TW201543745A - 以銅奈米線織布作為集電器的鋰離子電池 - Google Patents

以銅奈米線織布作為集電器的鋰離子電池 Download PDF

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TW201543745A
TW201543745A TW103117107A TW103117107A TW201543745A TW 201543745 A TW201543745 A TW 201543745A TW 103117107 A TW103117107 A TW 103117107A TW 103117107 A TW103117107 A TW 103117107A TW 201543745 A TW201543745 A TW 201543745A
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woven fabric
current collector
lithium
copper
nanowire
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Hsing-Yu Tuan
Wei-Chung Chang
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Nat Univ Tsing Hua
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Abstract

一種以銅奈米線織布作為集電器的鋰離子電池,包含有一陽極、一陰極以及一間隔單元。該陽極包含有一第一集電器以及一附著於該第一集電器的活性材料,該陰極包含有一第二集電器以及一依附於該第二集電器上以釋出或接收一鋰離子的鋰化合物,而該間隔單元設置於該陽極與該陰極之間,並包含有一供該鋰離子於該陽極與該陰極之間傳遞的電解液,其中,該第一集電器包含一銅奈米線織布。據此,藉由使用該銅奈米線織布形成該第一集電器,相較於習知使用一銅箔形成該第一集電器,可大幅減輕該陽極重量,使該陽極具有更高的能量密度。

