料形態を有し、該高密度の材料形態は、隣接する薄い金属副層に浸透し得るあらゆる酸素および／または水分の拡散経路を効果的にふさぐ。
本発明の一実施形態において、金属は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、Ａｌ、ならびに／あるいは、それらの合金などの周知のＯ２および／またはＨ２Ｏゲッタから選ばれ得る。拡散をふさぐ無機非結晶質またはガラス状の副層は、ＺｒＯ２、ＺｒＮ、Ｙ２Ｏ３、ＹＮ、Ｃｒ２Ｏ３、ＣｒＮ、Ａｌ２Ｏ３、ＡｌＮ、ならびに／または、ＴｉＡｌＮｘＯｙなどの多項化合物構成およびそれらの誘導体などの材料から選択され得る。
これらの薄膜のカプセル化副層は、例えば、試料変更のない１つの真空蒸着チャンバにおいて単一のスパッタカソードを用いる交互の化合物堆積による金属スパッタリングによって堆積され得る。このことは、同じ金属（例えば、ＴｉＡｌ）のＡｒスパッタリングとＡｒ−Ｎ２−Ｏ２スパッタリングとを単に前後に切り替えることによって実行され得る。その結果は、３μｍの厚さで、０．１μｍ ＴｉＡｌ／０．１μｍ ＴｉＡｌＮｘＯｙ／０．１μｍ ＴｉＡｌ／０．１μｍ ＴｉＡｌＮｘＯｙ／．．．の３０層構造であり得、このことはＯ２およびＨ２Ｏが垂直方向に浸透または透過することを困難にし得る。カプセル化基板界面（シール領域）におけるシールの漏れによるこの高性能のカプセル化を損なうことを避けるために、シール領域におけるこれらの層の実質的に欠陥のない堆積となるように特別な注意が払われ得る。この目的は、適切に作製された基板表面および実質的に欠点のない薄膜層の堆積によって達成され得る。
このタイプの多層の薄膜カプセル化の実施形態は、好ましくは約３μｍの薄さ（ＴＦＢの厚さを１５０μｍから約８０μｍに減少させる）であり得るのみならず、３μｍ ＬｉＣｏＯ２カソードなどの任意の他の電池構成要素層と実質的に同じほど柔軟性があり得る。多層の薄膜カプセル化の柔軟性の微調整は、物理蒸着法（ＰＶＤ）パラメータの変更、および／または、ＴｉＡｌ／ＴｉＡｌＮｘＯｙ／ＴｉＡｌ／．．．の代わりに、Ｚｒ／ＺｒＮ／Ｚｒ／Ｚｒ２Ｎ／Ｚｒ／Ｚｒｘ／Ｚｒ．．．の手段によるなどの材料選択における変更によって達成され得る。
金属リチウムアノードは、例えば、Ｚｒおよび／またはＺｒＮに対して化学的に安定している。しかしながら、金属リチウムアノードは、柔らかい場合があり、今日のほとんどのアノード材料について公知のように、ＴＦＢの動作中、実質的な拡張および収縮を受けやすい場合がある。これらなどの機械的な特徴は、多層の薄膜カプセル化にとって難しく、リチウムアノード／カプセル化インタフェースにおける応力の不均衡による亀裂を引き起こす可能性があり得る。カプセル化が裂けると、下にあるリチウムアノードは、空気に曝され得、従って、化学的に劣化し得る。
この応力不均衡を打ち消すために、Ｌｉｐｏｎの薄膜層などの応力調整層が、金属リチウムアノードと多層の薄膜カプセル化との間に導入され得る。Ｌｉｐｏｎは、ＴｉＡｌ、ＴｉＡｌＮｘＯｙ、Ｚｒ、ＺｒＮなど、ならびにリチウム合金、リチウム固溶体、および金属リチウムに対して、化学的、機械的に安定していることが証明されてきた。上にあるＬｉｐｏｎ応力調整層と共に、金属リチウムアノードの下に位置を定められるＬｉｐｏｎ電解質層は、Ｌｉｐｏｎが金属リチウムと適合するので、機械的のみならず化学的にも金属リチウムアノードを保護しながら、間に置かれた金属リチウムアノードをとどめ得る。金属リチウムアノードがＬｉｐｏｎの層内にとどめられるこの構成において、金属リチウムアノードがその融点の１８１℃を超えて加熱されたときでさえも、金属リチウムアノードは、その位置内に固定され、電気化学的に完全のままであり得る。この構成を利用するいくつかの実施形態のこの工学技術の設計は、ＴＦＢがハンダリフローまたはフリップチッププロセッシングにおいて用いられることを可能し得る。この設計による支援を受けて、多層の薄膜カプセル化は、産業界において現在用いられているサーリン（ｓｕｒｌｙｎ）／金属フォイルカプセル化よりも、はるかに薄い厚さをＴＦＢに提供するのみならず、はるかに高い温度安定性（＞１５０℃連続）をＴＦＢに提供する。
