JP7109790B2 - 炭素系材料を含むデバイス及びその製造 - Google Patents
炭素系材料を含むデバイス及びその製造 Download PDFInfo
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- JP7109790B2 JP7109790B2 JP2019511650A JP2019511650A JP7109790B2 JP 7109790 B2 JP7109790 B2 JP 7109790B2 JP 2019511650 A JP2019511650 A JP 2019511650A JP 2019511650 A JP2019511650 A JP 2019511650A JP 7109790 B2 JP7109790 B2 JP 7109790B2
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
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Description
本出願は、2016年8月31日に出願された米国仮特許出願第62/381,859号の利益を主張し、その出願は参照により本明細書に組み込まれるものとする。
図8は、様々な炭素形態805、810、815、820、及び825の例を概略的に示す。このような炭素形態は、様々な炭素系材料を形成し得る。炭素形態は、官能基を含み得る。所与の炭素形態は、例えば、1つ以上のヒドロキシル及び/またはエポキシ官能基830、1つ以上のカルボキシル官能基835、1つ以上の他の官能基(例えばカルボニル官能基)、またはこれらの任意の組み合わせを含み得る。炭素形態805は、例えばグラファイトであり得る。グラファイトは、それぞれが1原子の厚さである複数の炭素シート840(例えば約100以上、1,000以上、10,000以上、100,000以上、100万以上、1000万以上、1億以上、またはこれを超える数以上)を含み得る。複数の炭素シート840は、互いに上に積み重ねられ得る(例えば強いファンデルワールス力を受けて)。炭素シート840は互いに密着するため、堆積の内部はアクセス不可能であり得る(例えば上部及び底部シートのみアクセス可能であり得るが、内部のシートはファンデルワールス相互作用により互いに密着しているため、細孔は存在しない)。炭素形態805は、実質的に官能基を含み得ない。炭素形態810は、例えばグラフェンであり得る。グラフェンは、1原子の厚さである炭素シート845を含み得る。炭素形態810は、実質的に官能基を含み得ない。炭素形態815は、例えばグラフェン酸化物(例えば溶液中の単一グラファイト酸化物)であり得る。グラフェン酸化物は、1原子の厚さである炭素シート850を含み得る。いくつかの実施形態において、1つ以上の炭素形態815は凝集し得る。このような場合、個々の炭素シート815が分離され得る。炭素シートは、ファンデルワールス相互作用により凝集し得ない。炭素形態815は、1つ以上のヒドロキシル及び/またはエポキシ官能基830と、1つ以上のカルボキシル官能基835とを含み得る。ヒドロキシル及び/またはエポキシ官能基830は、炭素シート850の表面に付けられ得る、あるいは結合/接合され得る。カルボキシル官能基835は、炭素シート850の縁部に付けられ得る、あるいは結合/接合され得る。炭素形態825は、例えば数層のグラフェン酸化物(例えば溶液中の二層または三層のグラファイト酸化物)であり得る。数層のグラフェン酸化物は、それぞれが1原子の厚さである2枚以上の炭素シートまたは層860を含み得る。2枚以上の炭素シートまたは層860は、ファンデルワールス相互作用により共に保持され得る。いくつかの実施形態において、数層のグラフェン酸化物は、2枚以上、3枚以上、4枚以上、5枚以上、6枚以上、7枚以上、8枚以上、9枚以上、または10枚以上の炭素シートまたは層860を含み得る。一実施形態において、数層のグラフェン酸化物は、10枚以下の炭素シートまたは層860(例えば最大10枚の炭素シートまたは層)を含み得る。いくつかの実施形態において、数層のグラフェン酸化物は、2~3、2~4、2~5、2~6、2~7、2~8、2~9、2~10、3~4、3~5、3~6、3~7、3~8、3~9、3~10、4~5、4~6、4~7、4~8、4~9、4~10、5~6、5~7、5~8、5~9、5~10、6~7、6~8、6~9、6~10、7~8、7~9、7~10、8~9、8~10、または9~10枚の炭素シートまたは層860を含み得る。いくつかの実施形態において、数層のグラフェン酸化物は、2~4または2~3枚の炭素シートまたは層860を含み得る。一実施形態において、数層のグラフェン酸化物は、最大4枚の炭素シートまたは層860を含む。別の実施形態において、数層のグラフェン酸化物は、最大4枚の炭素シートまたは層860を含む。