Description

以銅奈米線織布作為集電器的鋰離子電池
本發明為有關一種電池,尤指一種以銅奈米線織布作為集電器的鋰離子電池。
1991年Sony公司首次推出商用化的鋰離子電池,對電子產品帶來了革命性的衝擊,使許多可攜式電子產品得以縮小體積與輕量化。鋰離子電池主要由正極、負極、隔離膜、電解液所構成,正極通常為鋰化合物並以鋁箔為電流的集流板,負極則是使用銅箔當作集流板,且碳材為其主要的活性材料。時至今日,仍有許多研究致力於改善正、負極材料與電解液,使得鋰離子電池的電容量與安全性可以不斷提升,未來除了可攜式電子產品外,也可望廣泛的用於電動車等交通工具上。 例如在歐洲發明專利公開第EP2654111號中,即揭示一種鋰離子二次電池所使用的電解銅箔,該電解銅箔在200~400℃的加熱處理後之0.2%的保證應力(proof stress)在250N/mm2 以上,伸縮在2.5%以上,該電解銅箔之表面被施以一活物質層、或是施以粗化處理而施以防鏽處理。據此,以該電解銅箔形成鋰離子二次電池的負極集電體,即使反覆進行充放電週期,也不會使得容量保持率下降,而具有較長壽命,且該負極集電體不會變形。 然而,一般使用銅箔作為鋰離子電池的負極集電體,其在重量上仍有改進的空間。
本發明的主要目的,在於解決習知的鋰離子電池,使用一銅箔製成一負極集電體,具有重量偏重的問題。 為達上述目的,本發明提供一種以銅奈米線織布作為集電器的鋰離子電池,包含有一陽極、一陰極以及一間隔單元。該陽極包含有一第一集電器以及一附著於該第一集電器的活性材料;該陰極包含有一第二集電器以及一依附於該第二集電器上以釋出或接收一鋰離子的鋰化合物;而該間隔單元設置於該陽極與該陰極之間,並包含有一供該鋰離子於該陽極與該陰極之間傳遞的電解液。 其中,該第一集電器包含一銅奈米線織布。 如此一來,本發明藉由使用該銅奈米線織布形成該第一集電器,可令所製備而成的該陽極具有優異的能量密度,並且相較於習知使用該銅箔形成該負極集電體,可大幅減輕75%的重量。
有關本發明的詳細說明及技術內容,現就配合圖式說明如下: 請參閱『圖1』所示,為本發明第一實施例的結構示意圖,如圖所示,本發明為一種以銅奈米線織布作為集電器的鋰離子電池,包含有一陽極10、一陰極30以及一間隔單元20。該陽極10包含有一第一集電器11以及一活性材料,該第一集電器11包含一銅奈米線織布111,該銅奈米線織布111為一片狀結構,該活性材料附著於該第一集電器上11,其型態可為顆粒、粉末、奈米線或其任意組合,而材質則可為碳材料、矽、磷化銅、鍺等,例如為矽奈米線、磷化銅奈米線、鍺奈米粒子、矽奈米粒子等。該陰極30相對該陽極10設置,包含有一第二集電器31以及一鋰化合物,該第二集電器31在此可為鋁,亦可形成為一片狀結構,例如為一鋁箔,該鋰化合物依附於該第二集電器31上以釋出或接收一鋰離子,該鋰化合物在此可為鋰鈷氧、鋰錳氧、鋰鐵磷、鋰鎳鈷錳氧等材料。而該間隔單元20設置於該陽極10與該陰極30之間,防止該陽極10與該陰極30相互接觸而短路,並包含有一電性連接於該陽極10與該陰極30之間的電解液,該間隔單元20具有複數個孔隙(圖未示),該孔隙可以吸收該電解液,令該電解液供該鋰離子於該陽極10與該陰極30之間傳遞,該電解液在此包含一溶質以及一溶劑,該溶質可為六氟磷酸鋰(Lithium hexafluorophosphate,LiPF6 ),該溶劑則可為碳酸二乙酯(Diethyl carbonate,DEC)、氟代碳酸乙烯酯(Fluoroethylene carbonate,FEC)、 碳酸乙烯酯(Ethylene carbonate,EC) 碳酸二甲酯(Dimethyl carbonate,DMC)。 請參閱『圖2A』至『圖2C』所示,為本發明第一實施例銅奈米線織布的製備流程圖,如『圖2A』所示,首先,將一銅奈米線溶液50置入一鐵氟龍模具40,該銅奈米線溶液50包含一第一有機溶液52以及複數個溶於該第一有機溶液52之中的銅奈米線51,該第一有機溶液52在此可為甲苯、苯、正已烷、三氯甲烷等,接著,如『圖2B』所示,等待該第一有機溶液52揮發,而留下該銅奈米線51,最後,如『圖2C』所示,將該鐵氟龍模具40放到一真空烘箱中烘烤,以將殘餘的該第一有機溶液52烘乾,並打開該鐵氟龍模具40,即可刮下該銅奈米線51,得到具彼此交織的該銅奈米線51的該銅奈米線織布111。 請參閱『圖3』所示,『圖3』為本發明第一實施例的銅奈米線織布與銅箔的塔弗曲線示意圖,在本實施例中,該銅奈米線織布111為設計成2cm×2cm的尺寸,但不以此尺寸為限制,將該銅奈米線織布111與同樣尺寸的一銅箔比較,經由一電性量測後,將結果繪成如『圖3』的塔弗曲線(Tafel curve),由圖中可知,該銅奈米線織布111具有與該銅箔相近的導電性,且該銅奈米線織布111的導電性不僅勝於該銅箔,更具有比該銅箔更輕的重量。 請參閱『圖4』所示,為本發明第二實施例的結構示意圖,在第二實施例中,與第一實施例相較,其特徵在於該陽極10選用一鍺奈米線織布112為該活性材料,該鍺奈米線織布112依附於該第一集電器11,而與該銅奈米線織布111層疊連接,在此為介於該銅奈米線織布111與該間隔單元20之間。 請參閱『圖5A』至『圖5D』所示,為本發明第二實施例鍺/銅奈米線織布的製備流程圖,如『圖5A』所示,先將該銅奈米線溶液50置入該鐵氟龍模具40,待該第一有機溶液52揮發完畢後,留下該銅奈米線51,如『圖5B』所示,再滴入一鍺奈米線溶液60,該鍺奈米線溶液60包含一第二有機溶液62以及複數個溶於該第二有機溶液62之中的鍺奈米線61,該第二有機溶液62在此可為甲苯、苯、正己烷、三氯甲烷,接著,如『圖5C』所示,等待該第二有機溶液62揮發,而留下該鍺奈米線61,再如『圖5D』所示,將該鐵氟龍模具40放到一真空烘箱中烘烤,以將殘餘的該第二有機溶液62烘乾,並打開該鐵氟龍模具40,即可刮下該銅奈米線織布111及層疊於該銅奈米線織布111上的該鍺奈米線織布112,再將該銅奈米線織布111及該鍺奈米線織布112置於一石英管中,通入一氬氣及一氫氣在約500°C的溫度下燒結,以去除表面的一油類物質(該鍺奈米線織布112上的該油類物質為1-dodecanethiol,該銅奈米線織布111上的該油類物質為Oleylamine,OLA)以及還原鍺與銅的氣化物,得到一鍺/銅奈米線織布,該鍺/銅奈米線織布即可供製作該鋰離子電池。 為進一步說明本發明之具體功效,請參閱以下依據本發明所進行之實驗例,此僅為例舉說明之目的提供,而不意欲來限制本發明之範圍。