JP2017536650A - カルシウム系二次電池用電解質、及びこれを含むカルシウム系二次電池 - Google Patents
カルシウム系二次電池用電解質、及びこれを含むカルシウム系二次電池 Download PDFInfo
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- JP2017536650A JP2017536650A JP2017517008A JP2017517008A JP2017536650A JP 2017536650 A JP2017536650 A JP 2017536650A JP 2017517008 A JP2017517008 A JP 2017517008A JP 2017517008 A JP2017517008 A JP 2017517008A JP 2017536650 A JP2017536650 A JP 2017536650A
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- Prior art keywords
- calcium
- electrolyte
- negative electrode
- battery
- secondary battery
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- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 92
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 13
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
Description
― 導電率計(例えば、Oakton CON 11標準導電率計)を用いて標準状態において測定したときに3mS/cmを超えるような高いイオン伝導性、
― バッテリ要素(セパレータ、電極等)に対して良好な濡れ性を示すこと、
― 例えば電解質は、水含量をカールフィッシャー滴定技術によって測定したときに、300ppm未満、例えば200ppm未満又は100ppm未満、例えば50ppm未満の水しか含まないように、実質的に水を含まないこと、
― サイクリックボルトアンペロメトリーを用いて約75℃において測定したときに、4.5Vを超えるように、電気化学安定窓(Electrochemical stability window)が広いこと。電気化学安定窓(ESW)は、ボルト単位で与えられる。このESWは、還元に対する安定性と酸化に対する安定性の差であり、従って使用する参照極によらずに同じになるであろうから、参照極の表示は不要である。ESWは、参照極としてのカルシウム金属、及び対極を有する3電極タイト(tight)電池を組み立て、75℃において、一般的に認知された方法:1mV/sの掃引速度におけるサイクリックボルトアンペロメトリーによって測定されてよい、
― 約−70℃及び300℃の間、例えば約−70℃及び270℃の間、又は約−70℃及び240℃の間、又は−30℃及び150℃の間に含まれる温度において測定したときの熱安定性。熱安定性は、例えばDSC 204F1 Netzsch カロリメータを用いて、10℃/分の昇温速度にて行われるDSC測定によって測定されてよい。電解質の安定性は、本質的にはこれに含有される溶媒の安定性によって決定される。溶媒は、その温度において分解しないときには、当該温度において熱的に安定であると考えられる。
― 例えば電解質の機械的特性を向上するために、架橋及び/又は熱硬化され得る成分、
― 例えば電解質のイオン伝導性を向上する、可塑剤、
― ナノ粒子/ナノセラミック、及び/又は
― カルシウム塩の解離を促進し、及び/又はカルシウム塩の溶解性を高める、(クラウンエーテルのような)成分
を含む。
― カルシウムイオンを受容及び放出する能力を有する負極活物質を含む負極、
― カルシウムイオンを受容及び放出する能力を有する正極活物質を含む正極、並びに
― 前記負極及び前記正極の間に配置された電解質、この電解質は、カルシウムイオン及び電解質媒体を含み、例えばこれらから成り、前記電解質は、標準状態において固体ではなく、且つ電解質媒体は少なくとも2つの別個の非水系溶媒を含む、
を含む、カルシウム系二次電池を開示する。
特記ない限り、本開示及び図面中の電位(ボルト単位)は、Ca2+/Ca対比の値である。電位は、定電圧電解装置によって擬参照電極対比で測定される。典型的にはフェロセン、又はコバルトセンのような同様の内部標準が使用される。フェロセンの使用は、非水系媒体中の作業に好適なものとして公知である。
― 負極活物質、例えば上記で定義されるカルシウム合金である成分(a1)、及び
― 電気伝導性及び/又は電極体積変化抑制機能を示す成分(a2)
から成るような、これらを含む混合物(a)に、圧縮等の加工をすることによって得ることができる。
成分(a1)は、混合物(a)の質量を基準として、約50%及び約100%の間、好ましくは約65%及び約95%の間、約70%及び約90%の間に含まれる量、例えば約75%で使用してよい。成分(a2)は、混合物(a)の質量を基準として、約0%及び約40%の間、好ましくは約10%及び約30%の間、例えば25%の量で使用してよい。
― 負極活物質、例えば上記で定義されるカルシウム合金である成分(b1)、
― 電気伝導性及び/又は電極体積変化抑制機能を示すを示す成分(b2)、
― バインダーである成分(b3)
― 溶媒である成分(b4)。
を含む、例えばこれらから成るスラリー(b)を処理することによって得ることができる。
― 電池のエネルギー密度が、市販のリチウム系二次電池のエネルギー密度よりも理論的に高いこと。特に本開示の負極の容量は、従来のリチウム系電池に典型的に使用されている、例えばグラファイト含有負極の容量よりも高いこと、及び
