TWI728063B - 減少排氣的方法 - Google Patents
減少排氣的方法 Download PDFInfo
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- TWI728063B TWI728063B TW106107582A TW106107582A TWI728063B TW I728063 B TWI728063 B TW I728063B TW 106107582 A TW106107582 A TW 106107582A TW 106107582 A TW106107582 A TW 106107582A TW I728063 B TWI728063 B TW I728063B
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- carbon
- ionic liquid
- tetrafluoroborate
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000010943 off-gassing Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- -1 tetrafluoroborate salt Chemical class 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
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- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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Abstract
一種減少由含碳電極及至少一種離子液體組成之超級電容器中之排氣的方法,其特徵在於以下步驟:(a)使該等含碳電極與四氟硼酸鹽接觸;(b)在與該鹽接觸的同時,於電荷儲存於該等電極上且自該等電極放電的循環期間,施加電勢差在該等含碳電極兩端;以及(c)繼續另外的步驟(b)之循環,直至基本上不再自該系統發生進一步排氣為止。
Description
發明領域 本發明係關於一種用於基本上防止採用離子液體電解質之超級電容器中之不當排氣的方法。
發明背景 在吾人之同在申請中申請案PCT/GB2015/053003及GB1518385.8中,吾人已教示由含石墨烯電極及電解質組成的超級電容器,含石墨烯電極由多孔膜隔開,電解質由一或多種離子液體組成,例如在低於1000℃之溫度下通常係液體的四級有機鹽。雖然此類超級電容器可以在超過2.5v之電壓下容易地充電且具有良好的電荷保持能力,但是其具有以下問題:在使用時且經過多個充電及放電循環,其具有排氣的趨勢。若超級電容器將用作諸如平板電腦或智慧型電話之消費型電子裝置的一部分或其配件,則排氣通常係不當的;且當超級電容器本身被構築為輕質可撓性袋時,自安全角度來看,排氣尤其是個問題。在該等情況下,袋本身往往會迅速膨脹,引起袋將爆裂的危險。在此排氣過程中形成的產物通常係氫氣、一氧化碳及二氧化碳以及少量其他揮發性有機物質,表明其源自系統中殘餘水的分解及/或所存在之石墨烯或其他碳組分之表面上的有機官能基之分解及/或電解質因系統中所存在之催化性有機及無機物種所致之分解。
吾人現已研發出一種解決此問題的方法,該方法涉及在將超級電容器用於顯著電荷儲存負荷之前用四氟硼酸鹽預處理電極。因此,根據本發明之一個態樣,提供一種減少由含碳電極及至少一種離子液體組成之超級電容器中之排氣的方法,該方法之特徵在於以下步驟:(a)使含碳電極與四氟硼酸鹽接觸;(b)在與鹽接觸的同時,於電荷儲存於電極上且自電極放電的循環期間,施加電勢差在含碳電極兩端;及(c)繼續另外的步驟(b)之循環,直至基本上不再自系統發生進一步排氣為止。