請參閱『圖6』及『表1』所示,『圖6』為不同結構與製程的奈米線織布的鋰電池循環測試示意圖,圖中所繪製的圖形點,僅為示意樣品1至樣品6之充放電循環次數(Cycle number)與電容量(Capacity)之間的關係,『表1』為不同結構與製程的奈米線織布的鋰電池循環測試結果歸納表,樣品1、樣品2與樣品3均為習知的鋰離子電池,係屬於比較例,樣品4與樣品5為本發明之鋰離子電池,屬於實驗例。樣品1至樣品5除陽極所使用的該第一集電器與該活性材料不同外,其餘結構與材料均為相同,係採用CR2032鈕扣型鋰電池。 從『表1』中可發現,樣品1為以未燒結過的一鍺奈米線織布為該陽極,由於未燒結過的該鍺奈米線織布導電性非常差,其鋰電池的測試在前幾個充放電循環,電容量就已經大幅衰退,經過100個充放電循環,電容量就只剩不到130 mAh/g。樣品2為以燒結過的一鍺奈米線織布為該陽極,雖然充放電循環較未燒結過的穩定,但經過100個循環後,電容量也僅剩507 mAh/g。樣品3為將一鍺奈米線織布放置於一銅箔上為該陽極,再組裝成鋰電池,由電池充放電循環測試的結果發現,加入該銅箔後,該鍺奈米線織布的電容量反而衰退更多,於100個充放循環後,電容量僅剩246 mAh/g,此結果可能是因為該鍺奈米線織布在該銅箔上的附著性非常差,所以在加入該銅箔後,反而增加了接觸電阻,且在充放電的過程中,其中鍺奈米線的膨脹收縮可能使其剝離銅箔,使得電池的充放電循環表現地更差。 樣品4為在該鍺奈米線織布112製作的過程中,加入該銅奈米線織布111,製成為該鍺/銅奈米線織布的該陽極,該鍺奈米線織布112可以很好地附著在該銅奈米線織布111上,且不易剝落,解決了該鍺奈米線織布112於該銅箔上不易附著的問題。該鍺/銅奈米線織布的鋰電池循環測試以EC/DMC為該電解液進行該鋰電池的測試,發現其充放電循環的穩定性比起其他製程的奈米線織布高出許多,5個循環後,仍有1120 mAh/g的電容量,但當超過50個循環後,電容量就會開始不斷的衰退,直到第100循環結束後,電容量僅剩776 mAh/g。 樣品5以該鍺/銅奈米線織布為該陽極,並改用FEC/DEC為該電解液來進行該鋰電池的測試,由結果發現,使用FEC/DEC為電解液的鍺/銅奈米線織布具有相當優異的充放電循環測試表現,經過100個循環後,其電容量仍然高達1092 mAh/g。 再請參閱『表2』所示,為不同陽極材料於1C充放電速率的電容量比較表,樣品A、樣品B與樣品C均為習知的陽極材料,係屬於比較例,樣品D為本發明之陽極材料,屬於實驗例。『表2』內所有的計算皆假設該陽極為1平方公分、鍺材料的搭載量為1毫克。從『表2』可知,在1 C高電流的充放電速率下,使用鍺奈米材料的樣品A至樣品D皆可以具有相當穩定的高電容量850 mAh/g~1152 mAh/g。不過當加入導電劑、黏著劑、集流板後,使用漿料式製程的樣品A至樣品C的該陽極,僅剩93~113 mAh/g的電容量,而使用鍺/銅奈米線織布的樣品D的該陽極仍有332 mAh/g的電容量,約是其他的3倍左右,所以使用鍺/銅奈米線織布的該陽極所製作的電池不僅可以達到輕量化的效果,當該陽極的面積越大時,其效果會越明顯,該陽極將具有較佳的能量密度。 a:第50個循環的放電電容量,參考文獻「Yuan, F.-W.; Yang, H.-J.; Tuan, H.-Y., Alkanethiol-Passivated Ge Nanowires as High-Performance Anode Materials for Lithium-Ion Batteries: The Role of Chemical Surface Functionalization. ACS Nano 2012, 6 (11), 9932-9942.」。 b:第100個循環的放電電容量,參考文獻「Chockla, A. M.; Klavetter, K. C.; Mullins, C. B.; Korgel, B. A., Solution-grown germanium nanowire anodes for lithium-ion batteries. ACS applied materials & interfaces 2012, 4 (9), 4658-64」。 c:第200個循環的放電電容量,參考文獻「Klavetter, K. C.; Wood, S. M.; Lin, Y.-M.; Snider, J. L.; Davy, N. C.; Chockla, A. M.; Romanovicz, D. K.; Korgel, B. A.; Lee, J.-W.; Heller, A.; Mullins, C. B., A high-rate germanium-particle slurry cast Li-ion anode with high Coulombic efficiency and long cycle life. Journal of Power Sources 2013, 238, 123-136」。 d:第100個循環的放電電容量。 綜上所述,本發明使用該銅奈米線織布形成該第一集電器,令所製備而成的該陽極具有優異的能量密度;其次,對比於同樣面積(1平方公分)的習知集電器,其具有的該銅箔有7.7毫克的重量;反觀,本發明的該銅奈米線織布的重量僅2~2.5毫克,所以在其他材料與參數不變動的狀況下,本發明的該鋰離子電池,可以減少達75%的重量,具備輕量化的優勢;再者,本發明還可使用該鍺/銅奈米線織布形成該陽極,不需要加一導電劑(Super p)與一黏著劑(PVDF),並具有相當良好的循環電容量表現,因此本發明極具進步性及符合申請發明專利的要件,爰依法提出申請,祈  鈞局早日賜准專利,實感德便。 以上已將本發明做一詳細說明,惟以上所述者,僅爲本發明的一較佳實施例而已,當不能限定本發明實施的範圍。即凡依本發明申請範圍所作的均等變化與修飾等,皆應仍屬本發明的專利涵蓋範圍內。
10‧‧‧陽極
11‧‧‧第一集電器
111‧‧‧銅奈米線織布
112‧‧‧鍺奈米線織布
20‧‧‧間隔單元
30‧‧‧陰極
31‧‧‧第二集電器
40‧‧‧鐵氟龍模具
50‧‧‧銅奈米線溶液
51‧‧‧銅奈米線
52‧‧‧第一有機溶液
60‧‧‧鍺奈米線溶液
61‧‧‧鍺奈米線
62‧‧‧第二有機溶液
圖1,為本發明第一實施例的結構示意圖。 圖2A至圖2C,為本發明第一實施例銅奈米線織布的製備流程圖。 圖3,為本發明第一實施例的銅奈米線織布與銅箔的塔弗曲線示意圖。 圖4,為本發明第二實施例的結構示意圖。 圖5A至圖5D,為本發明第二實施例鍺/銅奈米線織布的製備流程圖。 圖6,為不同結構與製程的奈米線織布的鋰電池循環測試示意圖。
10‧‧‧陽極
11‧‧‧第一集電器
111‧‧‧銅奈米線織布
20‧‧‧間隔單元
30‧‧‧陰極
31‧‧‧第二集電器

