201248285 六、發明說明： 【發明所屬之技術領域】 本發明係有關於-種電致變色裝置及其製程方法，特別係 有關於-種電極交錯平行交疊之封裝技術，藉由該技術可降低 5亥電致I色裝置所需之驅動電壓且縮短其調光時間。 【先前技術】 一般而3，電致變色裝置係指一種在提供一電場時，產生 電化學之氧化還原反應’造成光線穿透特性的改變，進而造成 顏色變化之裝置。其中，該過程為一可逆過程，當無外加電場 時，泫電致色變材料即恢復原有特性。利用電致變色材料之特 性’可製成電致色變顯示裝置。電致變色材料目前可應用於各 種領域，例如：車輛鑲嵌玻璃(如車窗、天窗）、大樓鑲嵌玻璃、 顯示裝置、光學元件、鏡體及電錢照射之遮蔽鱗等，其功 用在於可有效地阻隔外界(如光、熱)的干擾。其中，電致變色 材料係被分類為還原呈色材料與氧化呈色材料。還原呈色材料 係指因獲得電子而呈色者，一般包括氧化鷄；同時，氧化呈色 材料係指因失去電子而呈色者’―般包括氧鋪與氧化銘；其 他包括無機金屬氧化物之電致發光材料如：Ir(〇H)x，， V2〇5，Ti〇2等等。值得注意的是’上述之電致發紐料皆必須 在含有鐘離子或氫離子之電解質環境中方能產生顏色之變化。 參照美國專利公告號第5,441，827號，其揭示了一種具有 高效率、高反應速率之裝置’此製置之製備係於燒結自金屬氧 化奈米顆粒’具有奈米孔徑的薄膜電極表面，塗覆單一層電化 201248285 學活性有機紫精化合物。此外，此裝置利用了一鐘鹽與有機溶 劑如γ 丁内酯(Y〜bu_actone)與碳酸丙二醋__收 carbonate)之混合物作為電解f。然而，這種利用含有機溶劑作 為電解質之裝置，缺點在於其驟媳速率(quenehing咖)低在 驟熄後仍會出現殘影，且有機材料在顯影與驟熄之循環中容易 刀解。其中’更由於裝置使用含有機溶劑之液狀電解質，因此 更容易發生電解質揮發與耗盡之缺點，且電解質可能會從裝置 中溢漏出來，而造成不環保的問題，同時，薄膜成形或將產品 製成薄膜外型較不可行。此外，該專利亦未對最後上下電極之 封裝方法作詳細之指述，如此亦同時影響後續應用範圍。 參照美國專利公告第6，193,379號，其揭示一種電致變色裝 置係主要用於車内之後視鏡(rearview爪丨灯沉）。其中，該專利 之電致變色裝置之電致變色材料與用於傳導離子的電解質摻 混在一起，所以必須持續通入較高電壓，才可維持在變色狀 I因而無法具有著色記憶(color memory effect)之功效。然而， 該專利並未對最後上下電極之封裝方法作詳細之描述，再加上 忒電致變色材料為溶液狀，當整個裝置被f折時，將可能致使 T電致色變材料渗露出如此亦同時影響後續應用範ΐμ此外， 習知固態電解質(例如LiNb〇3或也〇5)需要在持續施加較高電 壓下才可7L成著色或去色，且所花費的調光時間較長。 職疋之故，申請人乃細心試驗與研究，並一本鍥而不捨的 精神’終於研究出一種電致變色裝置及其製程方法，特別係有 關於-種電極交錯平行交疊之封裝技術。藉由該封裝技術，本 4 201248285 發明之-種電致變色裝置及其製程方法可提倾電致變色裝 置所需之較低之驅動電壓與調光時間。 【發明内容】 本發明提出—種電致變色裝置，藉㈣極交錯平行交疊之 封裝結構’進而提供該電致變色裝置所需之較低之驅動電墨與 調光時間之功於。 六本發似提供-種電致變色裝置之製備方法，其係於電極 壓::::且之封裝技術的條件下’發展出-種可降低驅動電 壓與5周光時間之電致變色褒置。 诱=提出之電致變色裝置，包含:第-透明基材、第 ==導 變色層、第二透明基材、第二透明導電層、 層以及電解質。其中，第—透明導電層被覆於第 一透明基材之表面，形成第一 於第-透明導電層之表面1 Γ 電致變色層被覆 絲矣 a ’第—透日将電層被覆於第二透明基 ==材=第二透明導電基材；輔助電致變色層被覆於第 而成^ δ ’電解__子概與概聚合物所混合 而成，填充於電致變色層與輔助電致變色声 :一寬的範圍為。'5公尺至b公尺之間; 之第二透料電^㈣^電^與含有輔助電致變色層 娜線，敝 201248285 2長間之⑽雜為G.5至3公分之間，寬與寬之相對距離 马认5至3公分之間；電致變辛梦 支色裝置之驅動電壓為30伏特至 之間。寺之間’且電致變色裝置之調光時間為·毫秒至6〇秒 含種電致變色裝置之製程方法，其步驟包 之矣Ϊ 娜―_電層於第—透明基材 導ίΓ Γ第一透明導電基材’·沈積電致變色層於第一透明 第㈣鳴；沈账轉電層於該 變色層於第1明L形成第一透明導電基材；沈積輔助電致 一透明導電基材與含有辅助電致變色層之第二透賴2 二交第疊透以形成兩組W邊界線，交疊後之第 =導電基材與第二透明導電基材之長與長間之相對距離 ^至3公分之間，寬與寬之相對距離為G.5至3公分之間. 真充由^子賴鱗狀聚合物觀合耐之電 致 =Γ:Γ變色層之間;沿著該_型邊界線，以 3〇伏特至50伏特之η 支色欢置之驅動電壓為 根據秘明 光時間為⑽毫秒至6G秒之間。 明導電歸魏，其t含有魏賴色層之該第一透 預留二圍：_助交電二變色層— 透明導電翁之m 方法交疊，麵後之該兩 分之間。 。長及寬與寬之間之相對距離為0.5至3公 6 201248285 根據本發明之另一特徵，其中含有該膠狀聚合物係選自聚 甲基丙稀酸甲酉旨(polymethyl methacrylate, PMMA)、聚偏二氟乙 烯(polyvinylidene difluoride，PVDF)、聚氯乙烯（polyvinyl chloride，PVC)、聚氧化乙稀(polyethylene oxide，PEO)以及聚甲 基丙烯酸經乙自旨(polyhydroxyethyl methacrylate，PHEMA)、乙稀 一乙酸乙稀 g旨共聚物（Ethylene vinyl accetate copolymer, EVA)、聚乙烯醇(p〇lyV丨nyiaic〇h〇l，PVA)i—。 其中，電解質與PVB膠材(或其他膠材)的混合材料，可使 用方法有： 一、 直接塗佈（網印）於玻璃後再加熱烘乾硬化； 二、 將含電解質的膠材製成薄膜後裁剪適當大小覆貼於 玻璃後再經層壓機加熱壓合兩片玻璃。 本發明之一種電致變色裝置及其製程方法具有以下之功 效： 1. 該電致變色裝置之驅動電壓為30伏特至50伏特之間，且 調光時間為1〇〇毫秒至6〇秒之間； 2. 藉由本發明之電極交錯平行交疊之封裝技術比傳統封裝 方式之驅動電壓將可降低1/2〜1/3左右，並同時降低其調 光時間； ^ 3·藉由本發明之電極交錯平行交疊之封裝技術將可有效增 加離子傳導速度，並縮短去/著色時間； 4.藉由本發明之電致變色裝置，可使開放電路記憶數小時， 保持透射固定狀態且不須做電壓脈衝之修正。 201248285 為讓本發明之上述和其他目的、特徵、和優點能更明顯 易懂’下文特舉數個較佳實施例，並配合所附圖式’作詳細 說明如下。 【實施方法】 雖然本發明可表現為不同形式之實施例，但附圖所示者及 於下文中說明者係為本發明可之較佳實施例，並請暸解本文所 揭不者係考量為本發明之一範例，且並非意圖用以將本發明限 制於圖示及/或所描述之特定實施例中。 現請參考第1圖，其顯示為本發明之一種電致變色裝置 100之結構示意圖。該電致變色裝置1〇〇主要包含：第一透明 基材110 ;第一透明導電層120;電致變色層13〇;第二透明基 材140 ;第二透明導電層15〇 ;輔助電致變色層16〇 ;電解質 170。其中，第一透明導電層12〇被覆於第一透明基材u〇之 表面，形成第一透明導電基材；電致變色層13〇被覆於第一透 明導電層120之表面；第二透明導電㉟15〇被覆於第二透明基 材140之表面，形成第二透明導電紐；輔助電致變色層16〇， $覆於第二透明基材14〇之表面；電解質17〇係由離子液體與 膠狀聚合物所混合而成’填充於含有電致變色層n明導 電基材與含有輔助電致變色層之第二透明導電基材之間。其 中’第-透明基材110與第二透明基材刚係選自於玻璃基 板、塑膠基板、可撓性基板之―，且第_透明基材11G之長⑴ 與第二透明基材14G之長141 _範圍為丨公尺至3公尺之 間’而寬112與142的範圍為〇5公尺至i 5公尺之間。其元 201248285 件之不同點在於使用之導電基料同，若基材皆為玻璃，即為 穿透式元件，可應用於智慧型窗戶與濾光板，光線穿透量的多 寡可由導電基材的電位決定。若基材一面為透明導電玻璃，另 _面為具有反雜質的錢絲材，即献財元件，可應用 於後視鏡或顯示器上。 現請參考第2 ® ’其顯示為本發明之—種電 製程方法200。其包含下列之步驟： 、 步驟210:沈積第一透明導電層12〇於第—透明基材則之 表面，形成第一透明導電基材； 步驟220:沈積電致變色層13〇於第—透料電層1如之表 面； 乐二远明基材 步驟230 :沈積第二透明導電層1 之表面，形成第二透明導電基材； 步驟2你沈積輔助電致變色層16〇於第二透明導電層⑼ 之表面； 步驟250:分別將含有電致變色層之第—透明導電201248285 VI. Description of the Invention: [Technical Field] The present invention relates to an electrochromic device and a method for fabricating the same, and in particular to a packaging technique for staggered parallel overlap of electrodes, by which the technique can be reduced 5 hai electric to the driving voltage required for the I color device and shorten the dimming time. [Prior Art] In general, an electrochromic device refers to a device which produces an electrochemical redox reaction when an electric field is supplied, causing a change in light transmission characteristics, thereby causing a color change. Wherein, the process is a reversible process, and when no external electric field is applied, the xenon-induced color-changing material restores the original characteristics. An electrochromic display device can be fabricated using the characteristics of an electrochromic material. Electrochromic materials can be used in various fields, such as: vehicle mosaic glass (such as window, skylight), building inlaid glass, display device, optical components, mirror body and shielding scales of electric money irradiation, etc. The ground blocks interference from the outside world (such as light and heat). Among them, electrochromic materials are classified into a reducing coloring material and an oxidative coloring material. The reduced coloring material refers to the coloring due to the acquisition of electrons, generally including oxidized chicken; at the same time, the oxidative coloring material refers to the coloring due to the loss of electrons, including the oxygen coating and oxidation; other includes inorganic metal oxides. The electroluminescent material is, for example, Ir(〇H)x, V2〇5, Ti〇2 and the like. It is worth noting that the above-mentioned