201232910 λ •六、發明說明： 【發明所屬之技術領域】 本發明係有關-種全鈒液流電池之電極結構，尤其是使用石 墨氈單元嵌入具有流道結構的石墨集流板。 【先前技術】 在環保意識高漲且高油價時代的來臨，全世界的能源業者及 政府無不全力職各種可再生的綠色能源’比如海流發電、潮沙 # 魏、地熱能源、風力發電與太陽能電池，以取代日益枯竭的傳 統石化能源。由於再生能源所產生的電能變化起伏很大，常需要 輔助儲能纽以存過多的電力或穩定輸出電力，藉以在發電量充 足時將電力儲存起来，待發電量不足時將電力回饋至電力網路。 氧化還原電池(RedoxFlowBattery)常用於儲能系統中，而如 同一般的燃料電池，氧化還原電池的電極本身僅作觸媒催化用而 不參與反應，亦即電極不會有消耗及增長，而且反應物係由外部 送入電池内，並經轉化成具有化學能的產物後以流體形式儲存於 電池外。卩，且可依需要而將所儲存的化學能轉換成電能而釋放出 來，以達到儲能目的。所以，氧化還原電池很適合長時間充電戋 放電的應用中。 全鈒氧化還原液流電池(VRB, Vanadium Redox Flow Battery)，以下簡稱為全飢液流電池’由於具有可瞬時充放電、高 性能價格比以及使用壽命長的優點，因此是目前氧化還原電池中 極受矚目的技術，很適合當作大型的儲能設備。 參閱第一圖’習用技術全釩液流電池的示意圖。如第_圖所 示’一般的全鈒液流電池係包括多個正電極板10、多個負電極板 20、正極電解液30、負極電解液40、正極電解液儲存單元5〇以 4 201232910 及負極電解液儲存單元60，其中正極電解液3〇以及負極電解液 4〇分別健存於正極電解液儲存單元5〇以及負極電解液儲存單元 6〇中’且分聽以正極連接#線及貞極連接管線崎過正電極 10及負電極2G而形成個別的迴路，如圖中的箭頭所示。通常是 在連接官線上安置幫浦(圖中未顯示），用以將電解液持續的傳輸 至電極板。 此外，全釩液流電池可利用電源轉換單元9〇 ,比如直流至交 流轉換器(DC/AC Converter)，可經由正極連接線7〇以及負極連 鲁接線80而分別電氣連接該等正電極板1〇以及該等負電極板2〇, 同時可電氣連接外部輸入電源、92以及至外部負载94，用以將外 4輸入電源92的父流電轉換成直流電以供全鈒液流電池進行充 電，或將全釩液流電池放電所產生的直流電轉換成交流電而輸出 至外部負載94。 通常，使用不同價數之釩離子硫酸水溶液，比如v(Iy)/Y(V) 和v(n)/v(m)氧化還原對，以當作正極電解液3〇以及負極電解 液40，因此可進行以下的電化學反應： 充電 • V4+ 二V5+ + e- 故電 齐置 V3+ + e" ；- ΜI » γ2十 放電 全釩液流電池的優點包括： (1)電池的功率決定於電池的電池堆大小，也就是電極 表面積、單電池數目，電容量取決於電解液量的多寡，可輕易 實現大規模化。 201232910 (2) 不涉及相轉變，使得壽命大幅提升。 (3) 可深度放電且不對電池造成傷害。 (4) 可瞬時充放電。 (5) 電解液保存期限長，電池壽命得以增加。 (6) 電池架構簡早易於維修。 (7) 正負極使用相同活性物質，活性物質穿透過隔離膜 也不會對電解液造成損傷。 • 因此，全釩液流電池可用以解決可再生能源常具有的間歇性 發電特性，使得再生能源對電力網路供電的不確定性獲得改善。 目前，全釩液流電池已應用於：（1)電力公司，大規模的電力儲存、 平衡負載’（2)偏遠地區、中型電力用戶，為偏遠地區、工廠、公 司和大樓提供電力和緊急電力系統，（3)一般住家用戶，（4)風力' 太陽能可再生能源之配套儲能設備。 然而，上述習用技術的主要缺點包括電解液滯留(如3(1 volume)及濃度極化的現象，會影響到電池中電子交換的效率而 籲使整體的效料高。gj此，需要—種具有增加反應面積並改善電 4傳遞以提高電流密度及能量效率的全飢液流電池之電極結 構，以解決習用技術的問題。 【發明内容】 本發明之主要目的在提供一種全釩液流電池之電極結構，係 經連接官線連接全鈒液電解液儲存槽而與藉流動之全鈒液電解液 進仃氧化還原反應，用以儲存外部饋入之輸入電力或產生提供外 邛所需之輸出電力，該全鈒液流電池之電極結構係包括依序由外 而内對稱堆疊組合之質子交換膜、二石墨紙(―㈣）、二石 6 201232910 墨跋單元(Carbon Felt)、二塾片、二石墨集流板(Graphite Plate)、二 金屬片以及鎖固裝置，其中金屬片可由導電金屬構成，比如可為 銅片，鎖固裝置係用以將上述的質子交換膜、石墨紙、石墨氈單 元'塾片、石墨集流板以及金屬片組合成一體，而每個石墨集流 板具有溝槽狀的流道’且石墨氈單元為多個條狀結構體並可直接 故入流道中，且在嵌入石墨氈單元的流道上進一步覆蓋石墨紙， 使不同的電解液在相對應的流道中流動，同時質子交換膜當作隔 離膜’以隔開二側不同的電解液，進而形成電流迴路。 本發明的電極結構可應用於全釩液流電池，用以改善電解液 滯留的問題，並減少電解液濃度極化的現象，同時利用石墨氈單 元具有較大反應面積之特性，以提高電力轉換效率。 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做更詳細的說 明，俾使熟習該項技藝者在研讀本說明書後能據以實施。 參閱第二圖，為本發明全釩液流電池之電極結構的示意圖。 第二圖係顯示全釩液流電池之單-電池(Single Cell)的電極結構， 係用以當作清楚說明本發明的特徵的示範性實例，亦即本發明的 電極結構係可利用多個第二圖的結構而組合成大型的電極組合 體因此，如第二圖所示，本發明全飢液流電池之電極結構1〇〇 包括二金屬片（元件符號11G及112)、二石墨集流板(元件符號12〇 及122)、二石墨鼓單元(元件符號⑽及132)、二塾片（元件符號 140及142)、二石墨紙(元件符號⑼及⑸)以及質子交換膜160。 金屬片可由導電金屬構成，比如可為銅片。 本發明的石墨氈單元130及132以及石墨紙15〇及152具有 多孔性’且石魏單元13G及132進—步具有多個條狀之結構。 201232910 上述的一石墨紙150及152以三明治方式包夾住質子交換膜 160 ’而二墊片14〇及142進一步包夾住該二石墨紙15〇及152， 且墊片140及142個別具有单一中空洞或多個孔洞。要注意的是， 圖中的方形洞只是用以方便說明本發明特徵的實例而已，亦即墊 片140及142可包括長方形、圓形、橢圓形、菱形、三角形或多 邊形的單一中空洞或多個孔洞。 該二石墨集流板120及122在朝向石墨氈單元13〇及132的 表面上具有凹槽狀的流道，以使得具有多個條狀之結構的石墨童毛 單元130及132分別嵌入相對應的流道中，且該流道分別穿過二 墊片140及142的單一中空洞或該等孔洞。二石墨集流板12〇及 122再進一步分別包夾住該二墊片14〇及142，最後二金屬片（或銅 片）11〇及112包夾住該二石墨集流板12〇及122，並利用鎖固裝置 (圖中未顯示），比如螺絲，藉由多個穿孔17〇而將本發明的電極結 構100鎖固成一體。 因此，在本發明的全釩液流電池之電極結構100中，金屬片 110、石墨集流板120、石墨鼓單元130、墊片140、石墨紙150、 質子交換膜160、石墨紙152、墊片142、石墨鼓單元132、石墨 集流板122以及金屬片112係依序堆疊，如第二圖所示。 此外，s玄二石墨集流板120及122在相對面的二側邊上個別 具有快速接頭，用以分別當作電解液的注入口及排放口，讓電解 液流過流道。例如第三圖中所示的石墨集流板，其中石墨集流板 122包括溝槽狀的流道124以及連接外部的二快速接頭126及 127。此外，要注意的是，第三圖中流道】24的形狀係以單一蛇形 流場(serpentine)表示，但是本發明的範圍並未受限於此，因而流道 124的形狀可為多個蛇形流場、單一或多個指狀流場(interdigitated) 或平行流場(parallel)。 8 201232910 為進-步說明本發明的雜，請參閱第四圖，本發明電極結 構的簡化組合示賴。如第四_示，為簡化以方便說明進行電 化學反應的核心反應區之結構，因此圖中並未顯示出二塾片14〇 及142 ’而只顯示出二石墨集流板120及122、二石墨鼓單元130 及132、二石墨紙15〇及152以及質子交換膜16〇。