Claims (8)

  1. 一種以銅奈米線織布作為集電器的鋰離子電池,包含有: 一陽極,該陽極包含有一第一集電器以及一附著於該第一集電器的活性材料; 一陰極,該陰極包含有一第二集電器以及一依附於該第二集電器上以釋出或接收一鋰離子的鋰化合物;以及 一設置於該陽極與該陰極之間的間隔單元,該間隔單元包含有一供該鋰離子於該陽極與該陰極之間傳遞的電解液; 其中,該第一集電器包含一銅奈米線織布。
  2. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該活性材料為一鍺奈米線織布。
  3. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該活性材料的材質為選自碳材料、矽、磷化銅、鍺及其組合所組成的群組。
  4. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該活性材料的型態為選自顆粒、粉末及奈米線所組成的群組。
  5. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該第二集電器的材質為鋁。
  6. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該鋰化合物為選自鋰鈷氧、鋰錳氧、鋰鐵磷、鋰鎳鈷錳氧所組成的群組。
  7. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該電解液的一溶質為六氟磷酸鋰(Lithium hexafluorophosphate,LiPF6 ),一溶劑為選自碳酸二乙酯(Diethyl carbonate,DEC)、氟代碳酸乙烯酯(Fluoroethylene carbonate,FEC)、 碳酸乙烯酯(Ethylene carbonate,EC) 碳酸二甲酯(Dimethyl carbonate,DMC)所組成的群組。
  8. 如申請專利範圍第1項所述的以銅奈米線織布作為集電器的鋰離子電池,其中該銅奈米線織布包括複數個彼此交織的銅奈米線。
TW103117107A 2014-05-15 2014-05-15 以銅奈米線織布作為集電器的鋰離子電池 TW201543745A (zh)

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