electroluminescent materials must be able to produce a color change in an electrolyte environment containing a clock ion or a hydrogen ion. U.S. Patent No. 5,441,827, which discloses a device having a high efficiency and a high reaction rate, which is prepared by sintering a surface of a thin film electrode having a nanopore diameter from a metal oxide nanoparticle. A single layer of electrified 201248285 active organic purple essence compound. Further, this apparatus utilizes a mixture of a salt of a salt and an organic solvent such as γ-butyrolactone (Y~bu_actone) and propylene carbonate (carbonate) as the electrolysis f. However, such a device using an organic solvent as an electrolyte has a disadvantage in that its quenching rate is low after the quenching, and the organic material is easily cleaved in the cycle of development and quenching. Among them, because the device uses a liquid electrolyte containing organic solvent, it is more prone to the disadvantages of electrolyte evaporation and depletion, and the electrolyte may leak out of the device, causing environmental problems, and at the same time, film forming or It is not feasible for the product to be made into a film. In addition, the patent does not specify the final packaging method of the upper and lower electrodes, which also affects the scope of subsequent applications. Referring to U.S. Patent No. 6,193,379, it is disclosed that an electrochromic device is mainly used in a rearview mirror (rearview). Wherein, the electrochromic material of the electrochromic device of the patent is mixed with the electrolyte for conducting ions, so it is necessary to continuously pass a higher voltage to maintain the discoloration state I and thus cannot have color memory effect. ) The effect. However, this patent does not describe the final packaging method of the upper and lower electrodes. In addition, the electrochromic material is in the form of a solution. When the whole device is folded by f, it may cause the T electrochromic material to be exposed. At the same time, it affects the subsequent application. In addition, conventional solid electrolytes (such as LiNb〇3 or 〇5) need to be colored or decolored 7L while continuously applying a higher voltage, and the dimming time taken is longer. For the sake of the post, the applicant was carefully experimenting and researching, and a perseverance spirit finally developed an electrochromic device and its manufacturing method, in particular, the packaging technology for the staggered parallel overlap of electrodes. With the encapsulation technique, the electrochromic device and the method of the invention thereof are capable of improving the lower driving voltage and dimming time required for the tilting electrochromic device. SUMMARY OF THE INVENTION The present invention provides an electrochromic device that provides the lower driving ink and dimming time required for the electrochromic device by means of a (four) pole staggered parallel overlapping package structure. The invention provides a method for preparing an electrochromic device which is developed under the condition of electrode pressure:::: and packaging technology to develop an electrochromic enthalpy which can reduce the driving voltage and the 5-week light time. Set. The electrochromic device proposed by the inducer comprises: a first transparent substrate, a == color changing layer, a second transparent substrate, a second transparent conductive layer, a layer, and an electrolyte. Wherein, the first transparent conductive layer is coated on the surface of the first transparent substrate to form a surface of the first transparent conductive layer 1 Γ the electrochromic layer is coated with the wire ' a 'the first transparent layer is coated with the second layer Transparent base == material = second transparent conductive substrate; auxiliary electrochromic layer is coated with the first ^ δ 'electrolyte __ sub-and the general polymer, filled in the electrochromic layer and auxiliary electro-induced Discoloration: A wide range is. '5 meters to b meters; the second through the electricity ^ (four) ^ electricity ^ with the auxiliary electrochromic layer Na line, 敝 201248285 2 long room (10) miscellaneous between G. 5 to 3 cm, The relative distance between width and width is between 5 and 3 cm; the driving voltage of the electro-optic Xinmeng color device is between 30 volts. The dimming time between the temples and the electrochromic device is from milliseconds to 6 sec. The process method of the electrochromic device is included, and the steps are packaged in the ―- _ electrical layer on the first transparent substrate guide Γ The first transparent conductive substrate 'depositing the electrochromic layer is in the first transparent fourth (four) sound; the sinking turn-on layer forms the first transparent conductive substrate on the first color L; the deposition auxiliary electro-transparent conductive The substrate and the second permeable layer 2 containing the auxiliary electrochromic layer are formed to form two sets of W boundary lines, and the length and length of the overlapped second conductive substrate and the second transparent conductive substrate The relative distance is between ^ and 3 cm, and the relative distance between width and width is between G. 5 and 3 cm. The true charge is observed by the squamous polymer of the squamous squamous polymer = Γ: between the enamel color layers; Along the _-type boundary line, the driving voltage of the η color of 3 volts to 50 volts is between (10) milliseconds and 6 GHz seconds according to the secret light time. The conductive is returned to Wei, and the t contains the first transparent reserve of the Wei Lai layer: the _ help paying two color-changing layer - the transparent conductive type m method overlaps, between the two points behind the surface. . The relative distance between the length and the width and the width is 0.5 to 3 gongs. 