他の実施形態において、金属リチウムアノードに非常に類似して電気化学的に作用するリチウムの合金または固溶体（例えば、ＬｉｘＣｕ、ＬｉｘＺｒ、ＬｉｘＶ、ＬｉｘＷ）は、アノードとして用いられ得、柔らかいリチウムアノードと比較してより強い機械的特性を提供し、それによって、Ｌｉｐｏｎ応力調整層を使用することなく、多層の薄膜カプセル化の直接の堆積を可能にする。結果として生じる多層の薄膜カプセル化は、ちょうどＬｉｐｏｎ応力調整層によって構成されるもののように、ＴＦＢが高温安定性（＞１５０℃連続）を維持することをなおも可能にし得る。
特定の実施形態における多層の薄膜カプセル化が、ＴＦＢ動作中、金属リチウムアノードまたはリチウム合金に対して化学的および機械的に安定していることが論証されると、特定の実施形態における本発明は、多層の薄膜カプセル化を他の領域において選択的に伝導し、絶縁する方法で多層の薄膜カプセル化を堆積パターニングし得る。この方法で、多層の薄膜カプセル化はまた、金属の基板を通ってＴＦＢを短絡させることなくアノード集電体または負の端子として働き得、該金属の基板は、金属フォイル上に製作されたＩＰＳのＴＦＢにおける正の端子として構成される。
（実施形態の例）
（例１）
いくつかの実施形態は、水分および空気からリチウムアノードを保護するように説明されるカプセル化方法を用いる。これらの実施形態は、厚さが約５０μｍの寸法である１ ｉｎ２の金属フォイル基板を備えている。０．５μｍ厚の伝導性バリア層は、ここに説明される方法の他に一般的に当業者に使用可能である方法のうちの１つを用いて、基板の少なくとも１つの表面に配置される。３．５μｍ厚のＬｉＣｏＯ２正のカソードは、伝導性バリア層に配置される。１．２μｍ厚のＬｉｐｏｎ電解質層はカソード層に配置され、９μｍ厚のＬｉアノードは電解質に配置される。ＺｒＮの０．１μｍの１５個の副層と交互になった０．１μｍＺｒの１５個の副層から成る３μｍ厚の薄膜多層カプセル化は、次いで層にされたデバイスに配置される。この特定の実施形態は、８５℃／８５％ＲＨにおいて５００時間を達成し得る。
（例２）
他の実施形態は、前に論議された５個のカプセル化した電池セルを組み合わせ得る。この実施形態は、概して０．５ｍｍ未満の全厚を有し、２５℃において４．２〜２．０Ｖで１／２Ｃ速度で２．５ｍＡｈを供給する。
（例３）
本発明のさらに他の実施形態は、０．５μｍ伝導性バリア層と、約１２μｍの厚さを有するＬｉＣｏＯ２正カソードと、１．２μｍ Ｌｉｐｏｎ電解質層と、約１０μｍの厚さを有するＬｉアノードと、Ｌｉアノードの上部の２μｍ厚のＬｉｐｏｎ調整層とを備えている。これらの実施形態は、面積１ ｉｎ２の５０μｍ金属フォイル基板上に製作され得、３μｍ薄膜カプセル化によってカプセル化され得る。この実施形態は、８０μｍ未満の全厚を有し、概して２５℃において４．２〜２．０Ｖで１／２Ｃ速度で２ｍＡｈを供給する。
（例４）
さらに、本発明の他の実施形態は、例１からの電気化学デバイスを備え得る。Ｚｒ−ＺｒＮの高い融点（＞＞１，０００℃）のために、カプセル化は、長期間にわたって最高２６５℃の温度−鉛フリーのリフロープロセッシングにおいて遭遇する最高温度−に耐えることが可能である。電気化学デバイスのこの化学的安定性および物理的安定性は、しかしながら、これらの条件の下でＺｒまたはＺｒＮと反応しない金属リチウムアノードの融解にもかかわらず達成される。
（例５）
さらに、本発明の他の実施形態は、選択的伝導性のカプセル化を備え、この場合、シャドウマスキングによって達成され得るような薄膜堆積パターニングによって、カプセル化の特定の領域は、電気的伝導性に作られ、一方、いくつかの他の領域は、電気的絶縁性に製作される。電気的伝導性の領域は、金属の副層および／または電気的伝導性セラミックの副層を備え、一方、電気的絶縁性の領域は、例えばＺｒＯ２などのセラミックの不導体の副層を備えている。選択的伝導性カプセル化は、それが電気化学デバイスの電気的端子として用いられることを可能にする。