炭素形態825は、1つ以上のカルボキシル官能基835を含み得る。カルボキシル官能基835は、1枚以上の炭素シート860の縁部に付けられ得る、あるいは結合/接合され得る。いくつかの実施形態において、カルボキシル官能基835は、炭素シートまたは層860の堆積における上部及び底部炭素シート860の縁部に主に、または縁部にのみ、付けられ得る、あるいは結合/接合され得る。いくつかの実施形態において、カルボキシル官能基835は、炭素シート860のうちのいずれか(例えば、それぞれ、または少なくとも2、3、4枚以上)の縁部に付けられ得る、あるいは結合/接合され得る。炭素形態820は、例えば還元グラフェン酸化物(例えば溶液中の多孔質炭素シート(PCS)(複数可))であり得る。還元グラフェン酸化物は、1原子の厚さである炭素シート855を含み得る。炭素形態820は、1つ以上のカルボキシル官能基835を含み得る。カルボキシル官能基835は、炭素シート855の縁部に付けられ得る、あるいは結合/接合され得る。
図1は、PCSの作成の一例を概略的に示す。グラファイト101は、化学的に酸化され、グラファイト酸化物またはグラフェン酸化物102に剥離され得る。本開示の目的のため、グラファイト酸化物及びグラフェン酸化物という用語は、互換的に使用される。場合によっては、グラファイト酸化物及びグラフェン酸化物は、本明細書においてまとめて「GO」と称される。
本開示のエネルギー蓄積デバイスは、少なくとも1つの電極(例えば正極及び負極)を備え得る。本開示の炭素系材料は、正極(放電中のカソード)、負極(放電中のアノード)、または両方において提供され得る。特定の実施形態において、エネルギー蓄積デバイスは、リチウムイオンバッテリーであり得る。特定の実施形態において、エネルギー蓄積デバイスは、リチウム金属バッテリーであり得る。特定の実施形態において、エネルギー蓄積デバイスは、スーパーキャパシタであり得る。
リチウムイオンバッテリー(LIB)は、負極を含み得る。いくつかの実施形態において、LIBは、炭素ベースの負極(例えばグラファイトまたは炭素ナノチューブを含む)を備え得る。いくつかの実施形態において、LIBは、シリコン(Si)の負極を備え得る。いくつかの実施形態において、LIBは、合金ベースの負極(例えば錫合金を含む)を備え得る。いくつかの実施形態において、LIBは、酸化物または硫化物ベースの負極(例えば酸化マンガン(II)(MnO)または硫化マグネシウム(MgS)を含む)を備え得る。LIBは、例えば層状酸化物(例えばLiCoO2)、スピネル(例えばLiMn2O4)、またはかんらん石(例えばLiFePO4)といった酸化物を含む正極を備え得る。LIBは、導電性添加剤(複数可)を含み得る。導電性添加剤(複数可)は、正極、負極、またはその両方に提供され得る。導電性添加剤(複数可)には、例えば黒色炭素または炭素ナノチューブが含まれ得る。LIBは、バインダーを備えてもよく、バインダーは、第1のバインダー及び第2のバインダーのうち少なくとも1つを含む。いくつかの実施形態において、第1のバインダーは、第2のバインダーと同じである。いくつかの実施形態において、第1のバインダーは、第2のバインダーとは異なる。LIBは、電解質を含み得る。電解質には、例えば、有機溶液(例えば炭酸エチレン、炭酸ジメチル、または炭酸ジエチル)中のリチウム塩(例えば六フッ化リン酸リチウム(LiPF6)、四フッ化ホウ酸リチウム(LiBF4)、または過塩素酸リチウム(LiClO4))が含まれ得る。
以下、92%以下、91.5%以下、91%以下、90.5%以下、90%以下、89.5%以下、89%以下、88.5%以下、88%以下、87.5%以下、87%以下、86.5%以下、86%以下、85.5%以下、85%以下、84.5%以下、84%以下、83.5%以下、83%以下、82.5%以下、82%以下、81.5%以下、81%以下、80.5%以下、80%以下、79.5%以下、79%以下、78.5%以下、78%以下、77.5%以下、77%以下、76.5%以下、76%以下、75.5%以下、75%以下、74.5%以下、74%以下、73.5%以下、73%以下、72.5%以下、72%以下、71.5%以下、71%以下、70.5%以下、70%以下、69.5%以下、69%以下、68.5%以下、68%以下、67.5%以下、67%以下、66.5%以下、66%以下、65.5%以下、65%以下、64%以下、63%以下、62%以下、61%以下、60%以下、59%以下、58%以下、57%以下、56%以下、55%以下、54%以下、53%以下、52%以下、51%以下、または50%以下。このような活物質のうちの1つ以上は、1つ以上の他の材料(例えば本明細書で説明される1つ以上の他の電極材料及びそれらの濃度)と併せて、このような濃度で電極に存在し得る。
