TWI792937B - 用於電致變色裝置的全固態聚合物電解質膜及包含其的電致變色裝置 - Google Patents

用於電致變色裝置的全固態聚合物電解質膜及包含其的電致變色裝置 Download PDF

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TWI792937B
TWI792937B TW111108385A TW111108385A TWI792937B TW I792937 B TWI792937 B TW I792937B TW 111108385 A TW111108385 A TW 111108385A TW 111108385 A TW111108385 A TW 111108385A TW I792937 B TWI792937 B TW I792937B
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polymer electrolyte
solid polymer
electrolyte membrane
electrochromic device
anode
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黃文良
楊純誠
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明志科技大學
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Abstract

一種全固態聚合物電解質膜，是由一寡聚物組成物聚合而得，該寡聚物組成物包含乙氧基化多丙烯酸酯單體、聚醚胺寡聚物及鋰鹽。本發明還提供一種電致變色裝置，包含一陽極、一陰極及一如上所述的全固態聚合物電解質膜，該全固態聚合物電解質膜設置在該陽極及該陰極之間。該全固態聚合物電解質膜具有良好的鋰離子傳導效果，且包含其的電致變色裝置具有高變色量及高循環性。

Description

用於電致變色裝置的全固態聚合物電解質膜及包含其的電致變色裝置
本發明是有關於一種全固態聚合物電解質(solid polymer electrolyte, SPE)膜，特別是指一種用於電致變色裝置(electrochromic device, ECD)的全固態聚合物電解質膜及包含其的電致變色裝置。
電致變色裝置在可見光區的光穿透率可藉由外加電壓產生明顯改變而達到著色或去色，隨後移去電源，電致變色裝置可穩定維持其所呈現的顏色。上述電致變色裝置可應用於節能智慧窗(smart window)，其普遍使用金屬氧化物作為電致變色層材料，並使用電解質以使離子(例如鋰離子)在其中傳導移動。
上述電致變色裝置若採用液態電解質，通常具有良好的離子傳導效果，但其存在漏液及熱脹冷縮的風險；若採用固態電解質(例如聚合物電解質)，其離子傳導效果普遍較差。
因此，本發明之第一目的，即在提供一種用於電致變色裝置的全固態聚合物電解質膜，可以克服上述先前技術的缺點。
於是，本發明全固態聚合物電解質膜是由一寡聚物組成物(oligomer composition)聚合而得，該寡聚物組成物包含乙氧基化多丙烯酸酯單體(ethoxylated polyacrylate monomer)、聚醚胺寡聚物(polyetheramine oligomer)及鋰鹽。
較佳地，該聚醚胺寡聚物的重量平均分子量範圍為200~1000 g/mol。
較佳地，該乙氧基化多丙烯酸酯單體是乙氧基化三羥甲基丙烷三丙烯酸酯(ethoxylated trimethylolpropane triacrylate, ETPTA)。
較佳地，在該寡聚物組成物中，該乙氧基化多丙烯酸酯單體與該聚醚胺寡聚物的重量比例範圍為40：1~6：1。在本發明的具體實施例中，該乙氧基化多丙烯酸酯單體與該聚醚胺寡聚物的重量比例範圍為39：1~34：5。
較佳地，該寡聚物組成物還包含沸石咪唑鹽骨架(zeolitic imidazolate framework, ZIF)。在本發明的具體實施例中，該沸石咪唑鹽骨架是二甲基咪唑鈷(cobalt 2-methylimidazole, ZIF-67)。
較佳地，該寡聚物組成物還包含塑化劑及光起始劑。在本發明的具體實施例中，該塑化劑是丁二腈(succinonitrile, SN)，該光起始劑是焦蜜石酸二酐(pyromellitic dianhydride, PMDA)。
較佳地，該鋰鹽是選自於雙(三氟甲烷磺醯)亞胺鋰(lithium bis(trifluoromethanesulfonyl)imide, LiTFSI)、聚苯乙烯磺酸鋰(lithium polystyrene sulfonate, LiPSS)、碘化鋰(LiI)或其組合。
因此，本發明之第二目的，即在提供一種電致變色裝置，包含一陽極、一陰極及一如上所述的全固態聚合物電解質膜。該全固態聚合物電解質膜設置在該陽極及該陰極之間。