201248285 According to another feature of the invention, the gelatinous polymer is selected from the group consisting of polymethyl methacrylate (PMMA). , polyvinylidene difluoride (PVDF), polyvinyl chloride (PVC), polyethylene oxide (PEO), and polymethacrylate methacrylate (PHEMA), B Ethylene vinyl accetate copolymer (EVA), polyvinyl alcohol (p〇lyV丨nyiaic〇h〇l, PVA) i-. Among them, the mixed materials of electrolyte and PVB glue (or other glue) can be used as follows: 1. Direct coating (screen printing) on glass, then heating and drying hardening; 2. Making electrolyte containing electrolyte After the film is cut, it is appropriately sized and applied to the glass, and then the two glasses are heated and pressed by a laminator. An electrochromic device and a process method thereof according to the present invention have the following effects: 1. The electrochromic device has a driving voltage of between 30 volts and 50 volts, and the dimming time is from 1 millisecond to 6 sec. 2. The package voltage of the electrode staggered parallel overlap of the present invention can be reduced by about 1/2 to 1/3 compared with the conventional package mode, and at the same time, the dimming time is reduced; ^3. The encapsulation technique in which the electrodes are staggered in parallel will effectively increase the ion conduction velocity and shorten the de-coloring time; 4. With the electrochromic device of the present invention, the open circuit can be memorized for several hours, and the transmission is fixed and does not need to be done. Correction of the voltage pulse. The above and other objects, features, and advantages of the present invention will become more apparent from the <RTIgt; [Embodiment] The present invention may be embodied in different forms, and the embodiments shown in the drawings and the following description are preferred embodiments of the present invention, and it is understood that An example of the invention is not intended to limit the invention to the particular embodiments illustrated and/or described. Referring now to Figure 1, there is shown a schematic structural view of an electrochromic device 100 of the present invention. The electrochromic device 1〇〇 mainly comprises: a first transparent substrate 110; a first transparent conductive layer 120; an electrochromic layer 13A; a second transparent substrate 140; a second transparent conductive layer 15; Color changing layer 16 〇; electrolyte 170. The first transparent conductive layer 12 is coated on the surface of the first transparent substrate u to form a first transparent conductive substrate; the electrochromic layer 13 is coated on the surface of the first transparent conductive layer 120; the second transparent conductive 3515〇 is coated on the surface of the second transparent substrate 140 to form a second transparent conductive button; the auxiliary electrochromic layer 16〇, overlying the surface of the second transparent substrate 14〇; the electrolyte 17 is made of ionic liquid and glue The polymer is mixed to be 'filled between the electrically conductive substrate containing the electrochromic layer and the second transparent conductive substrate containing the auxiliary electrochromic layer. Wherein the first transparent substrate 110 and the second transparent substrate are selected from the group consisting of a glass substrate, a plastic substrate, and a flexible substrate, and the length (1) of the first transparent substrate 11G and the second transparent substrate 14G are The length 141 _ ranges from 丨 to 3 meters and the width 112 and 142 ranges from 〇 5 meters to i 5 meters. The difference between its element 201248285 is that the conductive base material used is the same. If the substrate is glass, it is a penetrating element, which can be applied to smart windows and filters. The amount of light penetration can be made of conductive substrate. The potential is determined. If one side of the substrate is a transparent conductive glass, the other side is a money wire with anti-impurities, that is, a wealth-saving component, which can be applied to a rear view mirror or a display. Please refer to Section 2 ® '''''''''''' The method includes the following steps: Step 210: depositing a first transparent conductive layer 12 on a surface of the first transparent substrate to form a first transparent conductive substrate; Step 220: depositing an electrochromic layer 13 on the first The electric layer 1 is as a surface; the Le Eryuan substrate step 230: depositing the surface of the second transparent conductive layer 1 to form a second transparent conductive substrate; Step 2: depositing the auxiliary electrochromic layer 16 on the second transparent conductive The surface of the layer (9); Step 250: respectively, the first transparent conductive layer containing the electrochromic layer