二石墨童毛單元 130及132分別嵌入該二石墨集流板12〇及122的流道中且二石 墨紙150及152分別覆蓋在流道上方以蓋住該二石墨鼓單元13〇 及132 ’藉以形成包括石魏、石墨紙以及石墨集流板的三種石墨 材料之咼效率複合電極結構。同時該二石墨紙15〇及152分別貼 附至質子交換膜160的二側面上。 因此，由外部輸入且包含不同價電之釩離子的正極電解液及 負極電解液可流過相對應的流道，並利用質子交換膜16〇當作電 池隔離膜，以進行質子交換而形成電流迴路。例如，可使用包含 一仏及二價釩離子的第一電解液，以及包含四價及五價釩離子的 第一電解液，藉該第一電解液及該第二電解液中釩離子的電化學 反應，以產生電力而輸出至外部，或將外部輸入的電力轉換成適 备的銳離子以儲存電力。更具體的是，在外部輸入電力時，第一 電解液的三價釩離子轉換成二價釩離子，且第二電解液的四價鈒 離子轉換成五價釩離子，以進行充電，並在輸出電力至外部時， 第—電解液的二價叙離子轉換成三價飢離子，且第二電解液的五 價飢離子轉換成四價釩離子，以進行放電。 石墨鼓單元可為2〜20 μηι的聚丙烯腈纖維(PAN)、介相瀝青 纖維(mesophase pitch)、纖維素纖維(cellulose)、丙烯酸系纖維 (acrylic)、苯酚纖維(phen〇1)或聚醯胺纖維纖維(ar〇maticp〇丨丫細丨如） 的原纖維經由碳化和高溫石墨化而構成。此外，條狀的石墨氈單 元的厚度為3.0〜8.0 mm，且石墨鼓單元的本體密度(Bulk density) 9 201232910 * 可大於0.09g/cm及小於〇 2〇g/cm3 ,而其電阻率可小於 cm ’且其所含的石墨之層間距、係小於3 5入。 石墨紙可為2〜20师的聚丙稀腈纖維(pAN)、介相遞青纖維 (沖咖Pltch)、纖維素纖維(cellulose)、丙雜系纖維(acryiic)、 苯_維(和〇1)或聚醯胺纖維纖維(a_ticp〇iyamide)的賴 經由碳化和高溫石墨麵構成。此外，石墨紙的厚度為0.K0 _ ’且石墨紙的本體密度大於_ ^3及小於_ —3，其電 阻率小於⑽地.em而所含的石墨的層間距CW小於3.5 A。 • 石墨集流板可使用天然石墨或人工石墨構成。較佳的石墨集 流板的厚度可為10〜2Gmm，其本體密度可大於丨9G(g/em3)，其電 阻率可小於0.03_ . cm)，且所含的石墨的層間距(如2)可小於 3’38 A墊片可為聚四氟乙烯或稱作聚四氟乙稀 〇x>lytetmfl_ethylene ’ PTFE)顧。耕，^ s紐板可製成雙 面極板之架構(bipolarcell)…亦即石墨集流板的二相對面上分別具 有供不同電解液流過的流道，可藉堆疊而組合成大型的複合電 極，用以提高電功率。如第五圖所示，本發明堆疊型電極結構的 _ 、组口示思圖，其中石墨集流板12〇在單一單面上具有流道，而石 墨集流板121係在二補面上分财有流道。第五圖巾的箭頭表 示多個石墨集流板的堆疊方向。 本發明的特點在於，利用由石墨氈單元、石墨紙以及石墨集 流板所組成的高效率複合電極結構，尤其是石墨集流板本身具有 了仏電解液流過的流道，以改善電解液滯留(dea(j v〇〖ume)的問題， 可減少電解液濃度極化的現象，同時使用石墨氈單元及石墨紙複 合連結，使得電極的反應面積增大，並可使在多種電極材料之間 形成良好的導電網路以增進電荷傳遞，進一步改善整體的能量轉 換效率。因此，本發明的電極結構可應用於全釩液流電池，適合 10 201232910 當作電力_峰_时衡貞荷、大顯太_賴力發電儲電 設備以及偏遠地區的電力來源。 以上所料僅為用以糖本發明之較㈣施例，麟企圖據以 對本發明雌何形式上之關，是以，凡有在相同之發明精神下所 作有關本發明之钟修飾讀更，皆仍應包括在本發明賴保護之 範。 【圖式簡單說明】 第一圖為習用技術全釩液流電池的示意圖。 第二圖為本發明全釩液流電池之電極結構的示意圖。 第三圖為本發明石墨流板的示意圖。 第四圖為本發明電極結構的簡化組合示意圖。 第五圖為本發明堆疊型電極結構的組合示意圖。 【主要元件符號說明】 ίο正電極板 2〇負電極板 _ 30正極電解液 40負極電解液 正極電解液儲存單元 60負極電解液儲存單元 70正極連接線 80負極連接線 90電源轉換單元 92外部輸入電源 94外部負載 201232910 100電極結構 110,112金屬片（銅片） 120石墨集流板 121石墨集流板 122石墨集流板 124流道 126，127快速接頭 130石墨氈單元 132石墨氈單元 140墊片 142墊片 150石墨紙 152石墨紙 160質子交換膜 170穿孔201232910 λ • VI. Description of the Invention: [Technical Field] The present invention relates to an electrode structure of a full-twist flow battery, in particular, a graphite current collecting plate having a flow path structure is embedded using a graphite felt unit. [Prior Art] In the era of high environmental awareness and high oil prices, energy companies and governments all over the world are working hard on various renewable green energy sources such as ocean current power generation, Chaosha #魏, geothermal energy, wind power and solar cells. To replace the increasingly depleted traditional petrochemical energy. Since the electric energy generated by the renewable energy varies greatly, it is often necessary to assist the energy storage to store excess power or stabilize the output power, so that the power is stored when the power generation is sufficient, and the power is fed back to the power network when the power generation is insufficient. . RedoxFlow Battery is commonly used in energy storage systems. Like a general fuel cell, the electrode of a redox battery itself is used only for catalyst catalysis and does not participate in the reaction, that is, the electrode does not consume and grow, and the reactants It is externally fed into the battery and converted into a chemically soluble product and stored as a fluid outside the battery.