TWI703759B - Storage module of distributed flow battery - Google Patents
Storage module of distributed flow battery Download PDFInfo
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- TWI703759B TWI703759B TW108132120A TW108132120A TWI703759B TW I703759 B TWI703759 B TW I703759B TW 108132120 A TW108132120 A TW 108132120A TW 108132120 A TW108132120 A TW 108132120A TW I703759 B TWI703759 B TW I703759B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Description
本發明係有關於一種分散式液流電池儲能模組,特別係指利用低 成本的隔離膜、電漿改質的碳氈、以及一體成型的複合澆鑄極板(含石墨板、邊框與新型流場設計),可將雙極板減薄,有效節省材料成本,並作為儲能模組在導電板、石墨板與石墨紙三者結合形式中有效提高電池堆的能量效率者。 The present invention relates to a decentralized flow battery energy storage module, in particular to low utilization Cost-effective isolation membrane, plasma-modified carbon felt, and integrally formed composite casting plate (including graphite plate, frame and new flow field design), which can reduce the thickness of the bipolar plate, effectively save material costs, and serve as storage The energy module can effectively improve the energy efficiency of the battery stack in the combination of conductive plate, graphite plate and graphite paper.
全釩電池係利用電解液中不同價態之釩離子進行氧化還原反應 以作為儲存或釋出電能。其電極本身不參與反應,而正負極之電解液係分開且儲存於外部之儲液槽,因此自放電率低且循環壽命長。其特點係電池之功率及所能儲存之能量可分開設計。 All vanadium batteries use vanadium ions of different valences in the electrolyte to perform redox reactions To store or release electrical energy. The electrode itself does not participate in the reaction, and the electrolyte of the positive and negative electrodes are separated and stored in an external storage tank, so the self-discharge rate is low and the cycle life is long. Its characteristic is that battery power and stored energy can be designed separately.
在電池結構方面之設計需考慮電解液在反應區內之分布及降低 分歧電流(Shunt Current)。全釩電池係由多個單電池串聯組合而成,而由於電解液具導電性,故連通任兩單電池間之電解液因電位差而產生電流(即分歧電流),此電流不供應外部負載所需,即為一種內耗。大部分降低此分歧電流之方式係增加主流道至反應區間電解液之流動長度,以增加此部分電解液之阻抗。此流道係設計在絕緣材質之外框上,因此增加了全釩電池結構之複雜度。 The design of the battery structure needs to consider the distribution and reduction of the electrolyte in the reaction zone Shunt Current. The vanadium battery is composed of multiple single cells in series, and because the electrolyte is conductive, the electrolyte connecting any two single cells generates current due to the potential difference (ie, branch current). This current is not supplied to the external load. Need is a kind of internal friction. Most of the ways to reduce this branch current are to increase the length of the electrolyte flowing from the main channel to the reaction zone to increase the impedance of this part of the electrolyte. The flow channel is designed on the outer frame of the insulating material, thus increasing the complexity of the structure of the all-vanadium battery.
全釩電池之傳統結構中,其雙極板係由二片絕緣框架夾合一片石 墨板而成,其中石墨板之功能係分隔正負極電解液及傳導電子,而分支流道即是位於絕緣框架上。在組裝時,每一層之接觸面均需設置氣密墊片,以防止電解液洩漏。惟此電池結構所需之零組件繁多,且組裝費時,造成電池成本增加,同時習知的雙極板體積大,不易成型超薄的雙極板。以致,組成一電池組後,也造成該電池組體積大。 In the traditional structure of the all-vanadium battery, the bipolar plate is sandwiched by two insulating frames. It is made of an ink plate, in which the function of the graphite plate is to separate the positive and negative electrolytes and conduct electrons, and the branch flow channel is located on the insulating frame. When assembling, the contact surface of each layer must be equipped with airtight gaskets to prevent electrolyte leakage. However, this battery structure requires a large number of components and time-consuming assembly, which increases the cost of the battery. At the same time, the conventional bipolar plate has a large volume and is not easy to form an ultra-thin bipolar plate. As a result, after forming a battery pack, the battery pack is also bulky.
鑑於傳統液流電池之雙極板係將石墨板夾合於絕緣框架中,惟此 種設計之雙極板包含了許多零件、體積大,且組裝過程所需花費之時間也較長。故,一般習用者係無法符合使用者於實際使用時之所需。 In view of the bipolar plate of the traditional flow battery, the graphite plate is sandwiched in the insulating frame, but this The bipolar plate of this design contains many parts, is large in size, and the assembly process takes a long time. Therefore, ordinary users cannot meet the needs of users in actual use.
