JP6746062B2 - 電解質抑制イオン伝導体を使用する電極保護 - Google Patents
電解質抑制イオン伝導体を使用する電極保護 Download PDFInfo
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Description
化学式:x(yLi2S+zLi2O)+MS2
(式中、Mは、Si、Ge、またはSnであり、y+z=1であり、xは0.5〜3の範囲であってもよい)
を有する。
化学式:x(yLi2S+zLi2O)+MS2
(式中、Mは、Si、Ge、またはSnであり、y+z=1であり、xは0.5〜3の範囲であってもよい)
を有してもよい。いくらかの態様において、xは、少なくとも0.5、少なくとも1.0、少なくとも1.5、少なくとも2.0、または少なくとも2.5である。他の態様において、xは、3.0以下、2.5以下、2.0以下、1.5以下、1.0以下、または0.5以下である。上記範囲の組合せも可能である。xの他の値も可能である。
x(yLi2S+zLi2O)+MS2
(式中、Mは、Si、Ge、またはSnであり、y+z=1であり、xは0.5〜3の範囲であってもよい)
を有してもよい。任意に、上記イオン伝導体層は、無機イオン伝導体材料の0〜30重量%の範囲のガラス形成添加剤を含む。上記イオン伝導体層は、本明細書中に記載された他の塩も可能であるが、任意に1以上のリチウム塩、例えばLiI、LiBr、LiCl、Li2CO3および/またはLi2SO4を含む。1つ以上のリチウム塩を、例えば0〜50モル%の範囲で、上記無機イオン伝導体材料に加えてもよい。
この実施例では、層の間の改善された接着強度を有する、自立型のセパレータ(例えば、イオン伝導性セパレータ複合体)上にイオン伝導体層を形成する方法を記載する。
リチウムオキシスルフィドイオン伝導体層が1μmの厚さを有した以外は、実施例1Aに記載したものと同様のイオン伝導体‐セパレータ複合体を形成した。上記リチウムオキシスルフィド層の付着前に、実施例1Aに記載したように、上記セパレータの表面をプラズマで処理した。
以下は、セパレータに不十分に結合されたイオン伝導体層を説明する比較例である。
上記イオン伝導体層の付着前に、上記セパレータをプラズマで処理しなかった以外は、
実施例1に記載された方法を用いて、イオン伝導体‐セパレータ複合体を形成した。
上記イオン伝導体‐セパレータ複合体はテープ試験に合格しなかったが、これはセパレータからのイオン伝導体層の剥離を実証する。
1μmのセラミックの厚さで、Gurley試験(TAPPI Standard T 536 om−12)によって測定された透気時間が9.7分未満であった。
この実施例では、リチウム‐硫黄電気化学電池における、実施例1のイオン伝導体‐セパレータ複合体の形成および性能を示す。
この比較例では、リチウム‐硫黄電気化学電池における、比較例1のイオン伝導体‐セパレータ複合体の形成および性能を示す。
この実施例では、透気試験(Gurley試験)によって示されるように、(実施例1に記載された方法と同様に製造された)イオン伝導体‐セパレータ複合体の流体に対するバリアとして作用する能力を実証する。各試料は、0.1〜0.5μmの範囲の細孔径を有する25μmの厚さのセパレータ、および上記セパレータの上にリチウムオキシスルフィドのコーティングを含んでいた。試料1、2、3、および6は、リチウムオキシスルフィドの添加前にプラズマ処理したセパレータを含んだ。試料4、5、および7は、リチウムオキシスルフィド層の添加前に処理されていないセパレータを含んだ。
多くの要素または要素のリストの、1つより多いも含む少なくとも1つ、任意に、リストに挙げられていない更なる項目を含むと解釈されるべきである。明確に示されている項目のみ、例えば、「〜の内の1つのみ」または「〜の内の正確に1つ」、或いは特許請求の範囲において使用される場合の「〜から成る」は、多くの要素または要素のリストの内の正確に1つを含むことを意味する。一般的に、本明細書中で用いられる用語「または」は、「どちらか」、「〜の内の1つ」、「〜の内の1つのみ」または「〜の内の正確に1つ」などの排他性を有する用語が先行する場合、排他的選択肢(即ち、「一方、または両方でない他方」)を示すものとして解釈されるのみである。特許請求の範囲において使用される場合の「本質的に〜から成る」は、特許法の分野で使用されるようなその通常の意味を有する。
102 … 第1電極
104 … 第2電極
106、500 … セパレータ
108 … 細孔
112、505 … イオン伝導体
504 … 構造体
510 … 電気活性材料
Claims (16)
- 電気活性材料としてのリチウムを含む第1電極;
第2電極;および
該第1電極および第2電極の間に配置された複合体;
を含み、
該複合体が、
5μm以下の平均細孔径を有する細孔を含むセパレータ;および
表面プラズマ処理された該セパレータに接合したイオン伝導体層;
を含み、
該セパレータが、少なくとも104[Ω・m]のバルク電気抵抗率を有し、
該イオン伝導体層が、少なくとも10−6[S/cm]のリチウムイオン伝導率を有し、