本明細書において説明される特定の方法論、化合物、材料、製造技術、使用法、および用途は変化し得るので、本発明がそれらに限定されないことは理解されるべきである。本明細書において用いられる用語は特定の実施形態を説明する目的のみのために用いられ、本発明の範囲を限定する意図はないこともまた理解されるべきである。本明細書および添付の特許請求の範囲において用いられるように、単数形「ａ」、「ａｎ」、および「ｔｈｅ」は、文脈が明らかに別のことを指示しない限り、複数の参照を含むことは注意されなければならない。従って例えば、「１つの要素」への参照は１または１より多い要素への参照であり、当業者にとって公知である要素の均等物を含む。同様に、別の例では、「１つのステップ」または「１つの手段」への参照は、１または１より多いステップまたは手段への参照であり、サブステップおよび補助の手段を含み得る。用いられるすべての接続詞は、可能な限り最も包括的な意味で理解されるべきである。従って単語「または」は、文脈が明らかに別のことを必要としない限り、論理「排他的または」の定義よりはむしろ論理「または」の定義を有するように理解されるべきである。本明細書に説明される構造は、そのような構造の機能上の均等物もまた参照するように理解されるべきである。近似を表現するように解釈されるべき言語は、文脈が明らかに別のことを指示しない限り、そのように理解されるべきである。
別に定義されない限り、本明細書において用いられるすべての科学技術用語は、本発明が属する分野の当業者によって共通に理解される意味と同じ意味を有する。好ましい方法、技術、デバイスおよび材料が説明されるが、但し、本明細書において説明されるものに類似するかまたは均等な任意の方法、技術、デバイスまたは材料が、本発明の実施または試験において用いられ得る。本明細書において説明される構造は、そのような構造の機能上の均等物も参照するように理解されるべきである。
識別されるすべての特許および他の刊行物は、例えば、本発明に関連して用いられ得る、そのような刊行物において説明される方法論を説明し開示する目的のために、本明細書に参考として援用される。これらの刊行物は、それらの刊行物の開示が本出願の出願日の前の場合のみ提供される。この点に関して、先行の発明または任意の他の理由で、本発明がそのような開示に先行する権利がないということを承認するものとして解釈されるべきでは全くない。
上に説明された実施形態および例は、例示にすぎない。当業者は、ここに具体的に説明された実施形態から変形を認識し得、該変形は、本開示および発明の範囲内にあることが意図される。そのようなものとして、本発明は、以下の特許請求の範囲によってのみ限定される。従って、本発明の修正が添付の特許請求の範囲およびその均等物の範囲内に入る限り、本発明が該修正を含むことが意図される。さらに本発明に従う電気化学デバイスの形成または性能に関する特定の説明または理論は、説明のためのみに提示され、本開示の範囲または特許請求の範囲に関して限定することとして考えられるべきではない。

Claims (33)

  1. 環境感受性層と、
    該環境感受性層の上に堆積するカプセル化層であって、金属の副層とセラミックの副層とが交互になった複数の層を含む、カプセル化層と
    を備えており、
    前記カプセル化層の少なくとも１つの領域は、金属の副層と電気的伝導性セラミックの副層とが交互になった複数の層を備える電気的伝導性領域であり、他の１つの領域は、複数の電気的絶縁性セラミックの副層を備える電気的絶縁性領域である、電気化学デバイスであって、
    前記電気的伝導性領域は、前記電気化学デバイスの電気的端子として働く、電気化学デバイス。
  2. 前記金属の副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素を備えている、請求項１に記載の電気化学デバイス。