較佳地，本發明電致變色裝置還包含一電極界面改質層，置於該陽極及該陰極之至少其中一者，以夾置在該陽極及該陰極之至少其中一者與該全固態聚合物電解質膜之間。
較佳地，該電極界面改質層是由一包括聚乙烯醇(polyvinyl alcohol, PVA)、乙氧基化多丙烯酸酯單體及鋰鹽的組成物所製成。
較佳地，該陽極是由包括一氧化鎳(NiO)的陽極材料所形成。
較佳地，該陰極是由包括三氧化鎢(WO 3)的陰極材料所形成。
本發明之功效在於：該全固態聚合物電解質膜具有良好的鋰離子傳導效果，且包含其的電致變色裝置具有高變色量及高循環性。
本發明將就以下實施例來作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。
[ 全固態聚合物電解質膜]
〈實施例1 〉
本發明實施例1的全固態聚合物電解質膜，是由包含以下步驟的方法所製得：
在氬氣環境下，將乙氧基化三羥甲基丙烷三丙烯酸酯(ETPTA，重量平均分子量為912 g/mol，購自於Sigma-Aldrich)、Jeffamine® M-1000(購自於Huntsman)、雙(三氟甲烷磺醯)亞胺鋰(LiTFSI，購自於Sigma-Aldrich)及丁二腈(SN，購自於Sigma-Aldrich)依39：1：30：30的重量比例混合，在室溫(25℃)中攪拌8 h，再加入1 wt%焦蜜石酸二酐(PMDA)(以ETPTA的重量為100 wt%)後持續均勻攪拌混合2 h，得到一寡聚物組成物(無溶劑)。
在氬氣環境下，將上述寡聚物組成物塗布於一基材上，再以30 mW/cm 2的365 nm紫外光照射約10~15 min，得到一透明的實施例1的全固態聚合物電解質膜(E1)。
〈實施例2~3 〉
實施例2~3的全固態聚合物電解質膜的製法皆與上述實施例1相似，差異之處在於在實施例2~3的製法中，將ETPTA與Jeffamine® M-1000的重量比例分別改變為38：2及37：3，最後分別得到實施例2~3的全固態聚合物電解質膜(E2~E3)。
〈實施例4~5 〉
實施例4~5的全固態聚合物電解質膜的製法皆與上述實施例1相似，差異之處在於在實施例4~5的製法中，將Jeffamine® M-1000分別改變為Jeffamine® D-230及Jeffamine® D-400，最後分別得到實施例4~5的全固態聚合物電解質膜(E4~E5)。
〈實施例6 〉
實施例6的全固態聚合物電解質膜的製法與上述實施例1相似，差異之處在於在實施例6的製法中，在加入PMDA前另外添加聚苯乙烯磺酸鋰(LiPSS)，其中ETPTA、Jeffamine® M-1000、LiPSS、LiTFSI、SN的重量比例為37：2：1：30：30，最後得到實施例6的全固態聚合物電解質膜(E6)。
〈實施例7 〉
實施例7的全固態聚合物電解質膜的製法與上述實施例4相似，差異之處在於在實施例7的製法中，在加入PMDA前另外添加碘化鋰(LiI)，其中ETPTA、Jeffamine® D-230、LiI、LiTFSI、SN的重量比例為34：5：1：30：30，最後得到實施例7的全固態聚合物電解質膜(E7)。
〈實施例8 〉
實施例8的全固態聚合物電解質膜的製法與上述實施例4相似，差異之處在於在實施例8的製法中，在加入PMDA前另外添加二甲基咪唑鈷(ZIF-67)，其中ETPTA、Jeffamine® D-230、ZIF-67、LiTFSI、SN的重量比例為34：5：1：30：30，最後得到實施例8的全固態聚合物電解質膜(E8)。
〈比較例1 〉
比較例1的全固態聚合物電解質膜的製法與上述實施例1相似，差異之處在於在比較例1的製法中，不加入Jeffamine® M-1000，其中ETPTA、Jeffamine® M-1000、LiTFSI、SN的重量比例為40：0：30：30，最後得到比較例1的全固態聚合物電解質膜(CE1)。
〈比較例2 〉
比較例2的全固態聚合物電解質膜的製法與上述實施例6相似，差異之處在於在比較例2的製法中，不加入Jeffamine® M-1000，其中ETPTA、Jeffamine® M-1000、LiPSS、LiTFSI、SN的重量比例為39：0：1：30：30，最後得到比較例2的全固態聚合物電解質膜(CE2)。
〈比較例3 〉
比較例3的全固態聚合物電解質膜的製法與上述實施例1相似，差異之處在於在比較例3的製法中，將Jeffamine® M-1000改變為聚乙二醇(PEG-400，購自於Sigma-Aldrich)，最後得到比較例3的全固態聚合物電解質膜(CE3)。
[ 電致變色裝置]
負極(陽極)極片—將一氧化鎳(NiO)溶膠(含2.3 wt% NiO)、pluronic® F108、pluronic® F127、pluronic® P123、四乙氧基矽烷(TEOS)、氣相成長碳纖維(vapor grown carbon fiber, VGCF，購自於新永裕應用科技材料，型號為GS013010)、LiTFSI依87.4：1：8：1：1.5：0.1：1的重量比例在乙醇中均勻攪拌混合，得到一負極漿料(陽極材料)。將該負極漿料利用球磨機(ball miller，購自於FRITSCH，型號為PULVERISETTE 7)進行球磨2 h(轉速為800 rpm，使用粒徑約為2 mm的瑪瑙球)，再塗布於一接觸電阻率(contact resistivity)約為5~8 Ω·cm 2並經大氣電漿(atmospheric plasma)表面處理的氧化銦錫(ITO)導電玻璃上，隨後在300℃中烘烤30 min以去除乙醇，得到一形成在ITO導電玻璃上且厚度約為200~500 nm的負極(陽極)。
