JP2018049833A - イオン性ゲル電解質、エネルギー貯蔵デバイス、およびそれらの製造方法 - Google Patents
イオン性ゲル電解質、エネルギー貯蔵デバイス、およびそれらの製造方法 Download PDFInfo
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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- 230000002269 spontaneous effect Effects 0.000 description 1
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- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】電気化学セルは、固体状態の印刷可能なアノード層、カソード層、ならびにアノード層およびカソード層に連結された非水性ゲル電解質層を含む。電解質層は、アノード層とカソード層との間を物理的に分離し、アノード層とカソード層との間で多価イオンの伝送を促進することによって、アノード層とカソード層との間にイオン性連通を提供するように構成される組成物を含む。前記セルは、追加のパッケージングを必要とせずに、4カ月間にわたって周囲環境で作動するように構成される。
【選択図】なし
Description
イオン液体は、ポリマーゲルに組み込まれる場合、それらは、他のポリマー性または固体状態電解質システムよりも数桁のオーダーで大きな液体様のイオン輸送特性を有する電解質を形成できる。こうしたイオン液体ゲル電解質はまた、構造的にロバスト性であることができ、圧縮下であっても電気化学セルの電極間に物理的分離を維持できる。さらに、周囲環境および室温条件において、ゲルは、イオン液体が無視できる程度の揮発性であるため、乾燥せず、または「発汗」もない。
さらに別の配置において、電気化学セル10は、キャパシタを含んでいてもよい。
Zn←→Zn2++2e− 式1
2e−+(2MnO2 −)Zn2+←→Zn2++2MnO2 式2
可能性としての基板の例としては、紙(例えばカード用紙または異なるタイプ/織り方/厚さの紙)、ポリマー性またはプラスチック材料(例えばポリエチレンテレフタレートまたはポリエステル(PET)、ポリエチレン、ポリプロピレン、Kapton、ポリイミド、ポリエステルエーテルケトン(PEEK)、ポリウレタン、ポリジメチルシロキサンまたは他のシリコーン樹脂)、種々の折り方およびメッシュの布地(例えば、ナイロン、綿、デニム)ケイ素、プリント回路基板(例えば硬化エポキシ樹脂基板、FR4、および可撓性回路基板)、ガラス、金属箔、またはこれらの組み合わせ(例えば布地裏打ちを有する布地)が挙げられるが、これらに限定されない。1つの配置において、基板は、用途に必要とされるようないずれかの形状に折り畳まれることができる。1つの配置において、デバイス、例えばマイクロプロセッサまたはMEMSデバイスは、基板68として使用できる。上述の基板のいずれかはまた、表面上にバッテリの一体化を可能にする接着性裏打ちを有していてもよい。
こうした単純性は、以前に可能であったよりも、多くのさらなる選択肢を有し、低コストの電気化学セルを製造することができる。
電解質厚さは、約15〜30μmであった。亜鉛スラリーは、電極およびそれ自体の集電体の両方として作用したが、ニッケル箔基板は、二酸化マンガン電極の集電体として使用した。
試験された多くのセルについて、適度に遅い充電および放電速度(C/2〜C/5)を用いて、活性化プロセスが、初期サイクル内で生じることが観測された。
試験セルは、容量において平均1mAh/cm2が得られ、面エネルギー密度において1.2mWh/cm2が得られた。
セルを、反対の極性を有するが、上記電位減衰試験と同じ大きさおよび時間長さを有する放電パルスに供することによって、バッテリは、興味深い「回復」挙動を示した。図27において観察されることは、放電パルス後の開回路に置かれる場合に、セルの電位が徐々に増大した。自己放電試験において適用されたように、セル電位と時間との関係を使用して、自己回復の機構を区別した。
典型的には、電子デバイスは、単一供給源、例えば一次バッテリからその電力を得る。その構成成分のいずれかが異なる供給電圧を必要とする場合に、追加の電力電気回路は、その必要とされる値にバッテリ電圧を変換するために必要とされる。電圧変換操作の効率は、使用される変換方法のタイプによって変動する:線形レギュレーターは、単純で低コストであるが、大きな電圧変化には全く不十分であり、所望でない熱散逸をもたらす。スイッチドモードの電圧コンバータ(例えばスイッチドキャパシタ)は、非常に効率良く(>75%)設計されることができ、これらのデバイスは、CMOS製作を用いて、線形レギュレーターに比べて領域を大量消費しないが、設計および一体化が複雑である。この議論において、典型的なワイアレスセンサは、オシレーターを通常含むマイクロコントローラおよび制御ユニット、通信手段構成成分、例えばトランシーバおよび/またはレシーバ、センサ、および電源を含有することが仮定される。
Claims (71)
- アノード層、
カソード層、および
前記アノード層およびカソード層に連結された非水性ゲル電解質層を含む電気化学セルであって、
前記電解質層は、前記アノード層と前記カソード層との間を物理的に分離し、