有輔助電致變色層之第二透明導電基材以交錯平狀方S 疊，以形成兩組L型邊界線121與151。交叠後之兩透明導= 基材之長與長及寬與寬之間之相對距離為〇 5至3公分之門. 步驟26〇:填充電解質170於含有電致變色層透 明導電基材11G與含有輔助電致變色層⑽之第二透明 材140之間； 土 201248285 一步驟27G :沿著兩組[型邊界線⑵及⑸，以封裝劑進行 于裝之動作。以封裝劑沿著abc與adc之兩組L型邊界線121 與151進行一封裝之動作。 其中，第-透明導電層120與第二透明導電層15〇係在 電致變色裝置1〇〇中扮演導電電極之角色，提供變色過程所 ，電”L因此必須採用兼具尚穿透率及高導電度之透明導 電材料。故’於本發明中，透明導電層係選自於氧化銦鍚 _啦Thl 0恤，IT〇)、氧化紹鋅㈧， AZ〇)、摻氟氧化錫薄膜(Fluorine Tin Oxide，FT0)之一。較佳 地，又由於摻氟氧化錫薄膜(FT〇)耐酸驗、耐熱、耐濕以及 成膜原料便宜且生產成本低，因此，在本發明中係使用摻氟 氧化錫薄膜。此外，第一透明導電層12〇與第二透明導電層 150之沈積方法係選自濺鍍法、蒸鍍法、電鍍法、化學氣相 沈積法、溶膠-凝膠法、喷霧裂解法、浸潰法、電化學法之 一’且成膜之厚度為50奈米至300奈米之間。 於本發明中，電致變色層130通常係選自於氧化鎢、氧 化鉬、氧化鈦、氧化鈮、氧化銥之一。其中，較佳地，目前 最受矚目且廣為研究的電致變色材料的是氧化鎢，因其具有 南的著色效率(Coloration efficiency)、可逆性佳、相對價格 低、壽命最長且無毒等優點。氧化鶴薄膜在1969年被發現 具有電致色變性質，其變色機制為施加負電位於氧化鎢時， 電子及陽離子（或質子）同時遷入於氧化鎢裡，而生成 201248285 mxwo3，其變色反應方程式如式所示： WO3+ xM++xe' <~~> MxW03 (無色或淡黃色）（藍色或深藍色） 其中，M+為H+、Li+或Na+等一價金屬陽離子，MxW〇3 俗稱為Tungsten bronze呈青銅色或深藍色，X值大約在0-0.5 之間，其大小是由通入薄膜的電量來決定。通入電流使氧化 鎢發生還原反應，此時M+及e-同時進入W03薄膜中，而形 成藍色的MxW〇3，為著色的反應。去色反應為MxW〇3薄膜 中的M+及e—同時離開而形成無色的w〇3。經由此一可逆的 電化學反應在氧化態與還原態之間作反覆的去色及著色。當 停止外加電位後，離子以極緩慢的擴散方法離開，形成電致 變色元件特有的記憶效應，相對於其它產品需隨時施以外加 電位，具有節能的優點。 另一方面，輔助變色層16〇可為一般電極或另一種電致 變色物質，用來加強顏色或穿透率變化。當輔助電極與另一 種工作電極搭配組成之電致變色元件稱為「互補式電致色變 元件」（Complementary electrochromic device)。若電致變色 層為還原態著色之㈣，辅助電極層則需使用氧化態著色之 材料。因此，互補式電致色變元件通電時兩極同時著色或去 色’具有高的著色效率以及較大的光學密度差等優點。而該 輔助電致變色層⑽通常健自魏她、氧化鎳、氧化 鉻、氧化Μ、氧化鐵、氧化銅、氧碰之—，圭地為氧化 201248285 鎳，其為廉價、高效社高穩定性之電致色變材料，其穿透 調節率料如氧__，其魏化_色，且具儲存離 子的能力’可以搭配還原態之氧化鶴薄膜製成互補式電致色 變元件。此外，氧輯_在著色㈣賴色，去色時為透 明無色’魅對比非常_，且具有良好的絲特性盎耐久 性質。當胁外加電錄魏_贿，祕料與電子同 時注入或移出’使薄膜氧倾原發生價數改變造成顏色變 化。而於本發明之-具體例巾，電致變色歧由氧化鶴所製 成，辅助電致變色層則是由氧化錄所製成。其中，電致變色 層uo與輔助電致變色層160之沈積方法係選自濺鍛法、蒸 鏟法、電触、化學氣相沈躲、轉_凝膠法、嘴霧裂解 法、浸潰法、電化學法之-，且成膜之厚度為⑻奈米至_ 奈米之間。 值得注意的是，含有電致變色層130 no與含有_f _色層16G之第二翻料基材i4〇預留 -邊界範圍，並以交錯平行之方法交疊，以形成兩虹型邊界 線m及15ι。㈣後之兩義導電基材之長與長及寬與寬之 -"〜叫，如圃j所示。由於此種交 疊方法可使第-透明導電基材110與第二透明導電基材⑽之 间之相對距離為 可用面積增大進而使整體元件之驅動電鱗低，其中，驅動電 壓又以30至40伏特為較佳。 於本發明中之電解質m層，其功⑽提供及傳導離子 201248285 給予電致變色材料’故須儲存大量的陽離子，並能快速擴散 進入變色層，使之反應產生顏色的變化，因此在應用上良好 的離子傳導層應具有高電子電阻值與良好的離子傳導能 . 力。其中，於本發明中電解質係選用固態、液態、膠態之一。 較佳地，係採用膠態。早期採用液態電解質在元件封裝上相 當不方便，而且有溢漏的疑慮，故現今多使用固態電解質組 成全固態電致色、憂元件（All-solid-state electrochromic device)。然而，習知固態電解質(例如UNb〇3或Ta2〇5)需要 在持續施加較高電壓下才可完成著色或去色，且所花費的時 間較長，而呈膠狀之電解質層將可有效增加離子傳導速度， 並縮短去/著色時間，同時僅需施加一較低電壓便可完成去 色或著色狀態。 其中，本發明中之膠態電解質17〇係由一離子液體與一膠 狀聚合物所混合而成。一般而言，該離子液體係由-金屬陽離 子以及-非金屬陰離子組成，如鹽溶解於8〇(rc高溫或 更高溫度’相反的’雜子親是指—以祕存在之離子鹽 類，溫度在lGGt或更低’更具體的，在室溫下以液態存在的 離子液體稱之為RTIL(room tempe_re — Uquid)。其中由 祕子液财具揮發性，因此沒絲⑽，且離子導電度也 高；更具體的說，由於離子液體具有高極性，所以對於無機或 有機化合物之簡雜好，且祕下之躲可以在廣大之溫度 範圍下呈現，因此可應用於多種化學領域，包括結晶學，分離 13 201248285 技術以及電化學。此外，因為離子液體之低對稱性，分子間吸 引力較弱以及電荷分佈於陽離子等特性，所以具有低熔點，甚 至，離子液體不具雜、不祕，溫度敎性高，其物化特性 優於具有環保特點之溶劑，因此可取代傳統具毒性之有機溶 劑。物化特性包括可在敍的溫度範圍下呈現為液態，高溶劑 化特性以及形成不解麟的能力。在實用上，本發明使用之 該離子液體與該膠狀聚合物所混合而成之電解質17〇的電致變 色裝置，提供了下述優點：⑴膠狀電解質可保持離子液體，並 解決電解質溢漏的問題；(2)因離子液體聚合之電解質之離 子濃度與傳統以有機溶劑為主之電解質為高，因此電致變色裝 置之顯影/驟熄速率較高。比較本發明電致變色裝置與一使用液 體電解質之電致變色裝置，其反應速率不相上下，因為離子液 體之離子導電度南達1()·3〜1〇·6 I之間。此外，本發明電致 變色裝置更提供—個具有S記憶賴Memory Effeet)之電致變 色裝置’⑶離子液體具有最大電化學電壓範IKeleetiOehemicai wmdow) ’也因此與—利用有機溶劑為主之電解質相比較，本 :二中:解質的分解可能性較低;⑷因本發明裝置使用一較 體’因此可降㈣致變色裝置之副反應；（5)離 Α σ解質沒有蒸汽麼力，因此沒有與電解質之揮發與 顯影題。料’利_錢進行電致變色裝置之色彩 濃二景^，會，離子導電度以及電解質170中之離子 溶^中的移’離子導電度的係制離子在電解質170 程度。因此，溶液黏度以及溶液中之離子濃度均 201248285 會影響離子導電度。當溶液中黏度下降，離子可自由移動，且 造成離子導電度上升；而當溶液中離子濃度增加，離子數量就 會增加，而造成離子導電度相對增加；傳統液體電解質具有較 低黏度’因此其離子濃度約為1〇-2〜l〇-4S/cm之間；而本發明 使用之該離子液體與該膠狀聚合物所混合而成之電解質17〇， 其離子導電度約在1〇-3〜1〇-6 S/cm之間。於本發明中，該離子 液體中之陽離子與陰離子皆無限制。另一方面，該膠狀聚合物 係選自聚甲基丙浠酸甲醋(p〇lymethyl methacrylate，PMMA)、聚 偏一氟乙婦(polyvinylidene difluoride, PVDF)、聚氣乙稀 (polyvinyl chloride，PVC)、聚氧化乙稀(polyethylene oxide, PEO) 以及聚甲基丙烯酸經乙酯（polyhydroxyethyl methacrylate, PHEMA)、乙烯一乙酸乙烯酯共聚物(Ethylene vinyl accetate copolymer, EVA)、聚乙烯醇(p〇lyvinyi alcohol，PVA)之一。 電解質與PVB膠材(或其他膠材)的混合材料，可使用方法 有： • 二、直接塗佈（網印）於玻璃後再加熱烘乾硬化； 四、將含電解質的膠材製成薄膜後裁剪適當大小覆貼於 玻璃後再經層壓機加熱壓合兩片玻璃。 在使用本發明之電致變色裝置100時，是將該裝置之第一 導電基材及第二導電基材與一直流電源電性連接，再藉由通入 電壓，即可使產生電致變色之效果。其中，藉由該交錯平行之 方法交疊之封裝技術可使該電致變色裝置100之驅動電壓為 30伏特至50伏特之間，且調光時間為100毫秒至60秒之間。 15 201248285 <實施例ι> 首先，將玻璃(1.4公尺xu公尺)首先經過脫脂劑處理， 已去除表面油污，再經過水洗後讓玻璃表面不殘留脫脂劑， 保持清潔，之後再以鹽酸在該玻璃表面進行清洗處理，復以 清水清洗以去除多餘的鹽酸溶液，最後將玻璃以濺鍍的方法 鍵上200奈米之FTO薄膜。另一方面，以濺鍵方法於FT〇 玻璃表面开〉成一層厚為3〇〇nmiw〇3工作電極；另一對向 電極也以上述方法於FT〇玻璃表面形成一厚度為3〇〇nm之 ΝιΟ，將作電極與對向電極在—預留邊界細區域外，以 一交錯平行之方法交疊，交疊後之該兩透明導電基材之長與 長及寬與寬之間之相對距離為〇 5公分之間。最後，沿著其 邊角以一含玻璃珠間隙子之封裝劑進行封裝，以形成一不含 電解質之電致變色裝置。 接著，準備一含有離子液體與一膠狀聚合物所混合而成之 電解質。其中該離子液體為鋰鹽之1M LiC104，以及混合有 [emim][bF4]之離子液體（其中EMIM為乙基甲基味嗤離子 【ethyl methyl imidaz〇lium】);而該膠狀聚合物為乙烯一乙酸乙 烯酉曰共聚物(Ethylene vinyl accetate copolymer, EVA)。將此電解 質/主入上述製備完成之含無機金屬氧化物W03 /NiO電極之電 致變色裝置中。其中，形成之膠狀聚合物電解質之離子導電度 在至溫下約為10_3s/cm。其中，電解質與膠材混時，係使用直 接塗佈（網印）於玻璃後再加熱烘乾硬化。最後，將兩電極與 201248285 -直流電源紐連接’縣由通人35簡之健，即可使產 生電致變色之效果，且調光時間為i秒。其中，製備完成之電 致變色裝置顯影出-深藍顏色，穿透率約為3〇%;在驟媳時， 此電致變色裝置為透明’且穿透率為6〇%。此外，由於上述電 致變色裝置使用膠狀電解質，因此沒有因為電解質溢漏或揮發 的問題，同時提供-絕佳之記憶效應，超過75小時以上。 <實施例2> 實施例2大致如實施例丨之步驟，其主要差異係：ρτ〇玻璃 表面形成之w〇3工作電極厚度及對向電極之則改為4〇〇 奈米’以-交錯平行之方法交叠，交4後之該兩透明導電基 材之長與長及寬與寬之間之相對距離改為15公分之間；混 合有[EMIM][BF4]之離子液體改為使用[BMIM][TFSI](其中 BMIM代表丁基曱基味唾離子【butylme%1脑減伽】）； 而《玄膠狀t合物改為聚乙稀醇(p〇lyVinyl alc〇h〇i，卩乂八）。其 中，形成之膠體聚合電解質之離子導電度約為3χ1〇·3 s/cm。 其申，電解質與膠材混合時係將含電解質的膠材製成薄膜後 裁剪適當大小覆貼於玻璃後再經層壓機加熱壓合兩片玻 璃。製備完成之電致變色裝置顯影出一深藍顏色，穿透率約. 為30% ;在驟熄時，此電致變色裝置為透明，且穿透率為 5〇%。如實施例丨所述，本電致變色裝置提供一絕佳之記憶 效應，超過75小時以上。值得注意的是，此電致變色裝置 之驅動電壓為4〇伏特，即可使產生電致變色之效果，且調 201248285 光時間可小於1秒。 <實施例3> 實施例3大致如實施例1之步驟，其主要差異係：將玻璃基 板之尺寸改為1公尺xG 5公尺，且將玻璃改以蒸鍍的方法鑛 上150奈米之FTO薄膜。另一方面，改以電鍍之方法於FT〇 玻璃表面形成—層厚為45〇nmiw〇3工作電極；另一對向 電極也以上述方法於FTO玻璃表面形成一厚度為 450nm 之 ΝιΟ，以一交錯平行之方法交疊，交疊後之該兩透明導電基 材之長與長及寬與寬之間之姆距敎為G.3公分之間；而 ^(polyvinyl chloride, PVC) ° 中，形成之膠體聚合電解質之離子導電度約為l〇-2S/cm。其 中’電解質與膠材混時’係使用直接塗佈（網印）於玻璃後 再加熱供乾硬化。需注意的是，電解質與轉混合時亦可以 將3電解質的膠材製成薄膜後裁剪適當大小覆貼於玻璃後 再經層壓機加熱壓合兩片玻璃，亦可以得到類似之特性。製 備完成之電致變色裝置㈣出—賴顏色，紐率約為 63% ;在驟熄時，此電致變色裝置為透明，且穿透率為55%。 如實施例1所述’本電致變色裝置提供—絕佳之記憶效應， 超過70小時以上。值得注意的是，此電致變色裝置之驅動 電C為42伏特’即可使產生電致變色之效果，且調光時間 可小於5秒。 <實施例4> 201248285 實施例4大致如實施例3之步驟，其主要差異係：玻璃基材 改為塑膠基材，且將此電致變色裝置彎折90°後待回復原狀 後接著進行以下測試：將兩電極與-32V直流電源電性連接， 再反覆且持續通入+32V或-32V電壓(當通入-32V電壓時， 該電致色變裝置會轉變為著色狀態，而當通入+32V電壓 時’該電致色變裝置則轉變為去色狀態），同時於650 nm之 波長下’利用紫外光·可見光光譜儀(UV-VIS spectroscope)進 行穿透率測試，可得知穿透率於約15秒内由72%變化至約 22%(穿透率變化值Δτ==完全去色時之穿透率—完全著色時 之穿透率~τ50%) ’且隨著時間的改變，可穩定地維持此穿透 率變化值，由此可證明該可撓式電致色變裝置確實具有極佳 的光調節度。 