CN101997129B - Liquid flow battery - Google Patents

Liquid flow battery Download PDF

Info

Publication number
CN101997129B
CN101997129B CN2009100134486A CN200910013448A CN101997129B CN 101997129 B CN101997129 B CN 101997129B CN 2009100134486 A CN2009100134486 A CN 2009100134486A CN 200910013448 A CN200910013448 A CN 200910013448A CN 101997129 B CN101997129 B CN 101997129B
Authority
CN
China
Prior art keywords
negative electrode
battery
flow battery
active material
storage tank
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2009100134486A
Other languages
Chinese (zh)
Other versions
CN101997129A (en
Inventor
刘建国
陈富于
陈晖�
严川伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Priority to CN2009100134486A priority Critical patent/CN101997129B/en
Publication of CN101997129A publication Critical patent/CN101997129A/en
Application granted granted Critical
Publication of CN101997129B publication Critical patent/CN101997129B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Landscapes

  • Fuel Cell (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明涉及液流电池领域,特别涉及一种新型液流电池:钒/锡电池,该电池可应用于大规模的储能系统。该液流电池的单电池主要设有正极、正极储液罐、负极、负极储液罐,正、负极由隔膜隔开,正极储液罐内装有正极电解液,正极电解液为含钒的酸性溶液,正极储液罐通过管道经由液泵接入正极构成回路;负极储液罐内装有负极电解液,负极为含锡的酸性溶液,负极储液罐通过管道经由液泵接入负极构成回路。在充放电过程中,正负极电解液在液泵推动下分别将电解液泵入电池内,保证电解液在储液罐和电池之间不断流动。本发明液流电池提高了电池电动势,克服电池比能量低的缺点,具有制造工艺简单、成本低、循环寿命高等优点。The invention relates to the field of flow batteries, in particular to a novel flow battery: a vanadium/tin battery, which can be applied to a large-scale energy storage system. The single cell of the flow battery is mainly equipped with a positive electrode, a positive electrode liquid storage tank, a negative electrode, and a negative electrode liquid storage tank. The positive electrode and the negative electrode are separated by a diaphragm, and the positive electrode liquid storage tank contains a positive electrode electrolyte. Solution, the positive electrode liquid storage tank is connected to the positive electrode through the pipeline through the liquid pump to form a circuit; the negative electrode liquid storage tank is equipped with the negative electrode electrolyte, the negative electrode is an acidic solution containing tin, and the negative electrode liquid storage tank is connected to the negative electrode through the pipeline through the liquid pump to form a circuit. During the charging and discharging process, the positive and negative electrolytes are respectively pumped into the battery under the push of the liquid pump to ensure the continuous flow of the electrolyte between the liquid storage tank and the battery. The liquid flow battery of the invention improves the electromotive force of the battery, overcomes the disadvantage of low specific energy of the battery, and has the advantages of simple manufacturing process, low cost, high cycle life, and the like.

Description

一种液流电池A flow battery

技术领域 technical field

本发明涉及液流电池领域,特别涉及一种新型液流电池:钒/锡电池,该电池可应用于大规模的储能系统。The invention relates to the field of flow batteries, in particular to a novel flow battery: a vanadium/tin battery, which can be applied to a large-scale energy storage system.

背景技术 Background technique

氧化还原液流电池是一种将能量储存于溶液中的电化学系统,该电化学系统的容量由电解液存储体积及电解液浓度决定,而电池功率由电堆大小决定。液流电池的突出优点主要有:寿命长,可靠性高,无污染排放和噪音,建设周期短,运行和维持费较低,是一种高效的大规模储存电能装置。A redox flow battery is an electrochemical system that stores energy in a solution. The capacity of the electrochemical system is determined by the storage volume and concentration of the electrolyte, while the power of the battery is determined by the size of the stack. The outstanding advantages of liquid flow batteries are: long life, high reliability, no pollution emissions and noise, short construction period, low operation and maintenance costs, and it is an efficient large-scale storage of electrical energy devices.