前記ゲル電解質層は、少なくとも1つのイオン液体および電解質塩が吸収されているポリマーを含み、
前記電解質層は、前記アノード層とカソード層との間に多価イオンの伝送を促進することによって、前記アノード層とカソード層との間のイオン性連通を提供するように構成される組成物を含む、電気化学セル。 - 前記アノード層、カソード層、および電解質層が、顕著な性能損失なく、変形できる可撓性の圧縮可能な層を含む、請求項1に記載の電気化学セル。
- 前記セルは、バッテリセルを含む、請求項2に記載の電気化学セル。
- 前記バッテリセルが再充電可能なバッテリセルである、請求項3に記載の電気化学セル。
- 前記カソードと電子連通した第1の集電体、および
前記アノードと電子連通した第2の集電体をさらに含む、請求項1に記載の電気化学セル。 - 1つ以上のアノード層、カソード層、電解質層および集電体が、液体形態で基板に堆積されるように構成され、しばらくした後に少なくとも半固体状態に固化する、請求項1に記載の電気化学セル。
- 前記セルが、追加のパッケージングを必要とせずに、4カ月間にわたって周囲環境で作動するように構成される、請求項1に記載の電気化学セル。
- 前記ポリマーネットワークが、ポリ(フッ化ビニリデン)(PVDF)、ポリ(フッ化ビニリデン)ヘキサフルオロホスフェート(PVDF−HFP)、ポリビニルアルコール(PVA)、ポリ(エチレンオキシド)(PEO)、ポリ(アクリロニトリル)(PAN)、およびポリ(メチルメタクリレート)(PMMA)、エポキシ誘導体、シリコーン誘導体からなる群から選択される1つ以上のポリマーを含む、請求項1に記載の電気化学セル。
- 前記イオン液体に溶解した前記電解質塩が、亜鉛イオン(Zn2+)、アルミニウム(Al3+)、マグネシウム(Mg2+)、およびイットリウム(Y2+)からなる群から選択されるカチオンを放出する、請求項1に記載の電気化学セル。
- 前記イオン液体に溶解した前記塩が、クロリド、テトラフルオロボレート(BF4−)、トリフルオロアセテート(CF3CO2−)、トリフルオロメタンスルホネート(CF3SO3−)、ヘキサフルオロホスフェート(PF6−)、ビス(トリフルオロメチルスルホニル)アミド(NTf2−)、ビス(フルオロスルホニル)イミド(N(SO2F)2−)からなる群から選択されるアニオンを放出する、請求項1に記載の電気化学セル。
- 前記イオン液体が、イミダゾリウム異型、ピロリジニウム異型、アンモニウム異型、ピリジニウム異型、ピペリジニウム異型、ホスホニウム異型、およびスルホニウム異型からなる群から選択される、室温でカチオンを有する塩である、請求項1に記載の電気化学セル。
- イオン液体が、クロリド、テトラフルオロボレート(BF4−)、トリフルオロアセテート(CF3CO2−)、トリフルオロメタンスルホネート(CF3SO3−)、ヘキサフルオロホスフェート(PF6−)、ビス(トリフルオロメチルスルホニル)アミド(NTf2−)、ビス(フルオロスルホニル)イミド(N(SO2F)2−)からなる群から選択される、室温でアニオンを有する塩である、請求項11に記載の電気化学セル。
- 前記アノードが、亜鉛、アルミニウム、マグネシウム、およびイットリウムからなる群から選択される構成成分を含む、請求項1に記載の電気化学セル。
- 前記カソードが金属酸化物を含む、請求項1に記載の電気化学セル。
- 金属酸化物が、五酸化バナジウム(V2O5)、二酸化マンガン(MnO2)、酸化コバルト(CoxOy)、酸化チタン(TixOy)、酸化鉛(PbxOy)からなる群の1つ以上から選択される構成成分を含む、請求項14に記載の電気化学セル。
- 前記集電体が、ニッケル、ステンレススチール、金、およびアルミニウムからなる群から選択される金属を含む金属箔を含む、請求項5に記載の電気化学セル。
- 前記アノード層および前記カソード層のそれぞれが、8μm〜60μmの厚さを有する、請求項1に記載の電気化学セル。
- 前記電解質がおおよそ1μm〜15μmの厚さを有する、請求項1に記載の電気化学セル。
- 前記集電体が、それぞれ8μm〜60μmの厚さを有する印刷された層を含む、請求項5に記載の電気化学セル。
- 前記集電体が、それぞれ1μm〜80μmの厚さを有する金属箔を含む、請求項5に記載の電気化学セル。
- 前記液体電解質が、イオン液体中、0.2〜0.75Mの亜鉛塩濃度を含む、請求項1に記載の電気化学セル。
- 前記液体電解質が、0.4〜0.75Mの亜鉛塩濃度を含む、請求項21に記載の電気化学セル。
- 前記液体電解質が、0.45〜0.65Mの亜鉛塩濃度を含む、請求項21に記載の電気化学セル。
- 前記液体電解質が2.3mS/cmを超えるイオン伝導度を有する、請求項22に記載の電気化学セル。