綜上所述，本發明之一種電致變色裝置及其製程方法具有 以下之功效： 1. 該電致變色裝置之驅動電壓為30伏特至50伏特之間，且 調光時間為100毫秒至6〇秒之間； 2. 藉由本發明之電極交錯平行交疊之封裝技術比傳統封裴 方式之驅動電壓將可降低1/2〜1/3左右，並同時降低其調 光時間； 3. 藉由本發明之電極交錯平行交4之封裝技術將可有效增 201248285 力口離子傳導速度，並縮短去/著色時間,· 4,藉由本發明之電致變色裝置，可使開放電路記憶數小時， 保持透射固定狀態且不須做電壓脈衝之修正。 雖然本發明已以前述較佳實施例揭示，然其並非用以限定 本發明’任何熟纽技藝者’在不麟本㈣之精神和範圍 田可作各種之更動與修改。如上述的解釋，都可以作各型 式的修正與變化，而不會破壞此發明的精神。因此本發明之保 濩範圍當概社巾料利難所界定者為準。 【圖式簡單說明】 第1圖顯示為本發明之一種電致變色裝置； 第2圖顯示為本發明之一種電致變色裂置之製備方法；及 第3圖顯示為本發明之—種電致變色裝置之俯視圖。 【主要元件符號說明】 1〇〇電致變色裝置 U0第一透明基材 in第一透明基材之長 112第一透明基材之寬 120第一透明導電層 121 l型邊界線 130電致變色層 140第二透明基材 20 201248285 141第二透明基材之長 142第二透明基材之寬 150第二透明導電層 151 L型邊界線 160輔助電致變色層 170電解質 200電致變色裝置之製備方法之流程圖 21The second transparent conductive substrate having the auxiliary electrochromic layer is stacked in a staggered plane to form two sets of L-shaped boundary lines 121 and 151. Two transparent guides after overlap = the relative distance between the length and the length and the width and width of the substrate is 〇5 to 3 cm. Step 26: filling the electrolyte 170 in the transparent conductive substrate 11G containing the electrochromic layer Between the second transparent material 140 and the second transparent material 140 containing the auxiliary electrochromic layer (10); soil 201248285, step 27G: along the two sets of [type boundary lines (2) and (5), the encapsulating agent is used for the loading operation. The encapsulation is performed along a set of L-shaped boundary lines 121 and 151 of abc and adc. Wherein, the first transparent conductive layer 120 and the second transparent conductive layer 15 are in the role of a conductive electrode in the electrochromic device 1 ,, providing a process of discoloration, and therefore the electric “L must be combined with the penetration rate and A highly conductive transparent conductive material. Therefore, in the present invention, the transparent conductive layer is selected from the group consisting of indium oxide 钖 _ Thl 0 shirt, IT 〇, zinc oxide (eight), AZ 〇), fluorine-doped tin oxide film ( One of Fluorine Tin Oxide, FT0). Preferably, since the fluorine-doped tin oxide film (FT〇) is acid-resistant, heat-resistant, moisture-resistant, and the film-forming raw material is inexpensive and the production cost is low, in the present invention, the blending is used. The tin oxyfluoride film. In addition, the first transparent conductive layer 12 〇 and the second transparent conductive layer 150 are deposited by sputtering, evaporation, electroplating, chemical vapor deposition, sol-gel, One of the spray pulverization method, the immersion method, and the electrochemical method, and the thickness of the film formed is between 50 nm and 300 nm. In the present invention, the electrochromic layer 130 is usually selected from tungsten oxide and oxidized. One of molybdenum, titanium oxide, cerium oxide, and cerium oxide. Among them, preferably, The most well-recognized and widely studied electrochromic material is tungsten oxide, which has the advantages of coloring efficiency, good reversibility, low relative cost, longest life and non-toxicity. The oxidized crane film was in 1969. It has been found to have electrochromic properties. The color change mechanism is that when a negative electric current is applied to the tungsten oxide, electrons and cations (or protons) simultaneously migrate into the tungsten oxide to form 201248285 mxwo3, and the color change reaction equation is as shown in the formula: WO3+ xM++xe' <~~> MxW03 (colorless or light yellow) (blue or dark blue) where M+ is a monovalent metal cation such as H+, Li+ or Na+, and MxW〇3 is commonly known as Tungsten bronze in bronze. Color or dark blue, X value is about 0-0.5, the size is determined by the amount of electricity flowing into the film. The current is passed to reduce the tungsten oxide, and M+ and e- enter the W03 film at the same time. The blue color of MxW〇3 is formed as a coloring reaction. The decoloring reaction is M+ and e- in the MxW〇3 film simultaneously leaving to form a colorless w〇3. Through this reversible electrochemical reaction in the oxidation state and reduction Reverse between states When the applied potential is stopped, the ions leave with a very slow diffusion method, forming a unique memory effect of the electrochromic element, and it is necessary to apply an external potential at any time with respect to other products, which has the advantage of energy saving. The auxiliary color changing layer 16 can be a general electrode or another electrochromic substance for enhancing color or transmittance change. The electrochromic element composed of the auxiliary electrode and another working electrode is called "complementary electrophoresis". "Complementary electrochromic device". If the electrochromic layer is colored in the reduced state (4), the auxiliary electrode layer needs to be colored in an oxidized state. Therefore, when the complementary electrochromic element is energized, the two poles are simultaneously colored or decolored, which has the advantages of high coloring efficiency and large optical density difference. The auxiliary electrochromic layer (10) is usually derived from Wei, nickel oxide, chromium oxide, cerium oxide, iron oxide, copper oxide, oxygen, and the ground is oxidized 201248285 nickel, which is cheap, high efficiency and high stability. The electrochromic material has a penetrating adjustment rate material such as oxygen__, which has