1982年D-G.Oei提出用SnCl2作液流电池负极活性物质,V2O5作为液流电池的正极活性物质,研究了电池的一些性能变化。但是由于V2O5微溶于水,在酸性溶液中的溶解度较小,导致电解液浓度较低,电池比能量受到电解液浓度的限制。同时,正极电极反应VO2 +/VO2+标准电极电势是1.00V,负极电极反应Sn4+/Sn2+标准电极电势是0.154V,组成电池电动势是0.846V。In 1982, DG.Oei proposed to use SnCl 2 as the negative electrode active material of the flow battery, and V 2 O 5 as the positive electrode active material of the flow battery, and studied some performance changes of the battery. However, because V 2 O 5 is slightly soluble in water, the solubility in acidic solution is small, resulting in a low electrolyte concentration, and the specific energy of the battery is limited by the concentration of the electrolyte. At the same time, the positive electrode reaction VO 2 + /VO 2+ standard electrode potential is 1.00V, the negative electrode reaction Sn 4+ /Sn 2+ standard electrode potential is 0.154V, and the electromotive force of the battery is 0.846V.

发明内容 Contents of the invention

本发明的目在于提出一种新型液流电池:钒/锡电池,该液流电池正极活性物质发生的电极反应VO2 +/VO2+,负极活性物质发生的电极反应为Sn2+/Sn,因为Sn2+/Sn标准电极电势是-0.136V,组成电池的电动势为1.136V,提高了电池电动势。同时,正极活性物质采用溶解度较大的四价钒V(IV)化合物,克服电池比能量低的缺点。另外,作为电极活性物质的锡化合物对环境没有污染且含量丰富,成本较低。The purpose of the present invention is to propose a new type of flow battery: vanadium/tin battery, the electrode reaction VO 2 + /VO 2+ generated by the positive active material of the liquid flow battery, and the electrode reaction generated by the negative active material is Sn 2+ /Sn , because the Sn 2+ /Sn standard electrode potential is -0.136V, the electromotive force of the battery is 1.136V, which increases the electromotive force of the battery. At the same time, the positive electrode active material adopts tetravalent vanadium V(IV) compound with high solubility to overcome the disadvantage of low specific energy of the battery. In addition, the tin compound as an electrode active material has no pollution to the environment and is rich in content, and the cost is low.

本发明的技术方案如下:Technical scheme of the present invention is as follows:

一种新型液流电池:钒/锡电池,该液流电池的单电池主要设有正极、正极储液罐、负极、负极储液罐,正、负极由隔膜隔开,正极储液罐内装有正极电解液,正极电解液为含钒的酸性溶液,正极储液罐通过管道经由液泵接入正极构成回路;负极储液罐内装有负极电解液,负极为含锡的酸性溶液,负极储液罐通过管道经由液泵接入负极构成回路。在充放电过程中,正负极电解液在液泵推动下分别将电解液泵入电池内,保证电解液在储液罐和电池之间不断流动。A new type of flow battery: vanadium/tin battery. The single battery of the flow battery is mainly equipped with a positive electrode, a positive electrode liquid storage tank, a negative electrode, and a negative electrode liquid storage tank. The positive and negative electrodes are separated by a diaphragm, and the positive electrode liquid storage tank is equipped with Positive electrode electrolyte, the positive electrode electrolyte is an acidic solution containing vanadium, the positive electrode storage tank is connected to the positive electrode through a pipeline through a liquid pump to form a circuit; the negative electrode liquid storage tank is equipped with negative electrode electrolyte, the negative electrode is an acidic solution containing tin, and the negative electrode storage The tank is connected to the negative electrode through the pipeline through the liquid pump to form a circuit. During the charging and discharging process, the positive and negative electrolytes are respectively pumped into the battery under the push of the liquid pump to ensure the continuous flow of the electrolyte between the liquid storage tank and the battery.