Romann等人在Electrochimica Acta 2014 125 第183-190頁中論述了離子液體四氟硼酸1-乙基-3-甲基咪唑鎓在碳電極表面上的分解。CN104867701教示一種製造超級電容器之方法,其中藉由在添加電解質之前使用真空及乾氮氣淨化之循環移除水及氧氣。JP2014179646教示使用具有極低水分含量的γ-丁內酯作為用於電解質之溶劑來製造超級電容器。US7924549揭示一種電化電容器,其中電解質係非質子性溶劑中之濃度為至少1.5 M的四氟硼酸四級銨鹽。最後,WO2012/056050教示一種提高雙層電容器之工作電壓的方法,其係藉由逐步施加逐漸升高的調節電壓,直至達成工作電壓。
發明概要 在本發明之一個較佳實施例中,含碳電極包含陽極及陰極表面,其基本上由呈可撓性薄片(例如鋁、銀或銅箔)形式的導電金屬集電器組成,該導電金屬集電器塗佈有由碳電荷攜帶元件組成的層。在另一實施例中,此等陽極及陰極表面中之至少一些安置於同一個集電器薄片之相對側上。適當地,此等電荷攜帶元件中之至少一些係平均最長維度小於1微米、較佳小於100奈米的碳粒子。較佳地,此等粒子展現介孔性,其中間隙孔的大小範圍係2至50奈米。在另一實施例中,碳電荷攜帶元件可以用其他可以賦予最終超級電容器一定程度之贗電容特性的材料之奈米粒子補充;例如金屬之鹽、氫氧化物及氧化物,該等金屬諸如鋰或具有超過一種氧化態的過渡金屬,包括鎳、錳、釕、鉍、鎢或鉬。
在一個較佳實施例中,層係由嵌入於導電聚合物黏合劑基質中的碳粒子組成且其特徵在於粒子與黏合劑之重量比在0.2:1至20:1之範圍內。在另一實施例中,碳粒子包括石墨烯粒子;在另一實施例中,碳粒子包括碳奈米管。在一個較佳實施例中,採用石墨烯及碳奈米管之混合物,視情況存在活性碳。在另一適合實施例中,碳粒子包含這三種組分之混合物,其中活性碳、碳奈米管及石墨烯係以重量比0.5-2000 : 0.5-100 : 1、較佳0.5-1500 : 0.5-80 : 1存在。
術語活性碳意謂表面積通常大於500 m2
g-1
、較佳係1000至3600 m2
g-1
且平均粒度小於1微米的任何高純度非晶碳。此類材料容易自多個商業來源獲得。所用的碳奈米管通常具有在2-200微米(較佳100-300微米)範圍內的平均長度及在100-150奈米範圍內的平均直徑。奈米管可以係單壁或多壁或兩者之混合物。
術語石墨烯意謂粒子結構基本上係二維的碳的同素異形體。在極端情況下,其包含具有石墨結構的單一原子層片層,但是出於本發明的目的,此組件可以包含少量的此類片層,一個堆疊在另一個上,例如1至20個、較佳1至10個片層。在一個實施例中,此等片層呈非氧化形式。在另一實施例中,如藉由穿透電子顯微術所量測,片層獨立地具有在1至4000奈米、較佳20至3000或10至2000奈米範圍內的平均尺寸。可以使用任何已知方法來製造此類材料,此類材料亦可商購;舉例而言,以名稱Elicarb®購自英國(United Kingdom)的Thomas Swan Limited。
在另一實施例中,碳電荷攜帶元件可以進一步包括高達20%、較佳1至20重量%的導電碳。適當地,此導電碳包含具有多晶結構及在1至500 m2
g-1
範圍內的表面積的高導電性非石墨化碳。在一個實施例中,其係碳黑;例如,已用作鋰離子電池中之導電添加劑的材料中之一者(例如Timical SuperC65®及/或Timical SuperC45)。
在一個實施例中,在執行本發明方法之後,電極之殘餘水分含量小於100 ppm;較佳小於50 ppm。
至於導電黏合劑,其適當地由一或多種導電聚合物組成且較佳選自纖維素衍生物、聚合物彈性體或其混合物。在一個實施例中,所採用的纖維素衍生物係羧烷基纖維素;例如羧甲基纖維素。在另一實施例中,彈性體係苯乙烯-丁二烯橡膠或具有等效性質的材料。
適當地,複合層中之電荷攜帶元件的總電荷攜帶表面積係> 250 m2
g-1
,較佳> 260 m2
g-1
。
至於離子液體電解質,此適當地包含在低於100℃下熔融且較佳在環境溫度下或低於環境溫度下熔融的有機離子鹽。在另一實施例中,其係由一或多種離子液體組成的混合物且混合物在25℃下之黏度係在10至80厘泊;較佳20至50厘泊範圍內。在另一實施例中,電解質係至少兩種組分之共晶或近共晶混合物,該至少兩種組分中之一者係離子液體。適當地,此等混合物之熔點低於100℃,較佳低於50℃,且更佳低於30℃。共晶特性係兩種或更多種組分之彼等混合物的熟知特徵,在指定組成範圍內,相對於可以基於拉午耳定律(Raoult's law)之基礎所預計的,該等混合物之熔點顯著降低。因此,此處術語『共晶或近共晶混合物』應理解為涵蓋根據本發明之組分的熔點顯示出如此降低的任何混合物;其中在實際共晶點處的降低超過50%、較佳降低超過90%者最佳。在尤佳實施例中,共晶組合物本身被用作電解質。在另一實施例中,所採用的離子液體中之至少一者對其電化學窗口具有超過3v的上限。