本發明之主要目的係在於,克服習知技藝所遭遇之上述問題並提 供一種應用於分散式液流電池,利用低成本的隔離膜、電漿改質的碳氈、以及一體成型的複合澆鑄極板(含石墨板、邊框與新型流場設計),可將雙極板減薄,有效節省材料成本,並作為儲能模組在導電板、石墨板與石墨紙三者結合形式中有效提高電池堆的能量效率之分散式液流電池儲能模組。 The main purpose of the present invention is to overcome the above-mentioned problems encountered by conventional techniques and to provide Provides a kind of application in distributed flow battery, using low-cost isolation membrane, plasma-modified carbon felt, and integrally formed composite casting plate (including graphite plate, frame and new flow field design), which can combine bipolar The board is thinner, effectively saving material costs, and as an energy storage module, it is a distributed flow battery energy storage module that effectively improves the energy efficiency of the battery stack in the combination of conductive plates, graphite plates and graphite paper.
為達以上之目的,本發明係一種分散式液流電池儲能模組,係根 據正、負極電解液進行電化學反應以產生及/或放出直流電能,並輸出反應後之正、負極電解液,其包括:二端板(end plate),其中之一端板係具有自一負極電解液來源之一輸入連接器,與回到負極電解液來源之一輸出連接器,另一端板係具有自一正極電解液來源之一輸入連接器,與回到正極電解液來源之一輸出連接器;二框架(frame),設於該二端板之間,係為塑料材質的絕緣框架;二導電板(current collector),設於該二框架之間,各該導電板前端係設有一石墨紙(graphite paper);二複合澆鑄極板(complex cast polar plate),設於該二導電板之間,係經由澆鑄成型方式,將一石墨板(graphite plate)與一設於該石墨板上之邊框一次性一體成型,複合澆鑄極板為單極板,該石墨板係於單面設有數個電解液流道,並經由該石墨紙使該導電板與具有該些電解液流道之石墨板之相反另一面接觸,將該導電板、該石墨板與該石墨紙三者結合在一起,而該邊框上設有數個分支流道及多個歧管孔,且該邊框的該些分支流道能引導該正、負極電解液流進與流出該石墨板;二電極,設於該二複合澆鑄極板之間,該二電極分別為正、負電極,係以電漿改質之碳氈(carbon felt)作為電極材料;一隔離膜(membrane),設於該二電極之間,係以原子轉移自由基聚合(Atom Transfer Radical Polymerization, ATRP)改質之聚碸系薄膜作為膜材料;以及三防漏墊片(gasket),其中二防漏墊片設置為自前後包夾住該二複合澆鑄極板其中之一者,另一防漏墊片設於另一複合澆鑄極板與相鄰之導電板之間。 To achieve the above objectives, the present invention is a distributed flow battery energy storage module, which is based on According to the electrochemical reaction of the positive and negative electrode electrolytes to generate and/or release DC electric energy, and output the positive and negative electrode electrolytes after the reaction, it includes: two end plates, one of which has a negative electrode An input connector for one of the electrolyte sources, and an output connector that returns to the negative electrolyte source, and the other end plate has an input connector from a positive electrolyte source, and an output connector that returns to the positive electrolyte source器; Two frames (frame), set between the two end plates, is an insulating frame made of plastic material; two conductive plates (current collector), set between the two frames, each of the conductive plate front end is provided with a graphite Paper (graphite paper); two complex cast polar plates (complex cast polar plate), set between the two conductive plates, through casting molding method, a graphite plate (graphite plate) and a set on the graphite plate The frame is integrally formed at one time, and the composite cast electrode plate is a unipolar plate. The graphite plate is provided with several electrolyte flow channels on one side, and the conductive plate and the graphite plate with the electrolyte flow channels are connected through the graphite paper. On the contrary, the other side is in contact, the conductive plate, the graphite plate and the graphite paper are combined together, and the frame is provided with a plurality of branch flow channels and a plurality of manifold holes, and the branch flow channels of the frame It can guide the positive and negative electrolytes to flow into and out of the graphite plate; two electrodes are arranged between the two composite cast electrode plates, the two electrodes are respectively positive and negative electrodes, which are carbon felt modified by plasma ( carbon felt) as the electrode material; an isolation membrane (membrane) arranged between the two electrodes, and a polymer film modified by Atom Transfer Radical Polymerization (ATRP) as the membrane material; and three A leak-proof gasket (gasket), wherein two leak-proof gaskets are set to clamp one of the two composite casting electrode plates from the front and back, and the other leak-proof gasket is set on the other composite casting electrode plate and adjacent Between conductive plates.
