TW202017240A - Flow battery stack - Google Patents
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Abstract
Description
本發明是有關於一種電化學儲能裝置,且特別是有關於一種液流電池堆。The invention relates to an electrochemical energy storage device, and in particular to a flow battery stack.
液流電池(flow battery),亦稱為氧化還原液流電池(redox flow battery)是一種電化學儲能裝置,是透過電解液(正極電解液與負極電解液)中氧化還原反應機制的離子價數變化,進行充電與放電的化學反應平台。A flow battery, also known as a redox flow battery, is an electrochemical energy storage device that is the ion value that passes through the redox reaction mechanism in the electrolyte (positive electrolyte and negative electrolyte) The number changes, and the chemical reaction platform for charging and discharging.
氧化還原液流電池具有安全性高、可以完全充放電、能量效率高、電池壽命長、電解液劣化少、不會排放有害環境的氣體以及電解液儲存槽增加即可增加系統儲電容量等特徵,可用於解決傳統再生能源具有的間歇特性,進而改善再生能源對於電力電網供電的不確定性。The redox flow battery has the characteristics of high safety, full charge and discharge, high energy efficiency, long battery life, less electrolyte degradation, no discharge of harmful environmental gases, and the increase of the electrolyte storage tank, which can increase the system storage capacity. , Can be used to solve the intermittent characteristics of traditional renewable energy, and thereby improve the uncertainty of renewable energy for power grid power supply.
然而,目前既有的串聯式液流電池堆尚存在以下問題,包括:電解液流通分布不均,發生死區(dead volume)造成電解液停滯及濃度極化,而影響電池內部質子與電子傳輸效能,使得電池整體效率不佳,並有電解液流通阻力過高造成電池洩漏與寄生電力損耗過高等問題。However, the current tandem flow battery stack still has the following problems, including: uneven distribution of electrolyte circulation, dead volume (dead volume) causes electrolyte stagnation and concentration polarization, which affects the internal proton and electron transport of the battery The efficiency makes the overall efficiency of the battery poor, and there are problems such as battery leakage and excessive parasitic power loss caused by excessive electrolyte flow resistance.
本發明提供一種液流電池堆,能有效提升可靠度並改善電解液流通分布不均的情形。The invention provides a flow battery stack, which can effectively improve the reliability and improve the uneven distribution of electrolyte circulation.
本發明的液流電池堆包括第一電極單元、第二電極單元、含有至少一雙極單元的電池單元、數個第一集電板與第二集電板。第一電極單元具有不相通的N個第一電化學反應區域,第二電極單元具有不相通的N個第二電化學反應區域,N為大於1的整數。第N個第二電化學反應區域與第N個第一電化學反應區域相通。電池單元介於第一與第二電極單元之間,其雙極單元具有不相通的N個第三電化學反應區域,且第N個第三電化學反應區域與第N個第一電化學反應區域相通。第一集電板則設置於第一電極單元外側,且每個第一集電板對應每個第一電化學反應區域。第二集電板設置於第二電極單元外側。The flow battery stack of the present invention includes a first electrode unit, a second electrode unit, a battery unit containing at least one bipolar unit, and a plurality of first current collector plates and second current collector plates. The first electrode unit has N first electrochemical reaction regions that are not connected, and the second electrode unit has N second electrochemical reaction regions that are not connected, and N is an integer greater than 1. The Nth second electrochemical reaction area is in communication with the Nth first electrochemical reaction area. The battery unit is interposed between the first and second electrode units, and its bipolar unit has N third electrochemical reaction regions that are not connected, and the Nth third electrochemical reaction region reacts with the Nth first electrochemical reaction region The areas are connected. The first collector plate is disposed outside the first electrode unit, and each first collector plate corresponds to each first electrochemical reaction area. The second current collector plate is disposed outside the second electrode unit.
基於上述,既可有效提升液流電池堆可靠度,又可以將電解液在電池中進行有效且均勻的流場分配,改善電解液流通分布不均,避免死區(dead volume)的發生,提升電池內部質子與電子傳輸效能及電池整體效率;降低電池流通阻力,減少輸送泵浦寄生電力的損耗,有利提升氧化還原電池的電流密度及能量效率的結構設計,以有效提升儲能系統的可靠度及穩健性。Based on the above, the reliability of the flow battery stack can be effectively improved, and the electrolyte can be effectively and uniformly distributed in the battery field to improve the uneven distribution of the electrolyte circulation and avoid the occurrence of dead volume. The internal proton and electron transmission efficiency of the battery and the overall efficiency of the battery; reduce the flow resistance of the battery and reduce the loss of the parasitic power of the pump, which is beneficial to the structural design of the current density and energy efficiency of the redox battery to effectively improve the reliability of the energy storage system And robustness.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the embodiments are specifically described below in conjunction with the accompanying drawings for detailed description as follows.