- 0.001mA/cm2〜100mA/cm2の範囲の電流密度出力を有する、請求項1に記載の電気化学セル。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項1に記載の電気化学セル。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、25μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項26に記載の電気化学セル。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項27に記載の電気化学セル。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、75μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項1に記載の電気化学セル。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項29に記載の電気化学セル。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、40μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項30に記載の電気化学セル。
- 6カ月を超える期間において周囲環境に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項1に記載の電気化学セル。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項1に記載の電気化学セル。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、25μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項33に記載の電気化学セル。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項34に記載の電気化学セル。
- 1日を超える期間において−20℃未満の温度に曝される間に、前記ゲル電解質層が、75μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項1に記載の電気化学セル。
- 電気機械セルにおけるアノードとカソードとの間を物理的に分離するように構成される電解質であって、
室温イオン液体電解質および非水性ゲルを形成するためにポリマー中に吸収された溶解塩を含み、
前記電解質を横断する多価イオンの伝送を促進することによって前記アノードとカソードとの間にイオン性連通を提供するように構成される組成物を含む、電解質。 - 前記電解質が、少なくとも1つのイオン液体および電解質塩が吸収されているポリマーを含む、請求項37に記載の電解質。
- 前記ポリマーが、ポリ(フッ化ビニリデン)(PVDF)、ポリ(フッ化ビニリデン)ヘキサフルオロホスフェート(PVDF−HFP)、ポリビニルアルコール(PVA)、ポリ(エチレンオキシド)(PEO)、ポリ(アクリロニトリル)(PAN)、およびポリ(メチルメタクリレート)(PMMA)、エポキシ誘導体、シリコーン誘導体からなる群から選択される1つ以上のポリマーを含む、請求項37に記載の電解質。
- 前記イオン液体が、イミダゾリウム異型、ピロリジニウム異型、アンモニウム異型、ピリジニウム異型、ピペリジニウム異型、ホスホニウム異型、およびスルホニウム異型からなる群から選択される、室温でカチオンを有する塩である、請求項38に記載の電解質。
- 前記イオン液体が、クロリド、テトラフルオロボレート(BF4−)、トリフルオロアセテート(CF3CO2−)、トリフルオロメタンスルホネート(CF3SO3−)、ヘキサフルオロホスフェート(PF6−)、ビス(トリフルオロメチルスルホニル)アミド(NTf2−)、ビス(フルオロスルホニル)イミド(N(SO2F)2−)からなる群から選択される、室温でアニオンを有する塩である、請求項40に記載の電解質。
- おおよそ1μm未満の厚さを有するゲル層に配置されるように構成される、請求項1に記載の電解質。
- 前記液体電解質が、イオン液体中、0.2〜0.75Mの亜鉛塩濃度を含む、請求項42に記載の電解質。
- 前記液体電解質が、0.4〜0.75Mの亜鉛塩濃度を含む、請求項43に記載の電解質。
- 前記液体電解質が、0.45〜0.65Mの亜鉛塩濃度を含む、請求項44に記載の電解質。
- 前記液体電解質が2.3mS/cmを超えるイオン伝導度を有する、請求項44に記載の電解質。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項42に記載の電解質。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、25μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項47に記載の電解質。
- 3カ月を超える期間において20℃〜45℃の範囲の温度に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項48に記載の電解質。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、75μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項42に記載の電解質。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項50に記載の電解質。
- 1カ月を超える期間において45℃〜90℃の範囲の温度に曝される間に、前記ゲル電解質層が、40μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項51に記載の電解質。