a Weihua_color, and has the ability to store ions', and can be combined with a reduced-state oxidized crane film to form a complementary electrochromic element. In addition, the oxygen series _ in the coloring (four) ray color, the color is transparent and colorless when the color is removed, and the glare contrast is very _, and has a good silk property and an endurance property. When the threat is added to the Wei-Bai, the secret and the electrons are injected or removed at the same time, causing the film to change its valence to cause a color change. In the specific embodiment of the present invention, the electrochromic aberration is made of oxidized crane, and the auxiliary electrochromic layer is made of oxidized recording. Wherein, the deposition method of the electrochromic layer uo and the auxiliary electrochromic layer 160 is selected from the group consisting of a sputtering method, a steaming method, an electric contact, a chemical vapor deposition, a transfer gel method, a nozzle mist cracking method, and a dipping Method, electrochemical method -, and the thickness of the film formation is between (8) nanometer and _ nanometer. It is worth noting that the electrochromic layer 130 no and the second flip substrate i4 containing the _f _ color layer 16G have a reserved-boundary range and overlap in a staggered parallel manner to form two rainbow borders. Line m and 15ι. (4) The length and width, width and width of the latter two-way conductive substrate -"~, as shown in 圃j. Because of the overlapping method, the relative distance between the first transparent conductive substrate 110 and the second transparent conductive substrate (10) is increased by the available area, so that the driving scale of the integral component is low, wherein the driving voltage is 30. It is preferred to 40 volts. In the electrolyte m layer of the present invention, the work (10) provides and conducts ions 201248285 to the electrochromic material', so a large amount of cations must be stored, and can rapidly diffuse into the color changing layer to cause a color change, so in application A good ion conducting layer should have a high electronic resistance value and good ion conduction energy. Among them, in the present invention, the electrolyte is selected from one of a solid state, a liquid state, and a colloidal state. Preferably, a colloidal state is employed. Early use of liquid electrolytes was inconvenient in component packaging, and there were concerns about spillage. Therefore, solid-state electrolytes are now used to form all-solid-state electrochromic devices. However, conventional solid electrolytes (such as UNb〇3 or Ta2〇5) need to be colored or decolored after continuous application of a higher voltage, and it takes a long time, and a gel-like electrolyte layer will be effective. Increasing the ion conduction velocity and shortening the de-coloring time can be accomplished by applying a lower voltage. Among them, the colloidal electrolyte 17 in the present invention is a mixture of an ionic liquid and a gel polymer. In general, the ionic liquid system consists of a metal cation and a non-metal anion, such as a salt dissolved in 8 〇 (rc high temperature or higher temperature 'opposite' heterophilic pro---the ionic salt present in the secret, The temperature is at lGGt or lower. More specifically, the ionic liquid present in a liquid state at room temperature is called RTIL (room tempe_re - Uquid). Among them, the secret liquid is volatile, so there is no wire (10), and ion conduction The degree is also high; more specifically, because the ionic liquid has high polarity, it is easy to be used for inorganic or organic compounds, and the secret hiding can be exhibited in a wide range of temperatures, so it can be applied to various chemical fields, including Crystallization, separation 13 201248285 Technology and electrochemistry. In addition, because of the low symmetry of ionic liquids, weaker intermolecular attraction and charge distribution in cations, it has a low melting point, and even ionic liquids are not complex or secret. High temperature enthalpy, its physicochemical properties are superior to those of environmentally friendly solvents, so it can replace traditional toxic organic solvents. Physicochemical properties include temperature In the range, it exhibits a liquid state, a high solvating property, and an ability to form a solution. In practical use, the electrochromic device of the electrolyte 17 混合 which is mixed with the ionic liquid and the gel polymer is provided by the present invention. The following advantages are obtained: (1) the gel electrolyte can maintain the ionic liquid and solve the problem of electrolyte leakage; (2) the ion concentration of the electrolyte which is polymerized by the ionic liquid is higher than that of the conventional organic solvent-based electrolyte, and thus electrochromic The developing/quenching rate of the device is relatively high. Comparing the electrochromic device of the present invention with an electrochromic device using a liquid electrolyte, the reaction rate is comparable, because the ionic conductivity of the ionic liquid is up to 1 ()·3~ In addition, the electrochromic device of the present invention further provides an electrochromic device having a S memory (e.g., ionic liquid having a maximum electrochemical voltage of IKeleeti Oehemicai wmdow). Compared with electrolytes based on organic solvents, this: two: the possibility of decomposition of the solution is low; (4) because the device of the present