於本發明上述實施例中,該複合澆鑄極板中間之石墨板,其厚度 至多為0.5 mm。 In the above embodiment of the present invention, the graphite plate in the middle of the composite cast pole plate has a thickness At most 0.5 mm.
於本發明上述實施例中,該邊框之材料包括聚氯乙烯(PVC)、 聚偏氟乙烯(PVDF)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)或聚四氟乙烯(PTFE)。 In the above embodiment of the present invention, the material of the frame includes polyvinyl chloride (PVC), Polyvinylidene fluoride (PVDF), polyethylene (PE), polypropylene (PP), polystyrene (PS) or polytetrafluoroethylene (PTFE).
於本發明上述實施例中,該隔離膜係將具有聚苯乙烯磺酸 (Polystyrene sulfonate, PSS)之塗層溶液施加至具有多孔特性之聚碸系薄膜進行ATRP改質,利用一過氧化物將該聚碸系薄膜與聚苯乙烯磺酸中之氫原子取代成為自由基,再經過加熱聚合反應後,使該聚碸系薄膜與該聚苯乙烯磺酸聚合與交聯,使其親水基團可生長在該聚碸系薄膜之孔洞與表面上,以改質成一較高親水性質之隔離膜者。 In the above embodiment of the present invention, the isolation film will have polystyrene sulfonic acid The coating solution of (Polystyrene sulfonate, PSS) is applied to the porous polymer film for ATRP modification, using a peroxide to replace the hydrogen atoms in the polystyrene sulfonate film and polystyrene sulfonic acid into free radicals After the heating and polymerization reaction, the polymerized film and the polystyrene sulfonic acid are polymerized and cross-linked, so that the hydrophilic group can grow on the pores and surface of the polymerized film to improve the quality Highly hydrophilic isolation membrane.
於本發明上述實施例中,該聚碸系薄膜係為聚碸(Polysulfone, PSF)、或聚醚碸(Polyethersulfone, PES),係以ATRP改質成PES-PSS或PSF-PSS之較高親水性質之隔離膜。 In the foregoing embodiment of the present invention, the polysulfone film is polysulfone (Polysulfone, PSF), or Polyethersulfone (PES), which is modified by ATRP into PES-PSS or PSF-PSS with higher hydrophilic properties.
於本發明上述實施例中,該過氧化物係為過硫酸鈉(Na 2S 2O 8) 或過硫酸鉀(K 2S 2O 8)。 In the above embodiment of the present invention, the peroxide is sodium persulfate (Na 2 S 2 O 8 ) or potassium persulfate (K 2 S 2 O 8 ).
於本發明上述實施例中,該親水基團係為磺酸鹽基團(SO 3-)。 In the above embodiments of the present invention, the hydrophilic group is a sulfonate group (SO 3 -).
請參閱『第1圖~第4圖』所示,係分別為本發明分散式液流電
池儲能模組之結構示意圖、本發明複合澆鑄極板之平面示意圖、本發明石墨板與導電板之結合示意圖、及本發明之結構最佳化測試與驗證結果示意圖。如圖所示:本發明係一種分散式液流電池儲能模組,係根據正、負極電解液進行電化學反應以產生及/或放出直流電能,並輸出反應後之正、負極電解液,其包括二端板(end plate)1、1a、二框架(frame)2、二導電板(current collector)3、二複合澆鑄極板(complex cast polar plate)4、二電極5、一隔離膜(membrane)6、以及三防漏墊片(gasket)7a、7b、7c所構成。
Please refer to the "Figure 1 to Figure 4", which are the distributed liquid flow of the present invention.