含锡的酸性溶液中,主要是以氧化亚锡、氢氧化亚锡、氯化亚锡、硫化亚锡、焦磷酸亚锡、硫酸亚锡、烷基磺酸亚锡或氟化亚锡作为单电池的负极活性物质,负极活性物质水溶液的浓度范围为0.01mol/L~2mol/L。In the acidic solution containing tin, mainly use stannous oxide, stannous hydroxide, stannous chloride, stannous sulfide, stannous pyrophosphate, stannous sulfate, stannous alkylsulfonate or stannous fluoride as the single The negative electrode active material of the battery, the concentration range of the negative electrode active material aqueous solution is 0.01mol/L-2mol/L.

含钒的酸性溶液中,主要是以二氧化钒或硫酸氧钒作为单电池的正极活性物质,正极活性物质水溶液的浓度范围为0.01mol/L~4mol/L。In the acidic solution containing vanadium, vanadium dioxide or vanadyl sulfate is mainly used as the positive electrode active material of the unit cell, and the concentration range of the positive electrode active material aqueous solution is 0.01mol/L-4mol/L.

电解液是酸性电解液,该电解液中酸的主要成分是以下一种或一种以上:硫酸、盐酸、硝酸、磷酸、碳酸,电解液的浓度范围为0.1mol/L~5mol/L。The electrolytic solution is an acidic electrolytic solution, and the main components of the acid in the electrolytic solution are one or more of the following: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, and the concentration range of the electrolytic solution is 0.1mol/L~5mol/L.

隔膜可以防止正负极电解液的交叉污染,同时又可以通过质子,隔膜可以采用常规的阳离子交换膜。The diaphragm can prevent the cross-contamination of the positive and negative electrolytes, and at the same time can pass protons. The diaphragm can use a conventional cation exchange membrane.

本发明中,单电池正负极电极材料为常规的多孔状碳毡类材料,如石墨毡、炭布、复合炭毡或碳纤维复合材料。In the present invention, the positive and negative electrode materials of the single cell are conventional porous carbon felt materials, such as graphite felt, carbon cloth, composite carbon felt or carbon fiber composite material.

本发明的优点:Advantages of the present invention:

1、本发明以四价钒化合物为液流电池正极活性物质,二价锡为液流电池负极活性物质,电池经充放电测试,具有循环寿命长,可深度放电的优点,电池效率比同样条件下的全钒液流电池效率高。1. In the present invention, the tetravalent vanadium compound is used as the positive electrode active material of the flow battery, and the divalent tin is used as the negative electrode active material of the flow battery. After the battery is charged and discharged, it has the advantages of long cycle life and deep discharge, and the battery efficiency is higher than that under the same conditions. The all-vanadium redox flow battery has high efficiency.

2、本发明中液流电池负极活性物质为二价锡化合物,二价锡化合物在发生氧化还原反应中转移两个电子,电池比容量比转移一个电子高。同时,锡化合物是一种环境友好性物质且价格低廉,不会对环境造成污染,完全符合液流电池绿色环保的特征。2. The negative electrode active material of the liquid flow battery in the present invention is a divalent tin compound, and the divalent tin compound transfers two electrons in the oxidation-reduction reaction, and the specific capacity of the battery is higher than that of transferring one electron. At the same time, the tin compound is an environmentally friendly substance with low price and will not pollute the environment, which is completely in line with the green characteristics of the flow battery.

3、本发明液流电池具有制造工艺简单、成本低、循环寿命高等优点。3. The liquid flow battery of the present invention has the advantages of simple manufacturing process, low cost, and high cycle life.

附图说明 Description of drawings

图1为本发明单电池结构图。Fig. 1 is a structural diagram of a single battery of the present invention.

图2为本发明单电池系统示意图。Fig. 2 is a schematic diagram of the single battery system of the present invention.