invention uses a relatively "thus" Means the color of side reactions; (5) from the solution quality without steam Α σ what force, so there is no volatilization of the electrolyte and the developing problems. The color of the electrochromic device is concentrated, and the ion conductivity and the ionization of the ion conductivity in the electrolyte 170 are at the electrolyte 170 level. Therefore, the viscosity of the solution and the ion concentration in the solution will affect the ionic conductivity of 201248285. When the viscosity in the solution drops, the ions can move freely and cause the ionic conductivity to rise. When the concentration of ions in the solution increases, the amount of ions increases, and the ionic conductivity increases relatively. The conventional liquid electrolyte has a lower viscosity. The ion concentration is about 1〇-2~1〇-4S/cm; and the electrolyte used in the present invention is a mixture of the electrolyte and the gelatin polymer, and the ionic conductivity is about 1〇- 3~1〇-6 S/cm. In the present invention, the cation and the anion in the ionic liquid are not limited. On the other hand, the gelatinous polymer is selected from the group consisting of p〇lymethyl methacrylate (PMMA), polyvinylidene difluoride (PVDF), and polyvinyl chloride (polyvinyl chloride). PVC), polyethylene oxide (PEO), and polyhydroxyethyl methacrylate (PHEMA), Ethylene vinyl accetate copolymer (EVA), polyvinyl alcohol (p〇) One of lyvinyi alcohol, PVA). The mixture of electrolyte and PVB glue (or other glue) can be used as follows: • 2. Direct coating (screen printing) on glass and then heating and hardening; 4. Making electrolyte containing electrolyte into film After cutting, the appropriate size is applied to the glass, and then the two glasses are heated and pressed by a laminator. When the electrochromic device 100 of the present invention is used, the first conductive substrate and the second conductive substrate of the device are electrically connected to the DC power source, and then the electrochromic property is generated by applying a voltage. The effect. Wherein, the driving voltage of the electrochromic device 100 can be between 30 volts and 50 volts by the interleaving method of the staggered parallel method, and the dimming time is between 100 milliseconds and 60 seconds. 15 201248285 <Example ι> First, the glass (1.4 m x ft) is first treated with a degreaser, the surface oil is removed, and after washing with water, the degreaser is left on the surface of the glass, kept clean, and then hydrochloric acid is used. The surface of the glass was cleaned, washed with water to remove excess hydrochloric acid solution, and finally the glass was sputtered onto a 200 nm FTO film. On the other hand, the surface of the FT glass is opened by a sputtering method to form a working electrode with a thickness of 3〇〇nmiw〇3; the other opposite electrode is also formed with a thickness of 3〇〇nm on the surface of the FT glass by the above method. Ν Ο Ο 将 将 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极 电极The distance is between 5 cm. Finally, it is packaged along its corners with an encapsulant containing a glass bead spacer to form an electrochromic device free of electrolyte. Next, an electrolyte containing an ionic liquid and a gel polymer is prepared. Wherein the ionic liquid is a lithium salt of 1M LiC104, and an ionic liquid mixed with [emim][bF4] (wherein EMIM is ethyl methyl imidazium); and the gelatinous polymer is Ethylene vinyl accetate copolymer (EVA). This electrolyte was mainly introduced into the above-described electrochromic device containing the inorganic metal oxide W03 / NiO electrode. Here, the ionic conductivity of the formed gel-like polymer electrolyte is about 10 _ 3 s/cm at a temperature. Wherein, when the electrolyte is mixed with the rubber material, it is directly coated (screen printing) on the glass, and then dried and hardened by heating. Finally, the two electrodes are connected to the 201248285-DC power supply. The county is made up of the genus 35, which can produce electrochromic effects with a dimming time of i seconds. Among them, the prepared electrochromic device developed a dark blue color with a transmittance of about 3%; at the time of the flash, the electrochromic device was transparent and the transmittance was 6〇%. Further, since the above electrochromic device uses a gel electrolyte, there is no problem of leakage or volatilization of the electrolyte, and at the same time, an excellent memory effect is provided, which is more than 75 hours. <Example 2> Example 2 is roughly as a step of the example, and the main difference is that the thickness of the working electrode of the w〇3 working surface of the ρτ〇 glass surface and the opposite electrode are changed to 4〇〇N' The method of staggered parallel overlaps, and the relative distance between the length and the length and width of the two transparent conductive substrates after the intersection of 4 is changed to 15 cm; the ionic liquid mixed with [EMIM][BF4] is changed to Use [BMIM][TFSI] (where BMIM stands for butyl sulfonyl salivary [butylme%1 brain minus gamma]); and "black gelatin t compound is changed to polyethyl alcohol (p〇lyVinyl alc〇h〇) i, 卩乂 eight). The ionic conductivity of the formed colloidal polyelectrolyte is about 3 χ 1 〇 3 s/cm. It is claimed that when the electrolyte is mixed with the rubber material, the electrolyte containing the electrolyte material is formed into a film, and then cut into a proper size and applied to the glass, and then the two