請參考以下實施例及隨附圖式,以便更充分地了解本發明,但是本發明仍可以藉由多種不同形式來實踐,且不應將其解釋為限於本文所述之實施例。為了方便理解,下述說明中相同的元件將以相同之符號標示來說明。而在圖式中,為求明確起見對於各構件以及其相對尺寸可能未按實際比例繪製。Please refer to the following embodiments and accompanying drawings to understand the present invention more fully, but the present invention can still be practiced in many different forms and should not be interpreted as being limited to the embodiments described herein. For ease of understanding, the same elements in the following description will be described with the same symbols. In the drawings, for the sake of clarity, the components and their relative sizes may not be drawn according to the actual scale.
圖1是依照本發明的一實施例的一種液流電池堆的爆炸示意圖。FIG. 1 is an exploded schematic view of a flow battery stack according to an embodiment of the invention.
請參照圖1,本實施例的液流電池堆10基本上包括第一電極單元100、第二電極單元110、含有至少一雙極單元120的電池單元121、第一集電板130與第二集電板140。雙極單元120可為一個或多個,以達到電池的電性規格。第一電極單元100具有不相通的N個第一電化學反應區域102,第二電極單元110具有數個不相通的N個第二電化學反應區域112,且文中的N是大於1的整數。第N個第二電化學反應區域112與第N個第一電化學反應區域102相通。以圖1為例,N是2,所以第1個第二電化學反應區域112與第1個第一電化學反應區域102相通,第2個第二電化學反應區域112與第2個第一電化學反應區域102相通。電池單元121介於第一與第二電極單元100與110之間,其中的每個雙極單元120如圖2所示具有不相通的N個第三電化學反應區域122,且第N個第三電化學反應區域122會與第N個第一電化學反應區域102相通。舉例來說,第1個第三電化學反應區域122、第1個第二電化學反應區域112與第1個第一電化學反應區域102是彼此相通且位置與大小均相近或相同;第2個第三電化學反應區域122、第2個第二電化學反應區域112與第2個第一電化學反應區域102也是彼此相通且位置與大小均相近或相同。Referring to FIG. 1, the
由於第N個第一、第二與第三電化學反應區域102、112與122是彼此相通,但是第一電化學反應區域102彼此不相通、第二電化學反應區域112彼此不相通、第三電化學反應區域122彼此也不相通,所以相通的多個電化學反應區域(102、112與122)成為一個子電池系統模組300,並與彼此不相通的其他電化學反應區域(102、112與122)的子電池系統模組300等構成一個如圖3所示的並聯系統。圖3顯示的是本發明的實施例的液流電池堆的方塊圖,其中每一個子電池系統模組300包含具有相通的電化學反應區域的電極單元與雙極單元,且由於不同子電池系統模組300的電化學反應區域不相通,所以本實施例能達成高可靠度的結果。舉例來說,若將可靠度均為RSS
的電池所構成的N個子電池系統模組300構成一個並聯系統,其可靠度的方程式以下式(1)表示: RSP
= 1 – (1-RSS
)N
(1)Since the Nth first, second and third
經由上式(1)計算,以兩個子系統進行並聯設計,在相同單電池組件的條件下,可靠度將可以提升至88.2%;以四個子系統進行並聯設計,在相同單電池組件的條件下,可靠度將可以提升至98.6%;若以八個子系統進行並聯設計,在相同單電池組件的條件下,可靠度將可以提升至99.9%。因此,以改善可靠度的觀點來看,本實施例中的電化學反應區域(102、112與122)的數量(N值)最佳可在2至8之間。Through the calculation of the above formula (1), two subsystems are designed in parallel, and the reliability can be increased to 88.2% under the condition of the same single cell component; four subsystems are designed in parallel, under the condition of the same single cell component Under the condition, the reliability can be increased to 98.6%; if eight subsystems are designed in parallel, the reliability will be increased to 99.9% under the condition of the same single cell component. Therefore, from the viewpoint of improving reliability, the number (N value) of the electrochemical reaction regions (102, 112, and 122) in this embodiment may be preferably between 2 and 8.