  3. 前記セラミックの副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素の窒化物を備えている、請求項１に記載の電気化学デバイス。
  4. 前記セラミックの副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素の酸化物を備えている、請求項１に記載の電気化学デバイス。
  5. 前記セラミックの副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素の炭化物を備えている、請求項１に記載の電気化学デバイス。
  6. 前記セラミックの副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素のケイ化物を備えている、請求項１に記載の電気化学デバイス。
  7. 前記セラミックの副層は、Ｚｒ、Ｙ、Ｔｉ、Ｃｒ、およびＡｌから成る群から選択される少なくとも１つの元素のホウ化物を備えている、請求項１に記載の電気化学デバイス。
  8. 前記環境感受性層は、リチウム合金、リチウム固溶体、金属リチウム、チタン、バナジウム、銅、ジルコニウム、タングステン、およびアルミニウムから成る群から選択される少なくとも１つの材料を備えている、請求項１に記載の電気化学デバイス。
  9. 前記環境感受性層と前記カプセル化層との間に配置される応力調整層をさらに備えている、請求項１に記載の電気化学デバイス。
  10. 前記応力調整層は、Ｌｉｐｏｎを備えている、請求項９に記載の電気化学デバイス。
  11. 前記環境感受性層は、リチウム合金、リチウム固溶体、および金属リチウムから成る群から選択される少なくとも１つの材料を備えている、請求項１に記載の電気化学デバイス。
  12. 前記カプセル化層の少なくとも１つの副層は、金属の標的からスパッタリングを用いて堆積される、請求項１に記載の電気化学デバイス。
  13. 前記カプセル化層の少なくとも１つの副層は、金属スパッタリング堆積法を用いて堆積される、請求項１に記載の電気化学デバイス。
  14. 前記環境感受性層は、アノードを備えている、請求項１に記載の電気化学デバイス。
  15. 前記電気化学デバイスは、２６５℃までのハンダリフロー条件の下で熱的に安定している、請求項１に記載の電気化学デバイス。
  16. カソードと、
    該カソード上に堆積する電解質と、
    該電解質上に堆積するアノードと、
    該アノードと該カプセル化層との間に堆積する応力調整層と
    をさらに備えている、請求項１に記載の電気化学デバイス。
  17. 前記カソードは、ＬｉＣｏＯ２を備えている、請求項１６に記載の電気化学デバイス。
  18. 前記電解質は、Ｌｉｐｏｎを備えている、請求項１６に記載の電気化学デバイス。
  19. 前記アノードは、リチウム合金、リチウム固溶体、および金属リチウムから成る群から選択される少なくとも１つの材料を備えている、請求項１６に記載の電気化学デバイス。
  20. 前記応力調整層の材料は、Ｌｉｐｏｎを備えている、請求項１６に記載の電気化学デバイス。
  21. 前記カソードの厚さは、０．５μｍ〜２００μｍである、請求項１６に記載の電気化学デバイス。
  22. 前記電解質の厚さは、５μｍ未満である、請求項１６に記載の電気化学デバイス。
  23. 前記アノードの厚さは、０．１μｍ〜３０μｍである、請求項１６に記載の電気化学デバイス。
  24. 前記交互になった金属の副層およびセラミックの副層の厚さは、各々少なくとも５００オングストロームである、請求項１６に記載の電気化学デバイス。
  25. 前記金属の副層とセラミックの副層とが交互になった複数の層には、少なくとも２つの金属の副層および少なくとも２つのセラミックの副層が含まれる、請求項１に記載の電気化学デバイス。
  26. 全ての金属の副層および全てのセラミックの副層の全厚は、５μｍ未満である、請求項２５に記載の電気化学デバイス。