图1-图2中,1双极板I;2电极I;3电极框I;4隔膜;5电极框II;6双极板II;7单电池;8储液罐I;9泵I;10正极;11负极;12电极II;13泵II;14储液罐II。In Figure 1-Figure 2, 1 bipolar plate I; 2 electrode I; 3 electrode frame I; 4 diaphragm; 5 electrode frame II; 6 bipolar plate II; 7 single cell; 8 liquid storage tank I; 9 pump I; 10 positive pole; 11 negative pole; 12 electrode II; 13 pump II; 14 liquid storage tank II.

具体实施方式 Detailed ways

如图1所示,本发明新型液流电池的单电池7主要包括:双极板I 1、电极I 2、电极框I 3、隔膜4、电极框II 5、双极板II 6等,电极I 2和电极II分别安装于电极框I 3和电极框II 5内,电极框I 3和电极框II 5内侧通过隔膜4隔开,电极框I 3和电极框II 5外侧分别安装双极板I 1和双极板II6。本发明中,单电池正、负极双极板为常规的导电复合材料、导电碳板或金属板。As shown in Figure 1, the single cell 7 of the novel liquid flow battery of the present invention mainly comprises: bipolar plate I 1, electrode I 2, electrode frame I 3, diaphragm 4, electrode frame II 5, bipolar plate II 6, etc., electrode I 2 and electrode II are respectively installed in electrode frame I 3 and electrode frame II 5, the inside of electrode frame I 3 and electrode frame II 5 are separated by diaphragm 4, and the outer sides of electrode frame I 3 and electrode frame II 5 are respectively installed with bipolar plates I 1 and bipolar plate II6. In the present invention, the positive and negative bipolar plates of the single cell are conventional conductive composite materials, conductive carbon plates or metal plates.

如图2所示,本发明新型液流电池的单电池系统主要包括电极I 2、隔膜4、储液罐I 8、泵I 9、正极10、负极11、电极II 12、泵II 13、储液罐II 14等,具体结构如下:As shown in Figure 2, the single cell system of the novel flow battery of the present invention mainly includes electrode I 2, diaphragm 4, liquid storage tank I 8, pump I 9, positive electrode 10, negative electrode 11, electrode II 12, pump II 13, storage tank Liquid tank II 14, etc., the specific structure is as follows:

储液罐I 8为正极储液罐,储液罐I 8出口端通过管路与正极10底部连通,在该管路上设有泵I 9,储液罐I 8入口端通过管路与正极10顶部连通,在储液罐I 8内装有正极电解液,正极电解液为含钒的酸性溶液,储液罐I 8通过管道经由液泵接入电池内部构成回路,在储液罐I 8内发生的电极反应为VO2 ++2H++e→VO2++H2O;The liquid storage tank I 8 is a positive electrode liquid storage tank, the outlet of the liquid storage tank I 8 communicates with the bottom of the positive electrode 10 through a pipeline, and a pump I 9 is arranged on the pipeline, and the inlet end of the liquid storage tank I 8 communicates with the positive electrode 10 through a pipeline. The top is connected, and the positive electrode electrolyte is installed in the liquid storage tank I 8. The positive electrode electrolyte is an acidic solution containing vanadium. The electrode reaction is VO 2 + +2H + +e→VO 2+ +H 2 O;

储液罐II 14为负极储液罐,储液罐II 14出口端通过管路与负极11底部连通,在该管路上设有泵II 13,储液罐II 14入口端通过管路与负极11顶部连通,在储液罐II 14内装有负极电解液,负极为含锡的酸性溶液,储液罐II 14通过管道经由液泵接入电池内部构成回路,在储液罐II 14内发生的电极反应为Sn2++2e→Sn;The liquid storage tank II 14 is a negative electrode liquid storage tank, the outlet of the liquid storage tank II 14 communicates with the bottom of the negative electrode 11 through a pipeline, and a pump II 13 is arranged on the pipeline, and the inlet of the liquid storage tank II 14 communicates with the negative electrode 11 through a pipeline. The top is connected, and the negative electrode electrolyte is installed in the liquid storage tank II 14, and the negative pole is an acidic solution containing tin. The reaction is Sn 2+ +2e→Sn;