本開示のエネルギー蓄積デバイスは、電極、セパレータ(複数可)、電解質、及び包装形態を含み得る。このような構成要素は、異なる方法で、製造され、組み立てられ得る。特定の実施形態では、個々の構成要素が製造され、後で組み立てられ得る。いくつかの実施形態において、構成要素は、巻き込みまたは回転により組み立てられ得る。(例えば図9及び図20を参照)。例えば、バッテリーセルを作る方法は、セパレータの第1のシートを用意することと、セパレータの第1のシート上に正極のシート(例えば本開示の炭素系材料を含む)を配置することと、正極のシート上にセパレータの第2のシートを配置することと、セパレータの第2のシート上に負極のシート(例えばグラファイトを含む)を配置することと、シートを回転させてバッテリーセル(巻込型セル)を形成することとを含み得る。いくつかの実施形態において、構成要素は、積層することにより組み立てられ得る(例えば図18及び図19参照)。
市販されているエネルギー蓄積デバイスは、約1000mAhの電荷蓄積容量、1キログラムあたり500~1500ワット(W/kg)の電力密度、及び500サイクルのサイクル安定性を提供し得る。しかしながら、これらの数値をさらに向上させるためには、当技術の幅広い採用、特に、電気自動車及び電力網規模のエネルギー蓄積などの大規模な適用が必要である(例えば電気自動車の価格を引き下げ、清潔で緑豊かな環境に貢献する)。
別段の定義がない限り、本明細書で使用される全ての技術用語は、本開示が属する技術分野の当業者により一般に理解される意味と同じ意味を有する。本明細書及び添付の特許請求の範囲で使用されるように、単数形「a」、「an」、及び「the」は、文脈上明らかに別段の指示がない限り、複数の言及を含む。本明細書における「または」へのいずれの言及も、別段の明記がない限り、「及び/または」を包含することが意図される。
例示のバッテリーは、表1に示されるように、グラファイトを含む負極(放電中のアノード)と、PCS/リチウムニッケルコバルトアルミニウム酸化物(NCA)を含む正極(放電中のカソード)とを備える少なくとも1つのセルを有する。
例示のバッテリーは、表2に示されるように、グラファイトを含む負極(放電中のアノード)と、PCS/リチウムニッケルマンガンコバルト酸化物(NMC)を含む正極(放電中のカソード)とを備える少なくとも1つのセルを有する。
例示のバッテリーは、表3に示されるように、グラファイトを含む負極(放電中のアノード)と、PCS/リン酸鉄リチウム(LFP)を含む正極(放電中のカソード)とを備える少なくとも1つのセルを有する。
Claims (26)
- a)第1の電極と、
b)第2の電極と、
c)前記第1の電極と前記第2の電極との間にセパレータと
を有するエネルギー蓄積デバイスであって、
前記第1の電極は、
i)グラフェンシートの縁部にのみ接合した1又はそれ以上のカルボキシル官能基を含む複数の多孔質グラフェンシートと、
ii)第1のバインダーとを備え、
前記第2の電極は、
i)活物質と、
ii)第2のバインダーと、
iii)導電性添加剤とを備える、
前記エネルギー蓄積デバイス。 - 前記第1のバインダー及び前記第2のバインダーのうちの少なくとも1つは、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ペルフルオロアルコキシポリマー、フッ素化エチレンプロピレン、ポリエチレンテトラフルオロエチレン、ポリエチレンクロロトリフルオロエチレン、ペルフルオロ化プラストマ、フッ化炭素、フッ化クロロトリフルオロエチレンビニリデン、フルオロエラストマ、テトラフルオロエチレン-プロピレン、ペルフルオロポリエーテル、ペルフルオロスルホン酸、ペルフルオロポリオキセタン、P(VDF-トリフルオロエチレン)、P(VDF-テトラフルオロエチレン)、またはこれらの任意の組み合わせを含む、請求項1に記載のデバイス。
- 前記導電性添加剤は、黒色炭素、アセチレンブラック、ファーネスブラック、気相成長炭素繊維、炭素ナノチューブ、多孔質炭素シート、またはこれらの任意の組み合わせを含む、請求項1に記載のデバイス。
- 前記活物質は、リン酸鉄リチウム、リチウムニッケルコバルトアルミニウム酸化物、リチウムニッケルマンガンコバルト酸化物、リチウムコバルト酸化物、リチウムマンガン酸化物、チタン酸リチウム、リチウム硫黄、またはこれらの任意の組み合わせを含む、請求項1に記載のデバイス。
- 約800ミリアンペア時(mAh)~約4,000mAhの蓄積容量を有する、請求項1に記載のデバイス。
- 少なくとも約800mAhの蓄積容量を有する、請求項1に記載のデバイス。
- 約80mAh/g~約1000mAh/gの蓄積容量を有する、請求項1に記載のデバイス。
- 少なくとも約80mAh/gの蓄積容量を有する、請求項1に記載のデバイス。
- 約500サイクル~約1500サイクルのサイクル寿命を有する、請求項1に記載のデバイス。
- 少なくとも約500サイクルのサイクル寿命を有する、請求項1に記載のデバイス。