卩, and the stored chemical energy can be converted into electrical energy and released as needed to achieve energy storage. Therefore, redox batteries are well suited for long-term charging and discharge applications. Vanadium Redox Flow Battery (VRB), hereinafter referred to as the whole hunger flow battery, is currently available in redox batteries due to its advantages of instantaneous charge and discharge, high performance and price ratio, and long service life. Highly attractive technology, it is suitable as a large energy storage device. See the first figure 'Study of a conventional vanadium redox flow battery. As shown in the figure, the general sputum flow battery system includes a plurality of positive electrode plates 10, a plurality of negative electrode plates 20, a positive electrode electrolyte 30, a negative electrode electrolyte 40, and a positive electrode electrolyte storage unit 5 〇 4 201232910 And the negative electrode electrolyte storage unit 60, wherein the positive electrode electrolyte 3〇 and the negative electrode electrolyte 4〇 are respectively stored in the positive electrode electrolyte storage unit 5〇 and the negative electrode electrolyte storage unit 6〇', and the positive electrode is connected to the # line and The drain connection line is over the positive electrode 10 and the negative electrode 2G to form an individual loop, as indicated by the arrows in the figure. Usually, a pump (not shown) is placed on the connecting official line to continuously transfer the electrolyte to the electrode plate. In addition, the all-vanadium flow battery can utilize a power conversion unit 9 such as a DC to AC converter, and can be electrically connected to the positive electrode plates via the positive connection line 7〇 and the negative connection line 80, respectively. 1〇 and the negative electrode plates 2〇, and can be electrically connected to an external input power source 92, and to an external load 94 for converting the parent current of the external 4-input power source 92 into a direct current for charging the full-flow battery. Or converting the direct current generated by discharging the all-vanadium flow battery into alternating current and outputting to the external load 94. Generally, different valence vanadium ion sulfuric acid aqueous solutions, such as v(Iy)/Y(V) and v(n)/v(m) redox couples, are used as the positive electrode electrolyte 3〇 and the negative electrode electrolyte 40, Therefore, the following electrochemical reactions can be carried out: Charging • V4+ Two V5+ + e-, then the V3+ + e";- ΜI » γ2 ten discharge all vanadium flow battery advantages include: (1) The power of the battery depends on the battery The size of the stack, that is, the surface area of the electrode, the number of cells, and the amount of capacitance depend on the amount of electrolyte, which can be easily realized on a large scale. 201232910 (2) Does not involve phase transitions, resulting in a significant increase in life. (3) Can be deeply discharged without causing damage to the battery. (4) Instantaneous charge and discharge. (5) The electrolyte has a long shelf life and battery life is increased. (6) The battery structure is easy to repair. (7) The same active material is used for the positive and negative electrodes, and the active material penetrates the separator without causing damage to the electrolyte. • Therefore, all-vanadium flow batteries can be used to address the intermittent power generation characteristics often associated with renewable energy sources, resulting in improved uncertainty in renewable energy supply to the power grid. At present, all vanadium redox flow batteries