― 電池は、穏やかな温度において効果的に操作することができること。実際、標準状態において電解質が固体状ではないので、例えば、電解質を液状、導電状態に維持するために、過激な高温の操作温度を採用する必要がない(電解質としてCaCl2等の溶融カルシウム塩が使用されるときに必要となる)。本電池の操作温度は、通常の用途の大多数を許容し、従来のリチウム系電池の操作温度と大きな範囲でオーバーラップする。このことは、本電池が、従来の情報関連デバイス、通信デバイス(例えば、パーソナルコンピュータ、ビデオカメラ、及び携帯電話)、自動車工業、及び定置型発電デバイスにおける電源として使用できることを意味する。
1つの視点において、本開示は、上記で定義される非水カルシウム二次バッテリを含む定置型発電装置を開示する。
ステンレス鋼の集電体を有するカルシウム金属負極、及び電解質として0.3MのCa(ClO4)2を含むEC0.5:PC0.5。
ステンレス鋼集電体を有するカルシウム金属負極、及び電解質として0.3MのCa(BF4)2を含むEC0.5:PC0.5。
銅集電体を有するカルシウム金属負極、及び電解質として0.3MのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1。
種々の集電体を有するカルシウム金属負極、及び電解質として0.3MのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1。
ステンレス鋼上に堆積した金により構成される集電体を有するカルシウム金属負極、及び電解質としてxMのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1(x=0.3;0.65;1)。
負極として銅集電体を有しスズを含む複合フィルム、及び電解質として0.3MのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1。
負極として、集電体としてステンレス鋼プランジャーを有しスズを含む複合粉体、及び電解質として0.3MのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1。
負極として銅集電体を有しケイ素を含む複合フィルム、及び0.3MのCa(BF4)2を含むEC0.45:PC0.45:DMC0.1。
ステンレス鋼集電体を有するカルシウム金属負極、及び電解質として0.3MのCa(BF4)2を含むEC0.5:PC0.5。
Claims (17)
- カルシウムイオン及び電解質媒体を含む電解質であって、
前記電解質は標準状態で固体ではなく、
前記電解質媒体は、少なくとも2種の別個の非水系溶媒を含む、
電解質。 - 約20℃の温度及び約1気圧の圧力において10cPよりも低い粘度を有する、請求項1に記載の電解質。
- 少なくとも2種の別個の非水系溶媒のそれぞれは、環状カーボネート、直鎖状カーボネート、環状エステル、環状エーテル、直鎖状エーテル、及びこれらの混合物から成る群から独立に選択される、請求項1又は2に記載の電解質。
- 前記媒体はエチレンカーボネート(EC)を含む、請求項3に記載の電解質。
- 前記媒体はエチレンカーボネート(EC)及びプロピレンカーボネート(PC)を含む、請求項4に記載の電解質。
- 前記媒体は、式ECh:PC1−h、ここで、前記の比は体積:体積で表され、hは0≦h≦1である、で示される組み合わせを含む、請求項5に記載の電解質。
- 前記媒体は、式ECx:PCy:DMCz、ここで、前記の比は体積:体積で表され、hは0≦x、y、z≦1、x+y+z=1である、で示される、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、及びジメチルカーボネート(DMC)の組み合わせを含む、請求項5に記載の電解質。
- ― カルシウムイオンを受容及び放出する能力を有する負極活物質を含む負極、
― カルシウムイオンを受容及び放出する能力を有する正極活物質を含む正極、
― 請求項1〜7のいずれか一項以上で定義され、前記負極及び前記正極の間に配置された、電解質
を含む、カルシウム系二次電池。 - 温度制御要素を更に含む、請求項8に記載の電池。
- 前記負極は、金属カルシウム又はカルシウム合金を含む負極活物質を含む、請求項8又は9に記載の電池。
- 前記負極活物質は金属カルシウムを含む、請求項10に記載の電池。
- 前記負極活物質は、負極の電位がCa2+/Ca対比約2.5Vより低く、且つ比容量が約200mAh/gよりも高くなるようなカルシウム合金を含む、請求項10に記載の電池。
- 前記合金は、式(I)CamB、ここで、mは0≦m≦3であり、Bは金属又は半導体元素である、で表される、請求項10又は12に記載の電池。
- 前記負極は複合フィルム負極である、請求項1に記載の電池。
- 請求項8〜14のいずれか一項以上に記載のカルシウム系二次電池の稼働方法であって、
前記方法は約30℃〜150℃の間の電池稼働温度に設定する工程を含む、
方法。 - 請求項8〜14のいずれか一項以上に記載のカルシウム系二次電池を含む、非水カルシウム系二次バッテリ。
- 請求項16に記載の非水カルシウム系二次バッテリを含む、車両、電子デバイス、又は定置型発電デバイス。
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CN107004834A (zh) | 2017-08-01 |
EP3201976B1 (en) | 2024-06-19 |
US20170250438A1 (en) | 2017-08-31 |
CN107004834B (zh) | 2020-04-21 |
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