請繼續參照圖1,第一集電板130設置於第一電極單元100外側,且第一集電板130的數量為N個,以使第N個第一集電板130對應第N個第一電化學反應區域102,所以圖1有兩個第一電化學反應區域102,就會有兩個第一集電板130,依此類推。第二集電板140是設置於第二電極單元110外側,且第二集電板140的數量可如圖1所示只有單一個;在另一實施例中,第二集電板140也為多個獨立的集電板,且每個集電板對應每個第二電化學反應區域112。第一集電板130與第二集電板140可以將液流電池堆10充電所需電力的導入或放電所產生的電力導出。此外,液流電池堆10還包括第一端板150與第二端板160,分別設置於第一集電板130外側以及第二集電板140外側。第一端板150上有多個進口孔152,第二端板160上有多個出口孔162,以使電解液進入與流出。而且,為了調節第一集電板130與其他單元構件之間的結構應變與應力,可選擇在第一端板150與第一集電板130之間加設第一彈性體單元170a,並在第二端板160與第二集電板140之間加設第二彈性體單元170b。尤其是第一集電板130的數量為多個,第一彈性體單元170a能進一步調節這些第一集電板130的接觸阻抗。第一與第二彈性體單元170a與170b能調節如螺帽172及螺桿174的緊固元件在進行鎖合過程所發生的結構應變與應力不均情形,同時可以達到隔絕第一與第二電極單元100與110熱傳導與電絕緣之功效。第一與第二彈性體單元170a與170b的材料例如含有碳、氫、氧與(或)矽的化合物矽橡膠,還可包括不飽和橡膠或飽和橡膠等。1, the
請參照圖1與圖2,本實施例中的雙極單元120可包括不參與電化學反應的不導電框架200和參與電化學反應的N個導電板210,且電池單元121更可包括離子交換膜126與石墨電極128。石墨電極128介於離子交換膜126與雙極單元120或離子交換膜126與第二電極單元110之間,且每個石墨電極128對應備配置於每個第三電化學反應區域122內,並搭配具有N個不相通的獨立區域182的密封單元180,第N個獨立區域182對應第N個電化學反應區域(102、112或122)。以圖2為例,密封單元180的第1個獨立區域182是對應第1個第三電化學反應區域122、第2個獨立區域182是對應第2個第三電化學反應區域122。當第三電化學反應區域122的數量是兩個,單一個密封單元180就有兩個獨立區域182;在其他實施例中,若是第三電化學反應區域122的數量是四個,單一個密封單元180就會有四個獨立區域182。因此,當本實施例的液流電池堆10組裝完成,可經由外部控制閥等裝置,各別控制正極電解液與負極電解液進入不同的獨立區域182;也就是說,如圖1的虛線所表示的電解液流向所示,正、負極電解液在同一個液流電池堆10中是流向兩個不相通的電化學反應區域,所以能改善電解液的均勻性並降低流阻,藉此避免死區的發生並有效降低寄生電力損耗。另外,雖然圖1中僅顯示一個離子交換膜126和兩個密封單元180,但應知本發明的雙極單元120的數量可有多個並與多個離子交換膜126搭配相應數量的石墨電極128和密封單元180,來組成液流電池堆10。1 and 2, the
請繼續參照圖2,本實施例的雙極單元120中的不導電框架200包括基板本體202與數個固定框204。基板本體202具有對應第三電化學反應區域122的N個容置空間202a,導電板210經由固定框204固設於容置空間202a內。而且,基板本體202對應每一個容置空間202a包括一個以上的獨立入口202b及一個以上的獨立出口202c。在一實施例中,基板本體202的高度H1>容置空間202a的高度H2,而且H2≥固定框204的高度H3≥導電板210的高度H4;基板本體202的寬度W1>兩倍的容置空間202a的寬度W2;W2≥固定框204的寬度W3≥導電板210的寬度W4。導電板210例如高度可耐酸耐鹼的碳板、導電高分子複合材料或不銹鋼金屬材料;基板本體202例如耐酸鹼高分子材料。以下將描述雙極單元的細部結構。Please continue to refer to FIG. 2. The
圖4是圖2的基板本體202的流體分配部206透視圖。在圖4中,基板本體202的獨立入口202b到容置空間202a的部分設有流體分配隧道400,將電解液由獨立入口202b進入後均勻分布至容置空間202a。同樣地,基板本體202的容置空間202a到圖2之獨立出口202c之間也可設有上述流體分配隧道400,以使電解液由容置空間202a均勻流出獨立出口202c,且流體分配隧道400是位於基板本體202內而不參與電化學反應機制。4 is a perspective view of the
圖5則是圖2的基板本體202的定位卡接部208之剖面示意圖,其中顯示一個定位結構500,用以使各個雙極單元120之間彼此卡接定位。定位結構500可設置於基板本體202的邊緣或角落,且可為圓錐銷。在一實施例中,定位結構500(例如為圓錐銷)的上端直徑為D1、底端直徑為D2,D2>D1,定位結構500具有圓錐孔槽502,其內孔直徑為D3、外孔直徑為D4,D4>D3,且D3≥D1,D4≥D2。除了基板本體202以外,第一電極單元、第二電極單元等具有不導電框架的構件,均可在相同位置設置定位結構500,以使雙極單元與第一電極單元之間彼此卡接定位,並使雙極單元與第二電極單元之間彼此卡接定位。當圖1的雙極單元120與第一、第二電極單元100和110裝配後可形成對位配合。FIG. 5 is a schematic cross-sectional view of the positioning and clamping