have been applied to: (1) power companies, large-scale power storage, balanced load '(2) remote areas, medium-sized power users, providing electricity and emergency power to remote areas, factories, companies and buildings System, (3) general home users, (4) wind energy solar energy renewable energy supporting energy storage equipment. However, the main disadvantages of the above-mentioned conventional techniques include electrolyte retention (such as 3 (1 volume) and concentration polarization phenomenon, which affects the efficiency of electron exchange in the battery and appeals to the overall effect of the material. An electrode structure of a total hunger flow battery having an increased reaction area and improved electric 4 transfer to increase current density and energy efficiency to solve the problems of the prior art. SUMMARY OF THE INVENTION The main object of the present invention is to provide an all-vanadium flow battery The electrode structure is connected to the full sputum electrolyte storage tank by connecting the official line to the redox reaction of the whole mash liquid electrolyte, for storing the externally fed input power or generating the external enthalpy Outputting electric power, the electrode structure of the full sputum flow battery comprises a proton exchange membrane sequentially stacked externally and internally symmetrically, two graphite papers (-(four)), two stones 6 201232910 ink element (Carbon Felt), two 塾Sheet, two graphite collector plates (Graphite Plate), two metal sheets and a locking device, wherein the metal sheet may be made of a conductive metal, such as a copper sheet, and the locking device is used to The proton exchange membrane, the graphite paper, the graphite felt unit 'bump, the graphite current collector and the metal sheet are combined into one body, and each graphite current collecting plate has a groove-shaped flow passage' and the graphite felt unit has a plurality of strip structures The body can be directly injected into the flow channel, and the graphite paper is further covered on the flow path embedded in the graphite felt unit, so that different electrolytes flow in the corresponding flow channels, and the proton exchange membrane acts as a separation membrane to separate the two sides. The electrolyte solution further forms a current loop. The electrode structure of the present invention can be applied to an all-vanadium flow battery to improve the retention of the electrolyte and reduce the polarization of the electrolyte concentration, while the graphite felt unit has a larger The characteristics of the reaction area are used to improve the power conversion efficiency. [Embodiment] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings and the reference numerals, and can be implemented by those skilled in the art after studying this specification. Referring to the second figure, it is a schematic diagram of the electrode structure of the all-vanadium redox flow battery of the present invention. The second figure shows the single-battery of the all-vanadium flow battery (Single The electrode structure of the cell is used as an illustrative example to clearly illustrate the features of the present invention, that is, the electrode structure of the present invention can be combined into a large electrode assembly using a plurality of structures of the second figure. As shown in the second figure, the electrode structure of the whole hunger flow battery of the present invention includes