該イオン伝導体層が、0.1〜20重量%の酸化物含有量を有するリチウムオキシスルフィドを含み、および/または該イオン伝導体層が、0.001:1〜1.5:1の硫黄原子に対する酸素原子の原子比(O:S)を有するリチウムオキシスルフィドを含む、電気化学電池。 - 前記イオン伝導体層が、0.01:1〜0.25:1の硫黄原子に対する酸素原子の原子比(O:S)を有するリチウムオキシスルフィドを含む、請求項1記載の電気化学電池。
- 前記リチウムオキシスルフィドを含むイオン伝導体層が、複数のイオン伝導体層を含む多層構造体の一部である、請求項1記載の電気化学電池。
- 前記セパレータが、少なくとも1010[Ω・m]のバルク電気抵抗率を有する、請求項1記載の電気化学電池。
- 前記セパレータが、固体の、ポリマーセパレータである、請求項1記載の電気化学電池。
- 前記セパレータが、ポリマーバインダーと、セラミックまたはガラス質セラミック材料を含む充填剤との混合物を含む固体である、請求項1記載の電気化学電池。
- 前記リチウムオキシスルフィドが、式:
x(yLi2S+zLi2O)+MS2
(式中、Mは、Si、Ge、またはSnであり、y+z=1であり、xは0.5〜3の範囲である)
を有する、請求項1記載の電気化学電池。 - 前記イオン伝導体層が、前記イオン伝導体層用無機材料の5〜30重量%のガラス形成添加剤を含み、該ガラス形成添加剤がSiO2、Li2SiO3、Li4SiO4、Li3PO4、LiPO3、Li3PS4、LiPS3、B2O3およびB2S3から成る群から選択される、請求項1記載の電気化学電池。
- 前記イオン伝導体層が、1つ以上のリチウム塩を含む、請求項1記載の電気化学電池。
- 前記1つ以上のリチウム塩を、10〜50モル%の範囲で、前記イオン伝導体層用無機材料に加える、請求項9記載の電気化学電池。
- 前記複合体が、25℃でのリチウムイオン伝導率少なくとも10−5[S/cm]を有する、請求項1記載の電気化学電池。
- 前記セパレータの平均細孔径に対する前記イオン伝導体層の厚さの比(イオン伝導体層の厚さ:セパレータの平均細孔径)が、少なくとも1.1:1である、請求項1記載の電気化学電池。
- 前記セパレータおよび前記イオン伝導体層の間の接着強度が、少なくとも350N/mである、請求項1記載の電気化学電池。
- 前記セパレータおよび前記イオン伝導体層の間の接着強度が、ASTM D3359‐02規格に準拠するテープ試験を合格する、請求項1記載の電気化学電池。
- 前記電気活性材料がリチウムを含む、請求項1記載の電気化学電池。
- 前記電気活性材料が、リチウム金属および/またはリチウム合金を含む、請求項1記載の電気化学電池。
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US61/941,734 | 2014-02-19 | ||
PCT/US2015/016281 WO2015126885A1 (en) | 2014-02-19 | 2015-02-18 | Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor |
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EP2915203B1 (en) | 2012-11-02 | 2016-08-03 | Basf Se | Polymers for use as protective layers and other components in electrochemical cells |
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JP2016511517A (ja) | 2013-03-15 | 2016-04-14 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | 保護電極構造 |
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US10490796B2 (en) | 2014-02-19 | 2019-11-26 | Sion Power Corporation | Electrode protection using electrolyte-inhibiting ion conductor |
KR102316170B1 (ko) | 2014-02-19 | 2021-10-21 | 시온 파워 코퍼레이션 | 전해질-억제 이온 전도체를 포함하는 복합체를 사용한 전극 보호 |
US9755268B2 (en) | 2014-03-27 | 2017-09-05 | Sion Power Corporation | Gel electrolytes and electrodes |
EP3149798B1 (en) | 2014-05-30 | 2018-04-11 | Basf Se | Polymer for use as protective layers and other components in electrochemical cells |
KR102493741B1 (ko) | 2014-10-23 | 2023-01-30 | 시온 파워 코퍼레이션 | 전기화학 셀용 이온-전도성 복합재 |
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