- 約5ミリオーム~約100ミリオームの等価直列抵抗を有する、請求項1に記載のデバイス。
- 最大約100ミリオームの等価直列抵抗を有する、請求項1に記載のデバイス。
- 電極を製造する方法であって、
a)バインダーと溶媒を混合することと、
b)前記バインダー及び前記溶媒を加熱することと、
c)グラフェンシートの縁部にのみ接合した1又はそれ以上のカルボキシル官能基を含む複数の多孔質グラフェンシートを、前記バインダー及び前記溶媒に混ぜて、スラリーを形成することと、
d)ホイル上に前記スラリーをロールコーティングすることと、
e)前記ホイル上の前記スラリーを乾燥させることと、
f)前記ホイル上の前記スラリーをロールプレスすることと、
g)前記ホイル上の前記スラリーを切断することと
を含む前記方法。 - 前記バインダーは、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ペルフルオロアルコキシポリマー、フッ素化エチレンプロピレン、ポリエチレンテトラフルオロエチレン、ポリエチレンクロロトリフルオロエチレン、ペルフルオロ化プラストマ、フッ化炭素、フッ化クロロトリフルオロエチレンビニリデン、フルオロエラストマ、テトラフルオロエチレン-プロピレン、ペルフルオロポリエーテル、ペルフルオロスルホン酸、ペルフルオロポリオキセタン、P(VDF-トリフルオロエチレン)、P(VDF-テトラフルオロエチレン)、またはこれらの任意の組み合わせを含む、請求項13に記載の方法。
- 前記溶媒は、2-ピロリドン、n-ビニルピロリドン、n-メチル-2-ピロリドン、メチルエチルケトン、またはこれらの任意の組み合わせを含む、請求項13に記載の方法。
- 前記スラリーは、リチウム化金属化合物をさらに含む、請求項13に記載の方法。
- 前記リチウム化金属化合物は、リチウムニッケルコバルトアルミニウム酸化物、リチウムニッケルマンガンコバルト酸化物、リン酸鉄リチウム、またはこれらの任意の組み合わせを含む、請求項16に記載の方法。
- 前記複数の多孔質グラフェンシートは、0.3~0.6w/w%の濃度で前記スラリー中に存在する、請求項13に記載の方法。
- 前記複数の多孔質グラフェンシートは、0.5~1.0w/w%の濃度で前記電極に存在する、請求項13に記載の方法。
- 前記バインダーは、約0.5~約10w/w%の濃度で前記スラリー中に存在する、請求項13に記載の方法。
- 前記バインダーは、約1~約15w/w%の濃度で前記電極に存在する、請求項13に記載の方法。
- 前記溶媒は、約10~約60w/w%の濃度で前記スラリー中に存在する、請求項13に記載の方法。
- 前記第1の電極は、前記複数の多孔質グラフェンシートを約0.5~約1質量%の濃度で含み、
前記第1の電極は、さらに、リチウムニッケルコバルトアルミニウム酸化物を約96~約97質量%の濃度で含み、
前記第1のバインダーは、ポリフッ化ビニリデンを含み、
前記第1の電極は、さらに、前記第1のバインダーを約2.5質量%の濃度で含む、請求項1に記載のデバイス。 - 前記第2の電極は、さらに、約95質量%のグラファイトを含み、
前記第2のバインダーは、ポリフッ化ビニリデンを含み、
前記導電性添加剤は、黒色炭素を含み、
前記第2の電極は、さらに、前記第2のバインダーを約5質量%の濃度で含み、
前記第2の電極は、さらに、前記導電性添加剤を約1質量%の濃度で含む、請求項1に記載のデバイス。 - 前記第1の電極は、前記複数の多孔質グラフェンシートを約0.5~約1質量%の濃度で含み、
前記第1の電極は、さらに、リチウムニッケルマンガンコバルト酸化物を約96~約97質量%の濃度で含み、
前記第1のバインダーは、ポリフッ化ビニリデンを含み、
前記第1の電極は、さらに、前記第1のバインダーを約2.5質量%の濃度で含む、請求項1に記載のデバイス。 - 前記第1の電極は、前記複数の多孔質グラフェンシートを約0.5~約1質量%の濃度
で含み、
前記第1の電極は、さらに、リン酸鉄リチウムを約96~約97質量%の濃度で含み、
前記第1のバインダーは、ポリフッ化ビニリデンを含み、
前記第1の電極は、さらに、前記第1のバインダーを約2.5質量%の濃度で含む、請求項1に記載のデバイス。
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KR102535218B1 (ko) | 2023-05-22 |
BR112019004128A2 (pt) | 2019-05-28 |
AU2017321294B2 (en) | 2021-12-09 |
WO2018044786A1 (en) | 2018-03-08 |
CN109845004A (zh) | 2019-06-04 |
TW201841422A (zh) | 2018-11-16 |
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