在一個較佳實施例中,所採用的電解質係由US5827602或WO2011/100232中所述之離子液體中之至少一者組成的混合物,例如共晶或近共晶混合物,US5827602或WO2011/100232可將讀者指向完整清單。在另一實施例中,混合物由該等離子液體中之至少兩者的混合物組成。
因此,電解質中所採用的離子液體或所採用的離子液體中之一者宜為烷基或經取代之烷基吡啶鎓、噠嗪鎓、嘧啶鎓、吡嗪鎓、咪唑鎓、哌啶鎓、吡咯啶鎓、吡唑鎓、噻唑鎓、噁唑鎓、三唑鎓或氮雜環庚烷鎓陽離子的四級鹽。在此情況下,與各陽離子有關的相對陰離子係大的多原子陰離子且凡得瓦(Van der Waals)體積超過50或100埃係較佳的(例如參見US 5827602,其又提供涵蓋在本發明範疇內之說明性實例)。所選擇的陰離子關於對應的陽離子具有非對稱形態,確保液體中之陽離子及陰離子不容易緊密擠在一起且不容易導致結晶亦係較佳的。在一個實施例中,相對陰離子選自由以下各者組成的群組:四氟硼酸鹽、六氟磷酸鹽、二氰亞胺、雙(氟磺醯基)醯亞胺(FSI)、雙(三氟甲基磺醯基)醯亞胺(TFSI)或雙(全氟C2
至C4
烷基磺醯基)醯亞胺,例如雙(全氟乙基磺醯基)醯亞胺陰離子或其類似物。在另一較佳實施例中,離子液體係選自此等陰離子之經C1
至C4
烷基取代之咪唑鎓、哌啶鎓或吡咯啶鎓鹽,且如本文所揭示般設想陽離子及陰離子之任何排列。在此清單中,以下二元系統係較佳的:哌啶鎓鹽與咪唑鎓鹽;哌啶鎓鹽與吡咯啶鎓鹽;及咪唑鎓鹽與吡咯啶鎓鹽。在替代實施例中,二元系統可以包含(a)以上所提及之陰離子中之一者的哌啶鎓鹽及任何經取代之龐大四級銨鹽,例如其三烷基(烷氧基烷基)銨鹽,其中烷基或烷氧基部分獨立地具有一、二、三或四個碳原子;或(b) WO2011/100232中所例示的氮雜環庚烷鎓鹽中之一或多者。在以上所提及的所有情況中,所採用的鹽較佳應該各自具有超過3伏的電化學窗口上限及低於30℃的熔點。
可以採用的電解質之具體非限制性實例包括衍生自以下陽離子的鹽或鹽之混合物:1-乙基-3-甲基-咪唑鎓(EMIM)、1-甲基-1-丙基吡咯啶鎓、1-甲基-1-丁基吡咯啶鎓及以上所提及的陰離子。在一個實施例中,電解質係此等陽離子之一或多種四氟硼酸鹽。在另一實施例中,其係與方法步驟(a)中所用相同的鹽。
離子液體之水含量宜小於100 ppm,較佳小於50 ppm。
在本發明方法之步驟(a)中,用四氟硼酸鹽處理含碳電極。在一個實施例中,此鹽可以相容性有機溶劑中之高度濃縮的溶液形式存在;在另一實施例中,鹽本身將在進行步驟(a)及(b)之條件下熔融。此等步驟通常係在0至100℃的溫度下進行。四氟硼酸鹽適當地以第IA族、第IIA族、四級銨或鏻鹽形式採用。在一個實施例中,步驟(a)及(b)中所用的鹽係具有對應於上文所述者之陽離子的離子液體。在另一實施例中,鹽係EMIM四氟硼酸鹽。在另一實施例中,所用的四氟硼酸鹽與隨後用作離子液體電解質的鹽相同。
在一個實施例中,步驟(b)適當地在環境溫度下或接近於環境溫度,在下文所述類型的密封袋中或在含有電極及鹽的預處理單元中,藉由在其兩端施加變化的電壓而進行。在另一實施例中,使用高達100℃的較高溫度。此意謂步驟(c)中,在一個循環中電極首先充電且隨後放電,然後重複。必要時,此循環之此充電及放電部分可以在不同溫度下進行。在步驟(c)中,循環通常重複至少3-5次,例如10至60次。在一個實施例中,在各循環期間施加的最大電壓係在3至7v之範圍內。此最大電壓較佳不超過電解質之電化學窗口的上限。在另一實施例中,預處理單元本身連接至可以量測隨著各循環所發生的排氣之程度的裝置(例如壓力計),使得能夠在觀察到排氣停止或減少至低於可接受的上限時終止步驟(c)。除了循環之外,亦可以使系統在所選電壓(例如1.5v、2.0v、2.5v、3.0v或3.5v)下浮動在2分鐘至12小時範圍內的指定持續時間。