The schematic diagram of the structure of the pool energy storage module, the schematic plan view of the composite casting electrode plate of the present invention, the schematic diagram of the combination of the graphite plate and the conductive plate of the present invention, and the schematic diagram of the structure optimization test and verification results of the present invention. As shown in the figure: the present invention is a distributed flow battery energy storage module, which is based on the electrochemical reaction of the positive and negative electrode electrolytes to generate and/or release DC electric energy, and output the positive and negative electrode electrolytes after the reaction. It includes two
上述所提之端板1、1a,其中之一端板1係具有自一負極電解
液來源之一輸入連接器11,與回到負極電解液來源之一輸出連接器12,另一端板1a係具有自一正極電解液來源之一輸入連接器11a,與回到正極電解液來源之一輸出連接器12a。
The
該二框架2係設於該二端板1、1a之間,係為塑料材質的絕緣
框架。
The two
該二導電板3係設於該二框架2之間,各該導電板3前端係設有
一石墨紙(graphite paper)31。
The two
該二複合澆鑄極板4係設於該二導電板3之間,係經由澆鑄成型
方式,將一石墨板(graphite plate)41與一設於該石墨板41上之邊框42一次性一體成型,該石墨板41表面設有數個電解液流道411,並經由該石墨紙31使該導電板3與該石墨板41接觸,將該導電板3、該石墨板41與該石墨紙31三者結合在一起,而該邊框42之材料可為聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)或聚四氟乙烯(PTFE),其上設有數個分支流道421及多個歧管孔422,且該邊框42的該些分支流道421能引導該正、負極電解液流進與流出該石墨板41。
The two composite
該二電極5係設於該二複合澆鑄極板4之間,該二電極5分別為
正、負電極,係以電漿改質之碳氈(carbon felt)作為電極材料。
The two
該隔離膜6係設於該二電極5之間。該隔離膜6係將具有聚苯乙
烯磺酸(Polystyrene sulfonate, PSS)之塗層溶液施加至具有多孔特性之聚碸系薄膜進行原子轉移自由基聚合(Atom Transfer Radical Polymerization, ATRP)改質,該聚碸系薄膜係為聚碸(Polysulfone, PSF)、或聚醚碸(Polyethersulfone, PES)。利用過硫酸鈉(Na
2S
2O
8)或過硫酸鉀(K
2S
2O
8)作為一過氧化物,以濃度為0.1~5.0wt.%之過硫酸鈉為例,將該聚碸系薄膜與包含親水高分子結構之聚苯乙烯磺酸中之氫原子取代成為自由基,再經過加熱聚合反應,於60~100°C溫度下反應1~24小時後,使該聚碸系薄膜與該聚苯乙烯磺酸聚合與交聯,使其親水基團-磺酸鹽基團(SO
3-)可生長在該聚碸系薄膜之孔洞與表面上,以改質成一較高親水性質之隔離膜,如PES-PSS或PSF-PSS。
The
該三防漏墊片7a、7b、7c其中二防漏墊片7a、7b係設
置為自前後包夾住該二複合澆鑄極板4其中之一者,另一防漏墊片7c設於另一複合澆鑄極板4與相鄰之導電板3之間。如是,藉由上述揭露之流程構成一全新之分散式液流電池儲能模組。
The three leak-
上述複合澆鑄極板4可因位置不同分成單極板或雙極板。於一實
施例中,雙極板意即該石墨板41係於雙面設有該數個電解液流道411;當運用時,上述導電板3、石墨板41與石墨紙31三者結合形式如第3圖(a)所示,其中石墨板41係雙面皆設有電解液流道411之雙極板。經由結構最佳化測試與驗證結果可知,雙面皆設有電解液流道之結構會使組裝後的電池堆在操作時有較高的接觸電阻,如第4圖所示橫紋長條圖。
The above
於另一實施例中,單極板意即該石墨板41係於單面設有該數個
電解液流道411,並經由該石墨紙31使該導電板3與具有該些電解液流
道411之石墨板41之相反另一面接觸;當運用時,上述導電板3、石墨板41與石墨紙31三者結合形式如第3圖(b)所示,其中石墨板41係單面設有電解液流道411之單極板,即石墨板41與石墨紙31對應的一面未設有流道結構。經由結構最佳化測試與驗證結果可知,僅單面設有電解液流道411之結構其接觸電阻較低,可使組裝後的電池堆可以操作在高電流密度的時候,還能有高能量效率,如第4圖所示斜紋長條圖。
In another embodiment, the unipolar plate means that the
藉此,本發明應用於分散式液流電池,利用低成本的隔離膜、電 漿改質的碳氈、以及一體成型的複合澆鑄極板(含石墨板、邊框與新型流場設計),可將雙極板減薄至僅需0.5 mm,有效節省材料成本,並作為儲能模組在導電板、石墨板與石墨紙三者結合形式中有效提高電池堆的能量效率。 In this way, the present invention is applied to a distributed flow battery, using a low-cost isolation membrane, electricity Pulp-modified carbon felt, and integrally formed composite casting plate (including graphite plate, frame and new flow field design), which can reduce the thickness of the bipolar plate to only 0.5 mm, effectively saving material costs and serving as energy storage The module effectively improves the energy efficiency of the battery stack in the combination of conductive plate, graphite plate and graphite paper.