圖6是圖2的I-I’線段的剖面示意圖,其中顯示基板本體202具有沿每個容置空間202a的邊緣內凹的凹槽600,用以容置導電板210及固定框204,且導電板210可以嵌入的方式置入凹槽600,再以固定框204將導電板210夾持膠合,但本發明並不限於此。由於基板本體202與固定框204的結合並無對外的接縫,所以即使有電解液從基板本體202與固定框204之間洩漏的情況,電解液也頂多從接縫602處流出。而且,基板本體202還可包括對應圖2之密封單元180結構的構槽604,所以即使電解液從接縫602處流出,仍會被密封單元180密封於液流電池堆內,而避免汙染。另外,基板本體202及固定框204與導電板210接觸面還可具有倒角606,以容置導電板210接合時之匹配誤差。6 is a schematic cross-sectional view taken along the line II′ of FIG. 2, wherein the
圖7顯示本實施例中的第一或第二電極單元的立體示意圖。請同時參照圖1與圖7,第一電極單元100類似圖2的雙極單元也包含不導電框架700與位在第一電化學反應區域102的導電板702。而且,第一電極單元100的不導電框架700還可包括數個電解液入口孔704以及數個封閉凸出結構706,其中電解液入口孔704以及封閉凸出結構706是設置於不導電框架700的對邊。電解液入口孔704與封閉凸出結構706沿II-II’線段的剖面如圖8所示,其中顯示不導電框架700內具有如圖4的流體分配隧道400,當電解液從電解液入口孔704流入會從流體分配隧道400均勻進入第一電化學反應區域102,再從流體分配隧道400均勻流出,並到達作為緩衝區的封閉凸出結構706內,因此能提升電解液在歧管通道的流場均勻,使電解液均勻進入與排出每一個電極單元。另外,在第一電極單元100的不導電框架700上還可具有圖5所示的圓錐銷作為定位結構500,以使雙極單元120與第一電極單元100之間彼此卡接定位。而且,不導電框架700上還可設有對應於緊固元件(如螺桿174)穿孔的集電板定位結構708,用以定位第一、第二集電板130與140,並可以達到電隔絕效果。FIG. 7 shows a perspective schematic view of the first or second electrode unit in this embodiment. 1 and FIG. 7 at the same time, the
同樣地,第二電極單元110也可與上述第一電極單元100一樣設有位置相對於封閉凸出結構706的電解液出口孔(未繪示)以及位置相對於電解液入口孔704的封閉凸出結構(未繪示),且第一電極單元100的封閉凸出結構706是往第一集電板130凸出,第二電極單元110的封閉凸出結構則會往第二集電板140凸出。此外,第二電極單元110同樣可具有圖5所示的圓錐銷作為定位結構500以及對應於緊固元件(如螺桿174)穿孔的集電板定位結構,以使雙極單元120與第二電極單元110之間彼此卡接定位,且可定位第一、第二集電板130與140,並可以達到電隔絕效果。Similarly, the
綜上所述,本發明藉由在電池堆中設計電解液互不相通的數個電化學反應區域,構成一個並聯系統,除了可提高可靠度,還具可量產性及降低製造成本的效果,另外,本發明獨立的電化學反應區域因為電解液互不相通,所以藉由分區控制達成高均勻與低流阻的分布電解液,可以有效降低寄生電力損耗的液流電池堆結構。To sum up, the present invention forms a parallel system by designing several electrochemical reaction areas in the battery stack that are not connected to each other, in addition to improving reliability, but also having the effect of mass production and reducing manufacturing costs In addition, since the independent electrochemical reaction regions of the present invention do not communicate with each other, the distribution of electrolyte with high uniformity and low flow resistance can be achieved by zone control, which can effectively reduce the parasitic power loss of the flow battery stack structure.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.