two metal sheets (component symbols 11G and 112), two graphite current collecting plates (component symbols 12A and 122), and two graphite drum units ( Component symbols (10) and 132), two dies (component symbols 140 and 142), two graphite paper (component symbols (9) and (5)), and proton exchange film 160. The metal sheets may be composed of a conductive metal, such as a copper sheet. The graphite felt units 130 and 132 and the graphite papers 15 and 15 have a porosity ' and the stone elements 13G and 132 have a plurality of strip-like structures. 201232910 The above-mentioned graphite papers 150 and 152 sandwich the proton exchange film 160' in a sandwich manner, and the two spacers 14 and 142 further sandwich the two graphite papers 15 and 152, and the spacers 140 and 142 are individually single. Hollow hole or multiple holes. It should be noted that the square holes in the figures are merely examples for facilitating the description of the features of the present invention, that is, the spacers 140 and 142 may include a single hollow hole or a plurality of rectangular, circular, elliptical, diamond, triangular or polygonal shapes. Holes. The two graphite current collecting plates 120 and 122 have groove-like flow paths on the surfaces facing the graphite felt units 13 and 132, so that the graphite children's hair units 130 and 132 having a plurality of strip structures are respectively embedded in the corresponding ones. In the flow path, the flow path passes through a single hollow hole or holes of the two spacers 140 and 142, respectively. The two graphite current collectors 12 and 122 further sandwich the two gaskets 14 and 142 respectively, and the last two metal sheets (or copper sheets) 11 and 112 sandwich the two graphite current collectors 12 and 122. And the electrode structure 100 of the present invention is locked into one body by a plurality of through holes 17 by means of a locking device (not shown) such as a screw. Therefore, in the electrode structure 100 of the all-vanadium redox flow battery of the present invention, the metal sheet 110, the graphite current collecting plate 120, the graphite drum unit 130, the gasket 140, the graphite paper 150, the proton exchange film 160, the graphite paper 152, and the mat The sheet 142, the graphite drum unit 132, the graphite current collecting plate 122, and the metal piece 112 are sequentially stacked as shown in the second figure. In addition, the smectite graphite collector plates 120 and 122 have individual quick joints on the opposite sides of the opposite side for respectively serving as an injection port and a discharge port of the electrolyte to allow the electrolyte to flow through the flow path. For example, the graphite current collecting plate shown in the third figure, wherein the graphite current collecting plate 122 includes a groove-shaped flow path 124 and two quick joints 126 and 127 connected to the outside. In addition, it should be noted that the shape of the flow path 24 in the third figure is represented by a single serpentine flow field, but the scope of the present invention is not limited thereto, and thus the shape of the flow path 124 may be plural. A serpentine flow field, single or multiple interdigitated or parallel flow fields (parallel). 