- 6カ月を超える期間において周囲環境に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項42に記載の電解質。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、50μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項42に記載の電解質。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、25μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項54に記載の電解質。
- 3カ月を超える期間において−20℃〜20℃の範囲の温度に曝される間に、前記ゲル電解質層が、15μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項55に記載の電解質。
- 1日を超える期間において−20℃未満の温度に曝される間に、前記ゲル電解質層が、75μA/cm2未満の出力リーク電流密度を維持するように構成される、請求項42に記載の電解質。
- 第1の電極インクおよび第2の電極インクを提供する工程と、
液体電解質インクを提供する工程と、
第1の電極インクの第1の電極層を印刷する工程と、
電解質インクの層を印刷する工程と、
第2の電極インクの第2の電極層を印刷する工程と、
を備え、
前記電解質インクの層は、第1の電極層と第2の電極層との間を物理的に分離して、電気化学セルを形成し、
前記電解質の層は、第1の電極層と第2の電極層との間で多価イオンの伝送を促進することにより、第1の電極層と第2の層との間にイオン性連通を提供するように構成される、電気化学セルを製造する方法。 - 集電体インクを提供する工程と、
前記第1の電極層および第2の電極層の1つ以上に隣接する集電体インクの層を印刷する工程と、をさらに備えた、請求項58に記載の方法。 - 前記電気化学セルが周囲温度で製作される、請求項58に記載の方法。
- 前記電気化学セルが周囲圧力で製作される、請求項60に記載の方法。
- 前記インクが、溶液、懸濁液およびスラリーからなる群から選択される液体である、請求項58に記載の方法。
- 前記第1の電極インクおよび第2の電極インクが、活性電極粒子、ポリマー結合剤、任意の添加剤、および溶媒のスラリーを含む、請求項58に記載の方法。
- 前記電解質が、少なくとも1つのイオン液体および少なくとも1つの電解質塩が吸収されているポリマーを含む、請求項58に記載の方法。
- 前記ポリマーが、ポリ(フッ化ビニリデン)(PVDF)、ポリ(フッ化ビニリデン)ヘキサフルオロホスフェート(PVDF−HFP)、ポリビニルアルコール(PVA)、ポリ(エチレンオキシド)(PEO)、ポリ(アクリロニトリル)(PAN)、およびポリ(メチルメタクリレート)(PMMA)、エポキシ誘導体、シリコーン誘導体からなる群から選択される1つ以上のポリマーを含む、請求項64に記載の方法。
- 前記イオン液体が、イミダゾリウム異型、ピロリジニウム異型、アンモニウム異型、ピリジニウム異型、ピペリジニウム異型、ホスホニウム異型、およびスルホニウム異型からなる群から選択される、室温でカチオンを有する塩である、請求項64に記載の方法。
- 前記イオン液体が、クロリド、テトラフルオロボレート(BF4−)、トリフルオロアセテート(CF3CO2−)、トリフルオロメタンスルホネート(CF3SO3−)、ヘキサフルオロホスフェート(PF6−)、ビス(トリフルオロメチルスルホニル)アミド(NTf2−)、ビス(フルオロスルホニル)イミド(N(SO2F)2−)からなる群から選択される、室温でアニオンを有する塩である、請求項66に記載の方法。
- 前記第1の電極層が、亜鉛、アルミニウム、マグネシウム、およびイットリウムからなる群から選択される構成成分を含む、請求項64に記載の方法。
- 前記第2の電極層が、金属酸化物からなる群から選択される粒子を含む、請求項64に記載の方法。
- 前記印刷工程の少なくとも1つが、直接描画ディスペンサ方法を用いて行われる、請求項58に記載の方法。
- 前記印刷工程の少なくとも1つが、以下の方法から選択される方法を用いて行われる、請求項58に記載の方法:スクリーン印刷、グラビア印刷、パッド印刷、インクジェット印刷、フレキソコーティング、スプレーコーティング、超音波スプレーコーティングまたはスロットダイコーティング。
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US20140059820A1 (en) | 2014-03-06 |
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US10826119B2 (en) | 2020-11-03 |
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US20160344062A1 (en) | 2016-11-24 |
US10297862B2 (en) | 2019-05-21 |
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US9368283B2 (en) | 2016-06-14 |
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