glasses are heated and pressed by a laminator. The prepared electrochromic device developed a dark blue color with a transmittance of about 30%; at the time of quenching, the electrochromic device was transparent and had a transmittance of 5%. As described in Example 本, the electrochromic device provides an excellent memory effect for more than 75 hours. It is worth noting that the driving voltage of the electrochromic device is 4 volts, which can produce electrochromic effect, and the light time of 201248285 can be less than 1 second. <Example 3> Example 3 is substantially the same as that of Example 1, and the main difference is that the size of the glass substrate is changed to 1 m x 5 m, and the glass is changed to a vapor deposition method. FTO film of rice. On the other hand, it is formed by electroplating on the surface of FT glass - a layer thickness of 45 〇nmiw 〇 3 working electrode; the other counter electrode also forms a thickness of 450 nm on the surface of the FTO glass by the above method, The cross-parallel method overlaps, and the distance between the length and the length and the width of the two transparent conductive substrates after the overlap is G.3 cm; and ^(polyvinyl chloride, PVC) ° The colloidal polyelectrolyte formed has an ionic conductivity of about 1 〇 -2 S/cm. Here, the 'electrolyte mixed with the rubber material' is directly coated (screen printing) on the glass and then heated for dry hardening. It should be noted that when the electrolyte is mixed with the mixture, the electrolyte of the 3 electrolyte can be made into a film, and then cut into a proper size and coated on the glass, and then heated and pressed by the laminator to obtain two similar glasses, and similar characteristics can be obtained. The prepared electrochromic device (4) has a color-dependent color ratio of about 63%; in the case of quenching, the electrochromic device is transparent and has a transmittance of 55%. The present electrochromic device as described in Example 1 provides an excellent memory effect for more than 70 hours. It is worth noting that the driving power C of the electrochromic device is 42 volts to produce an electrochromic effect, and the dimming time can be less than 5 seconds. <Example 4> 201248285 Example 4 is substantially the same as the step of Example 3, the main difference is that the glass substrate is changed to a plastic substrate, and the electrochromic device is bent at 90° and then returned to the original state, followed by The following test: the two electrodes are electrically connected to the -32V DC power supply, and then repeatedly and continuously input +32V or -32V voltage (when the voltage of -32V is applied, the electrochromic device will change into a colored state, and when When the voltage is +32V, the electrochromic device is changed to the decolorized state, and at the wavelength of 650 nm, the transmittance test is performed by UV-VIS spectroscope. The penetration rate changes from 72% to about 22% in about 15 seconds (transmission rate change value Δτ==penetration rate when completely decolored - penetration rate at full coloring ~τ50%)' and with time The change of the transmittance can be stably maintained, and it can be confirmed that the flexible electrochromic device does have excellent light regulation. In summary, an electrochromic device and a process method thereof according to the present invention have the following effects: 1. The electrochromic device has a driving voltage of between 30 volts and 50 volts, and the dimming time is 100 milliseconds to 6 volts. Between the leap seconds; 2. The driving voltage of the electrode staggered parallel overlap of the present invention can be reduced by about 1/2 to 1/3 compared with the conventional sealing method, and at the same time reduce the dimming time; The encapsulation technique of the electrode staggered parallel intersection 4 of the present invention can effectively increase the ion transmission velocity of the 201248285 and shorten the de-coloring time. 4, the open circuit can be kept for several hours by the electrochromic device of the present invention. The transmission is fixed and there is no need to correct the voltage pulse. Although the present invention has been disclosed in the foregoing preferred embodiments, it is not intended to limit the invention, and the invention may be variously modified and modified in the spirit and scope of the invention. As explained above, various modifications and variations can be made without departing from the spirit of the invention. Therefore, the scope of protection of the present invention is subject to the definition of the difficulty of the general towel. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an electrochromic device of the present invention; FIG. 2 shows a method for preparing an electrochromic crack of the present invention; and FIG. 3 shows a type of electricity of the present invention. Top view of the chromogenic device. [Main component symbol description] 1〇〇 electrochromic device U0 first transparent substrate in the length of the first transparent substrate 112 width of the first transparent substrate 120 first transparent conductive layer 121 l type boundary line 130 electrochromic Layer 140 second transparent substrate 20 201248285 141 second transparent substrate length 142 second transparent substrate width 150 second transparent conductive layer 151 L-shaped boundary line 160 auxiliary electrochromic layer 170 electrolyte 200 electrochromic device Flow chart of preparation method 21