8 201232910 For a further description of the invention, reference is made to the fourth figure, a simplified combination of the electrode structures of the present invention. As shown in the fourth example, in order to simplify the structure of the core reaction zone for electrochemical reaction, the two sheets 14〇 and 142' are not shown, and only the two graphite collector plates 120 and 122 are shown. Two graphite drum units 130 and 132, two graphite papers 15 and 152, and a proton exchange membrane 16A. Two graphite children's hair units 130 and 132 are respectively embedded in the flow paths of the two graphite current collecting plates 12 and 122, and two graphite papers 150 and 152 are respectively covered over the flow path to cover the two graphite drum units 13 and 132'. A three-dimensional graphite composite material including a stone, a graphite paper, and a graphite current collector is used to form a composite electrode structure. At the same time, the two graphite papers 15 and 152 are attached to the two sides of the proton exchange membrane 160, respectively. Therefore, the positive electrode electrolyte and the negative electrode electrolyte which are externally input and contain vanadium ions of different valences can flow through the corresponding flow channels, and use the proton exchange membrane 16 〇 as a battery separator to perform proton exchange to form a current. Loop. For example, a first electrolyte containing mono- and divalent vanadium ions, and a first electrolyte containing tetravalent and pentavalent vanadium ions may be used, by which the first electrolyte and the second electrolyte are electrochemically converted The reaction is performed to generate electric power and output to the outside, or the externally input electric power is converted into a suitable sharp ion to store electric power. More specifically, when externally inputting electric power, the trivalent vanadium ions of the first electrolyte are converted into divalent vanadium ions, and the tetravalent europium ions of the second electrolyte are converted into pentavalent vanadium ions for charging, and When the power is output to the outside, the divalent sulfide of the first electrolyte is converted into a trivalent star, and the pentavalent star of the second electrolyte is converted into a tetravalent vanadium ion for discharge. The graphite drum unit may be a polyacrylonitrile fiber (PAN) of 2 to 20 μηι, a mesophase pitch, a cellulose fiber, an acrylic, a phenol fiber (phen〇1) or a poly The fibrils of the amide fiber (ar 〇 〇丨丫 〇 丨 经由 经由 经由 经由 经由 经由 。 。 。 。 。 。 。 。 。 。 。 。 In addition, the thickness of the strip-shaped graphite felt unit is 3.0 to 8.0 mm, and the bulk density of the graphite drum unit 9 201232910 * can be greater than 0.09 g/cm and less than 〇2〇g/cm3, and the resistivity can be Less than cm 'and the layer spacing of the graphite contained therein is less than 35 in. Graphite paper can be 2~20 division of polyacrylonitrile fiber (pAN), mesophase green fiber (Puchch), cellulose fiber (cellulose), acrylic fiber (acryiic), benzene_dimensional (and 〇1 Or the polyamide fiber fiber (a_ticp〇iyamide) is composed of carbonized and high-temperature graphite surface. Further, the thickness of the graphite paper is 0.K0 _ ' and the bulk density of the graphite paper is larger than _ ^ 3 and smaller than _ -3 , and the resistivity is less than (10) Å. The layer spacing CW of graphite contained is less than 3.5 A. • Graphite headers can be constructed using natural graphite or artificial graphite. A preferred graphite current collector plate may have a thickness of 10 to 2 Gmm, a bulk density of greater than 丨9 G (g/em3), a resistivity of less than 0.03 