綜上所述,本發明係一種分散式液流電池儲能模組,可有效改善 習用之種種缺點,係應用於分散式液流電池,利用低成本的隔離膜、電漿改質的碳氈、以及一體成型的複合澆鑄極板(含石墨板、邊框與新型流場設計),可將雙極板減薄,有效節省材料成本,並作為儲能模組在導電板、石墨板與石墨紙三者結合形式中有效提高電池堆的能量效率,進而使本發明之產生能更進步、更實用、更符合使用者之所須,確已符合發明專利申請之要件,爰依法提出專利申請。 In summary, the present invention is a decentralized flow battery energy storage module, which can effectively improve The conventional shortcomings are applied to distributed flow batteries, using low-cost isolation membranes, plasma-modified carbon felt, and integrally formed composite casting plates (including graphite plates, frame and new flow field design), The bipolar plate can be thinned, effectively saving material costs, and used as an energy storage module to effectively improve the energy efficiency of the battery stack in the combination of conductive plates, graphite plates and graphite paper, thereby making the production of the present invention more advanced , It is more practical and more in line with the needs of users, and it has indeed met the requirements of an invention patent application. A patent application is filed in accordance with the law.
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定 本發明實施之範圍;故,凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾,皆應仍屬本發明專利涵蓋之範圍內。 However, the above are only preferred embodiments of the present invention, and should not be limited by this The scope of implementation of the present invention; therefore, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the description of the invention should still fall within the scope of the patent of the present invention.
1、1a:端板
11、11a:輸入連接器
12、12a:輸出連接器
2:框架
3:導電板
31:石墨紙
4:複合澆鑄極板
41:石墨板
411:電解液流道
42:邊框
421:分支流道
422:歧管孔
5:電極
6:隔離膜
7a、7b、7c:防漏墊片
1, 1a:
第1圖,係本發明分散式液流電池儲能模組之結構示意圖。 第2圖,係本發明複合澆鑄極板之平面示意圖。 第3圖,係本發明石墨板與導電板之結合示意圖。 第4圖,係本發明之結構最佳化測試與驗證結果示意圖。 Figure 1 is a schematic diagram of the structure of the distributed flow battery energy storage module of the present invention. Figure 2 is a schematic plan view of the composite casting plate of the present invention. Figure 3 is a schematic diagram of the combination of the graphite plate and the conductive plate of the present invention. Figure 4 is a schematic diagram of the structure optimization test and verification results of the present invention.
1、1a:端板 1, 1a: end plate
11、11a:輸入連接器 11, 11a: input connector
12、12a:輸出連接器 12, 12a: output connector
2:框架 2: frame
3:導電板 3: conductive plate
31:石墨紙 31: Graphite paper
4:複合澆鑄極板 4: Composite casting plate
41:石墨板 41: Graphite board
411:電解液流道 411: Electrolyte flow channel
42:邊框 42: border
421:分支流道 421: branch runner
422:歧管孔 422: Manifold hole
5:電極 5: Electrode
6:隔離膜 6: Isolation film
7a、7b、7c:防漏墊片 7a, 7b, 7c: leak-proof gasket
Claims (7)
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CN100468837C (en) * | 2003-09-08 | 2009-03-11 | 中国科学院大连化学物理研究所 | Method for preparing porous carbon radical electrode of sodium polysulfate / bromine energy storage cell |
CN105702976A (en) * | 2016-03-23 | 2016-06-22 | 中国东方电气集团有限公司 | Electrode, flow cell and flow cell stack |
CN105814725A (en) * | 2013-09-23 | 2016-07-27 | 洛克希德马丁尖端能量存储有限公司 | Bipolar plate design with non-conductive picture frame |
CN109074966A (en) * | 2016-03-23 | 2018-12-21 | 加利福尼亚大学董事会 | Device and method for high voltage and application of solar energy |
CN109314256A (en) * | 2016-06-15 | 2019-02-05 | 3M创新有限公司 | Membrane electrode assembly component and the method for preparing component |
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CN100468837C (en) * | 2003-09-08 | 2009-03-11 | 中国科学院大连化学物理研究所 | Method for preparing porous carbon radical electrode of sodium polysulfate / bromine energy storage cell |
CN105814725A (en) * | 2013-09-23 | 2016-07-27 | 洛克希德马丁尖端能量存储有限公司 | Bipolar plate design with non-conductive picture frame |
CN105702976A (en) * | 2016-03-23 | 2016-06-22 | 中国东方电气集团有限公司 | Electrode, flow cell and flow cell stack |
CN109074966A (en) * | 2016-03-23 | 2018-12-21 | 加利福尼亚大学董事会 | Device and method for high voltage and application of solar energy |
CN109314256A (en) * | 2016-06-15 | 2019-02-05 | 3M创新有限公司 | Membrane electrode assembly component and the method for preparing component |
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