在步驟(c)完成後,即可在商業超級電容器單元中與離子液體電解質及多孔膜組合使用電極。應瞭解,因為單元的內容物不再傾向於排氣,所以超級電容器可以由可撓性相對較大且重量較輕的材料製造;例如可密封的可撓性塑膠袋,其中電極係支撐在金屬箔集電器上,該等金屬箔集電器經調適以藉助於凸耳自其凸起。此設計尤其適用於空間及重量常常很重要或者袋子需要符合由將使用該設計的裝置之精美外觀所決定的幾何結構的消費型電子裝置。
雖然不希望受理論的限制,但是目前認為,在步驟(a)至(c)中用鹽處理電極引起鹽因任何殘留的水而部分地水解,從而使電極之水含量降低至以上所提及之可接受的範圍內。因此,超級電容器之後續排氣傾向顯著降低或甚至完全消除。
此係本發明之第二態樣,提供一種由含碳陽極及陰極、中間多孔膜及離子液體電解質組成的超級電容器,其特徵在於陽極及陰極的水含量係小於100 ppm水。水含量較佳小於50 ppm。
超級電容器之組件宜容納在不透水的聚合物袋中。在一個實施例中,離子液體之水含量同樣小於100 ppm;較佳小於50 ppm。
較佳實施例之詳細說明 現在藉由以下比較性測試說明本發明。 實例1
藉由沿著四條相應側邊中之三者熱密封兩個正方形可撓性聚乙烯薄片製造正方形聚合物袋。之後,將一對陽極及陰極電極與中間物聚乙烯及包含EMIM四氟硼酸鹽的鹽一起引入中袋中。各電極包括鋁箔集電器,上面安置著由嵌入於10重量%之基質中的碳奈米管、石墨烯、活性碳(佔總重量之85%)、導電碳(5%)之混合物組成的電極層,該基質包含苯乙烯-丁二烯橡膠及羧甲基纖維素(50:50)。隨後將袋暫時密封且在4安培之電流下,自0至3.5v經歷十個充電-放電循環。在這段時間結束時,打開袋子,再密封且使電極再經歷200個循環。在此後續循環階段,未觀察到對應於顯著排氣的袋子膨脹。 比較性測試
在比較性實驗中,在引入各組分之後立即將袋密封。之後在以上所提及之條件下且在不打開且不重新密封之情況下50個充電-放電循環之後,袋因為排氣而發生劇烈膨脹,使得該袋基本上不適合使用。 實例2
除了在前十個循環之後在重新密封發生之前用離子液體EMIM TFSI替換四氟硼酸鹽之外,重複實例1之方法。在另外200個循環之後,再次未見到發生顯著充氣。
(無)
Claims (6)
- 一種減少包含有含碳電極及至少一種離子液體之超級電容器中之排氣的方法,該方法之特徵在於以下步驟:(a)用四氟硼酸鹽接觸該等含碳電極,該四氟硼酸鹽是烷基或經取代之烷基吡啶鎓、噠嗪鎓、嘧啶鎓、吡嗪鎓、咪唑鎓、哌啶鎓、吡咯啶鎓、吡唑鎓、噻唑鎓、噁唑鎓、三唑鎓或氮雜環庚烷鎓陽離子的四級鹽之離子液體,其中該接觸係在0℃至100℃的溫度下進行;(b)在存在該鹽時,在電荷儲存於該等電極上且自該等電極放電的循環期間,於該等含碳電極兩端施加變化的電勢差,其中該循環之充電及放電部分在不同溫度下進行,其中步驟(b)係在最高至100℃的溫度下進行;以及(c)繼續步驟(b)之循環至少10至60次,直至基本上不再自該系統發生進一步排氣為止的時間,其中在各循環期間所施加之最大電壓不超過電解質之電化學窗口的上限。
- 如請求項1之方法,其中,該等含碳電極包括石墨烯、碳奈米管或其混合物。
- 如請求項1或請求項2之方法,其中,該離子液體亦為四氟硼酸鹽。
- 如請求項1或請求項2之方法,其中,該離子液體係至少一種經C1至C4烷基取代之咪唑鎓、哌啶鎓或吡咯啶鎓鹽。
- 如請求項1或2之方法,其中,該四氟硼酸鹽係EMIM四氟硼酸鹽。
- 如請求項1或2之方法,其中,超級電容器包括含有該等含碳電極及該(等)離子液體的塑膠袋。
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CN109074965B (zh) | 2021-08-13 |
US10490362B2 (en) | 2019-11-26 |
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GB2548128A (en) | 2017-09-13 |
TW201801110A (zh) | 2018-01-01 |
GB201604056D0 (en) | 2016-04-20 |
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