cm.cm, and a layer spacing of graphite (eg, 2). The gasket may be less than 3'38 A. The gasket may be polytetrafluoroethylene or polytetrafluoroethylene &x>lytetmfl_ethylene 'PTFE. The cultivating, ^ s plate can be made into a bipolar cell structure (bipolarcell)... that is, the opposite surfaces of the graphite current collecting plate respectively have flow channels for different electrolyte flows, which can be combined into a large one by stacking. Composite electrode to increase electrical power. As shown in the fifth figure, the stacked electrode structure of the present invention has a _ and a group port diagram, wherein the graphite current collecting plate 12 has a flow path on a single surface, and the graphite current collecting plate 121 is on the two complementary surfaces. There is a flow of money. The arrow of the fifth figure shows the stacking direction of the plurality of graphite current collecting plates. The invention is characterized in that a high-efficiency composite electrode structure composed of a graphite felt unit, a graphite paper and a graphite current collecting plate is used, in particular, the graphite current collecting plate itself has a flow path through which the bismuth electrolyte flows to improve the electrolyte. Retention (dev (jv 〇 〖 ume) problem, can reduce the phenomenon of electrolyte concentration polarization, while using graphite felt unit and graphite paper composite connection, so that the reaction area of the electrode is increased, and can be between various electrode materials Forming a good conductive network to enhance charge transfer, further improving the overall energy conversion efficiency. Therefore, the electrode structure of the present invention can be applied to a full vanadium redox flow battery, suitable for 10 201232910 as power _ peak _ time 贞 load, large显太_Lai Li power storage equipment and power sources in remote areas. The above information is only used to compare the four (4) examples of the invention, and the lining is based on the female form of the invention. The clock-modified readings of the present invention in the spirit of the same invention should still be included in the protection of the present invention. [Simplified Schematic] The first picture shows the full use of the technology. BRIEF DESCRIPTION OF THE DRAWINGS The second figure is a schematic view of the electrode structure of the all-vanadium redox flow battery of the present invention. The third figure is a schematic view of the graphite flow plate of the present invention. The fourth figure is a simplified combination diagram of the electrode structure of the present invention. The figure is a schematic diagram of the combination of the stacked electrode structures of the present invention. [Main component symbol description] ίο positive electrode plate 2 〇 negative electrode plate _ 30 positive electrode electrolyte 40 negative electrode electrolyte positive electrode electrolyte storage unit 60 negative electrode electrolyte storage unit 70 positive connection Line 80 negative connection 90 power conversion unit 92 external input power supply 94 external load 201232910 100 electrode structure 110, 112 metal sheet (copper sheet) 120 graphite current collector 121 graphite current collector 122 graphite current collector plate 124 flow path 126, 127 quick connector 130 graphite felt unit 132 graphite felt unit 140 gasket 142 gasket 150 graphite paper 152 graphite paper 160 proton exchange membrane 170 perforation