正極(陰極)極片—將三氧化鎢(WO 3)溶膠(含4 wt% WO 3)、PEG-400、VGCF依98.9：1：0.1的重量比例在乙醇中均勻攪拌混合，得到一正極漿料(陰極材料)。將該正極漿料塗布於一接觸電阻率約為5~8 Ω·cm 2並經大氣電漿表面處理的ITO導電玻璃上，隨後在260℃中烘烤30 min以去除乙醇，得到一形成在ITO導電玻璃上且厚度約為150~200 nm的正極(陰極)。
電極界面改質層—在氬氣環境下，將聚乙烯醇(PVA，重量平均分子量為89,000~98,000 g/mol，購自於Sigma-Aldrich)、ETPTA(重量平均分子量為912 g/mol)、LiTFSI、SN、二甲基亞碸(DMSO)依7：1：2.8：2.8：86.4的重量比例混合，在80℃中均勻攪拌2 h，得到一電極界面改質組成物。將該電極界面改質組成物以浸塗法分別塗布於上述負極(陽極)及正極(陰極)側上，隨後在80℃中烘乾，分別得到形成在上述負極(陽極)及正極(陰極)側上的電極界面改質層。
分別將實施例1~8及比較例1~3的寡聚物組成物(無溶劑)塗布於上述負極(陽極)極片的負極(陽極)側的電極界面改質層上，再將上述正極(陰極)極片的正極(陰極)側的電極界面改質層朝向寡聚物組成物貼合，再以30 mW/cm 2的365 nm紫外光照射上述寡聚物組成物約10~15 min，分別形成全固態聚合物電解質膜E1~E8及CE1~CE3，並以Surlyn®膜(購自於DuPont)封邊，分別得到實施例1~8及比較例1~3的電致變色裝置ECD E1~ECD E8及ECD CE1~ECD CE3。
[ 電性測試]
用夾具分別將實施例1~8及比較例1~3的固態聚合物電解質膜E1~E8及CE1~CE3固定在25℃恆溫箱內，以恆電位儀AUTOLAB(購自於Metrohm AG，型號為PGSTAT302N)使用交流阻抗頻譜法(AC impedance spectroscopy)，以固定振幅為5 mV、掃描頻率在100,000~100 Hz之間量測其體阻抗值(R b)，並以下式計算其鋰離子電導率(lithium ion conductivity, σ i )，結果分別如下表1所示。
Figure 02_image001
在上式中，σ i 表示鋰離子電導率(S/cm)，L表示厚度(cm)，R b表示體阻抗值(Ω)，A表示截面積(cm 2)。 【表1】
  體阻抗值R b(Ω) 鋰離子電導率 (S/cm)
E1 10.25 1.52×10 -4
E2 11.85 1.72×10 -4
E3 12.50 1.46×10 -4
E4 8.04 2.25×10 -4
E5 14.71 1.28×10 -4
E6 11.09 1.51×10 -4
E7 5.00 5.29×10 -4
E8 4.45 2.15×10 -4
CE1 32.14 7.10×10 -5
CE2 25.09 7.06×10 -5
CE3 38.99 4.80×10 -5
由表1可以看出，實施例1~8的固態聚合物電解質膜E1~E8的體阻抗值R b(皆為15 Ω以下)皆明顯小於比較例1~3的固態聚合物電解質膜CE1~CE3的體阻抗值R b(皆為25 Ω以上)，實施例1~8的固態聚合物電解質膜E1~E8的鋰離子電導率(皆為1.2×10 -4S/cm以上)皆明顯大於比較例1~3的固態聚合物電解質膜CE1~CE3的離子電導率(皆為7.1×10 -5S/cm以下)，顯示實施例1~8的固態聚合物電解質膜E1~E8具有較佳的鋰離子傳導效果。
在25℃中以波長為550 nm的可見光測量上述實施例2的電致變色裝置ECD E2循環4次(每次循環：施加電壓為-2 V、施加電流為0.3 µA、施加時間為30 s，以及施加電壓為2 V、施加電流為0.3 µA、施加時間為30 s)隨時間變化的光穿透率，結果如圖1所示。由圖1可以看出，實施例2的電致變色裝置ECD E2在每次循環中的光穿透率變化皆可達20%以上，顯示其在25℃中具有高變色量及高循環性。
綜上所述，本發明全固態聚合物電解質膜具有良好的鋰離子傳導效果，且包含其的電致變色裝置具有高變色量及高循環性，故確實能達成本發明之目的。
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。
本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： ［圖1］是以波長為550 nm的可見光測量本發明實施例2的電致變色裝置ECD E2循環4次所得的時間-光穿透率關係圖。