10:液流電池堆100:第一電極單元102:第一電化學反應區110:第二電極單元112:第二電化學反應區域120:雙極單元121:電池單元122:第三電化學反應區域126:離子交換膜128:石墨電極130:第一集電板140:第二集電板150:第一端板152:進口孔160:第二端板162:出口孔170a:第一彈性體單元170b:第二彈性體單元172:螺帽174:螺桿180:密封單元182:獨立區域200、700:不導電框架202:基板本體202a:容置空間202b:獨立入口202c:獨立出口204:固定框206:流體分配部208:定位卡接部210、702:導電板300:子電池系統模組400:流體分配隧道500:定位結構600:凹槽602:接縫604:構槽606:倒角704:電解液入口孔706:封閉凸出結構708:集電板定位結構D1、D2、D3、D4:直徑H1、H2、H3、H4:高度W1、W2、W3、W4:寬度10: Flow battery stack 100: First electrode unit 102: First electrochemical reaction zone 110: Second electrode unit 112: Second electrochemical reaction zone 120: Bipolar unit 121: Battery unit 122: Third electrochemical reaction Area 126: ion exchange membrane 128: graphite electrode 130: first collector plate 140: second collector plate 150: first end plate 152: inlet hole 160: second end plate 162:
圖1是依照本發明的一實施例的一種液流電池堆的爆炸示意圖。 圖2是本發明的實施例中的雙極單元的分解示意圖。 圖3是本發明的實施例的液流電池堆的方塊圖。 圖4是圖2的基板本體的流體分配部的透視圖。 圖5是圖2的基板本體的定位卡接部之剖面示意圖。 圖6是圖2的I-I’線段的剖面示意圖。 圖7是本發明的實施例中的第一或第二電極單元的立體示意圖。 圖8是圖7的II-II’線段的剖面示意圖。FIG. 1 is an exploded schematic view of a flow battery stack according to an embodiment of the invention. FIG. 2 is an exploded schematic view of the bipolar unit in the embodiment of the present invention. 3 is a block diagram of a flow battery stack according to an embodiment of the present invention. 4 is a perspective view of the fluid distribution portion of the substrate body of FIG. 2. 5 is a schematic cross-sectional view of the positioning and engaging portion of the substrate body of FIG. 2. Fig. 6 is a schematic cross-sectional view taken along the line I-I' of Fig. 2. 7 is a schematic perspective view of the first or second electrode unit in the embodiment of the present invention. Fig. 8 is a schematic cross-sectional view taken along the line II-II' of Fig. 7.
10:液流電池堆 10: Flow battery stack
100:第一電極單元 100: first electrode unit
102:第一電化學反應區 102: The first electrochemical reaction zone
110:第二電極單元 110: second electrode unit
112:第二電化學反應區域 112: Second electrochemical reaction area
121:電池單元 121: battery unit
120:雙極單元 120: Bipolar unit
126:離子交換膜 126: ion exchange membrane
128:石墨電極 128: graphite electrode
130:第一集電板 130: The first collector plate
140:第二集電板 140: second collector plate
150:第一端板 150: first end plate
152:進口孔 152: inlet hole
160:第二端板 160: second end plate
162:出口孔 162: Exit hole
170a:第一彈性體單元 170a: the first elastomer unit
170b:第二彈性體單元 170b: second elastomer unit
172:螺帽 172: Nut
174:螺桿 174: screw
180:密封單元 180: sealed unit
704:電解液入口孔 704: electrolyte inlet hole
706:封閉凸出結構 706: Closed convex structure
Claims (17)
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