  27. カソードと、
    該カソード上に堆積する電解質と、
    該電解質上に堆積する環境感受性アノードと、
    該アノード上に堆積する応力調整層と、
    カプセル化層であって、該応力調整層上に堆積する複数の交互になった金属副層およびセラミック副層を備えている、カプセル化層と
    を備えており、
    前記カプセル化層の少なくとも１つの領域は、金属の副層と電気的伝導性セラミックの副層とが交互になった複数の層を備える電気的伝導性領域であり、他の１つの領域は、複数の電気的絶縁性セラミックの副層を備える電気的絶縁性領域である、電気化学デバイスであって、
    前記電気的伝導性領域は、前記電気化学デバイスの電気的端子として働く、電気化学デバイス。
  28. ＬｉＣｏＯ２層と、
    該ＬｉＣｏＯ２層上に堆積する第１のＬｉｐｏｎ層と、
    該第１のＬｉｐｏｎ層上に堆積するリチウム層と、
    該リチウム層上に堆積する第２のＬｉｐｏｎ層と、
    カプセル化層であって、該第２のＬｉｐｏｎ層上に堆積する複数の交互になった金属副層およびセラミック副層を備えている、カプセル化層と
    を備えており、
    前記カプセル化層の少なくとも１つの領域は、金属の副層と電気的伝導性セラミックの副層とが交互になった複数の層を備える電気的伝導性領域であり、他の１つの領域は、複数の電気的絶縁性セラミックの副層を備える電気的絶縁性領域である、電気化学デバイスであって、
    前記電気的伝導性領域は、前記電気化学デバイスの電気的端子として働く、電気化学デバイス。
  29. ０．５μｍより大きく、２００μｍ未満の厚さのカソードと、
    ５μｍ未満の厚さの電解質と、
    ０．１μｍより大きく、３０μｍ未満の厚さのアノードと、
    応力調整層と、
    カプセル化層であって、複数の交互になった金属の副層およびセラミックの副層を備え、各副層は５μｍ未満の厚さである、カプセル化層と
    を備えており、
    前記カプセル化層の少なくとも１つの領域は、金属の副層と電気的伝導性セラミックの副層とが交互になった複数の層を備える電気的伝導性領域であり、他の１つの領域は、複数の電気的絶縁性セラミックの副層を備える電気的絶縁性領域である、電気化学デバイスであって、
    前記電気的伝導性領域は、前記電気化学デバイスの電気的端子として働く、電気化学デバイス。
  30. 電気化学デバイスを製造する方法であって、
    環境感受性層を堆積させることと、
    複数の交互になった金属の副層およびセラミックの副層を備えるカプセル化層を堆積させることと
    を包含し、
    前記カプセル化層の少なくとも１つの領域は、金属の副層と電気的伝導性セラミックの副層とが交互になった複数の層を備える電気的伝導性領域であり、他の１つの領域は、複数の電気的絶縁性セラミックの副層を備える電気的絶縁性領域である、方法であって、
    前記電気的伝導性領域は、前記電気化学デバイスの電気的端子として働く、方法。
  31. 前記環境感受性層は、リチウム合金、リチウム固溶体、および金属リチウムから成る群から選択される少なくとも１つの材料を備えている、請求項３０に記載の方法。
  32. 前記環境感受性層の上に堆積する応力調整層をさらに含む、請求項３０に記載の方法。
  33. 前記環境感受性層は、リチウム合金、リチウム固溶体、および金属リチウムから成る群から選択される少なくとも１つの材料を備えている、請求項３０に記載の方法。
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US9029012B2 (en) 2015-05-12
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US20150349301A1 (en) 2015-12-03
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