Claims (12)

  1. 一種用於電致變色裝置的全固態聚合物電解質膜，該全固態聚合物電解質膜是由一寡聚物組成物聚合而得，該寡聚物組成物包含：乙氧基化多丙烯酸酯單體、聚醚胺寡聚物及鋰鹽。
  2. 如請求項1所述的全固態聚合物電解質膜，其中，該聚醚胺寡聚物的重量平均分子量範圍為200~1000g/mol。
  3. 如請求項1所述的全固態聚合物電解質膜，其中，該乙氧基化多丙烯酸酯單體是乙氧基化三羥甲基丙烷三丙烯酸酯。
  4. 如請求項1所述的全固態聚合物電解質膜，其中，在該寡聚物組成物中，該乙氧基化多丙烯酸酯單體與該聚醚胺寡聚物的重量比例範圍為40：1~6：1。
  5. 如請求項1所述的全固態聚合物電解質膜，其中，該寡聚物組成物還包含沸石咪唑鹽骨架。
  6. 如請求項1所述的全固態聚合物電解質膜，其中，該寡聚物組成物還包含塑化劑及光起始劑。
  7. 如請求項1所述的全固態聚合物電解質膜，其中，該鋰鹽是選自於雙(三氟甲烷磺醯)亞胺鋰、聚苯乙烯磺酸鋰、碘化鋰或其組合。
  8. 一種電致變色裝置，包含：一陽極、一陰極及一如請求項1所述的全固態聚合物電解質膜，該全固態聚合物電解質膜設置在該陽極及該陰極之間。
  9. 如請求項8所述的電致變色裝置，還包含一電極界面改質層，置於該陽極及該陰極之至少其中一者，以夾置在該陽極及該陰極之至少其中一者與該全固態聚合物電解質膜之間。
  10. 如請求項9所述的電致變色裝置，其中，該電極界面改質層是由一包括聚乙烯醇、乙氧基化多丙烯酸酯單體及鋰鹽的組成物所製成。
  11. 如請求項8所述的電致變色裝置，其中，該陽極是由包括一氧化鎳的陽極材料所形成。
  12. 如請求項8所述的電致變色裝置，其中，該陰極是由包括三氧化鎢的陰極材料所形成。
TW111108385A 2022-03-08 2022-03-08 用於電致變色裝置的全固態聚合物電解質膜及包含其的電致變色裝置 TWI792937B (zh)

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TW201703332A (zh) * 2015-04-21 2017-01-16 羅地亞經營管理公司 固體聚合物電解質和包含其的電化學裝置
JP2017149667A (ja) * 2016-02-24 2017-08-31 学校法人 関西大学 多孔性錯体複合体およびその製造法
US20210020949A1 (en) * 2019-07-16 2021-01-21 Lionano Se Inc. Composition, article, method of forming article, anode-free rechargeable battery and forming method thereof, and battery
CN113131005A (zh) * 2021-04-19 2021-07-16 清华大学深圳国际研究生院 聚合物电解质膜及其制备方法、金属锂电池及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201703332A (zh) * 2015-04-21 2017-01-16 羅地亞經營管理公司 固體聚合物電解質和包含其的電化學裝置
JP2017149667A (ja) * 2016-02-24 2017-08-31 学校法人 関西大学 多孔性錯体複合体およびその製造法
US20210020949A1 (en) * 2019-07-16 2021-01-21 Lionano Se Inc. Composition, article, method of forming article, anode-free rechargeable battery and forming method thereof, and battery
CN113131005A (zh) * 2021-04-19 2021-07-16 清华大学深圳国际研究生院 聚合物电解质膜及其制备方法、金属锂电池及其制备方法

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