正极10与负极11内分别装有电极I 2、电极II 12,正极10与负极11之间通过隔膜4隔开,在充放电过程中,正、负极电解液在液泵推动下分别将电解液泵入电池内,保证电解液在储液罐和电池之间不断流动;本发明中,多组单电池可串联成电堆。Positive electrode 10 and negative electrode 11 are respectively equipped with electrode I 2 and electrode II 12, and the positive electrode 10 and negative electrode 11 are separated by diaphragm 4. During the charging and discharging process, the positive and negative electrolytes are pushed by the liquid pump to separate the electrolyte respectively. Pumped into the battery to ensure the continuous flow of electrolyte between the liquid storage tank and the battery; in the present invention, multiple groups of single cells can be connected in series to form a stack.

实施例1Example 1

向单电池负极储液罐中加入1mol/L二价锡离子(氧化亚锡)和2mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入2mol/L四价钒离子(硫酸氧钒)和2mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为50mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在88%,平均库仑效率94.85%,平均能量效率83.24%。高于同样条件下全钒液流电池的效率。Add 1mol/L divalent tin ion (stannous oxide) and 2mol/L sulfuric acid electrolyte as negative electrode electrolyte in single cell negative electrode liquid storage tank, add 2mol/L tetravalent vanadium ion ( vanadyl sulfate) and 2mol/L sulfuric acid electrolyte as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 50mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 88%, the average coulombic efficiency is 94.85%, and the average energy efficiency is 83.24%. Higher than the efficiency of all-vanadium redox flow battery under the same conditions.

实施例2Example 2

向单电池负极储液罐中加入1mol/L二价锡离子(氢氧化亚锡)和2mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入2mol/L四价钒离子(硫酸氧钒)和2mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为100mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在83.7%,平均库仑效率94.4%,平均能量效率79.1%。Add 1mol/L divalent tin ion (stannous hydroxide) and 2mol/L sulfuric acid electrolyte to the single-cell negative electrode liquid storage tank as the negative electrode electrolyte, and add 2mol/L tetravalent vanadium ions to the single-cell positive electrode liquid storage tank (vanadyl sulfate) and 2mol/L sulfuric acid electrolyte as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 100mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 83.7%, the average coulombic efficiency is 94.4%, and the average energy efficiency is 79.1%.

实施例3Example 3

向单电池负极储液罐中加入1mol/L二价锡离子(氯化亚锡)和2mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入2mol/L四价钒离子(二氧化钒)和2mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为160mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在75.6%,平均库仑效率92.5%,平均能量效率69.9%。Add 1mol/L divalent tin ion (stannous chloride) and 2mol/L sulfuric acid electrolyte to the single-cell negative electrode liquid storage tank as the negative electrode electrolyte, and add 2mol/L tetravalent vanadium ions to the single-cell positive electrode liquid storage tank (vanadium dioxide) and 2mol/L sulfuric acid electrolyte as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 160mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 75.6%, the average coulombic efficiency is 92.5%, and the average energy efficiency is 69.9%.

实施例4Example 4

向单电池负极储液罐中加入0.5mol/L二价锡离子(硫化亚锡)和2.5mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入1mol/L四价钒离子(硫酸氧钒)和2.5mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为50mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在87.8%,平均库仑效率95.7%,平均能量效率84.1%。Add 0.5mol/L divalent tin ion (stannous sulfide) and 2.5mol/L sulfuric acid electrolyte to the negative electrode liquid storage tank of the single cell as the negative electrode electrolyte, and add 1mol/L tetravalent vanadium to the positive electrode liquid storage tank of the single cell Ion (vanadyl sulfate) and 2.5mol/L sulfuric acid electrolyte as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 50mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 87.8%, the average coulombic efficiency is 95.7%, and the average energy efficiency is 84.1%.

实施例5Example 5

向单电池负极储液罐中加入0.5mol/L二价锡离子(焦磷酸亚锡)和2.5mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入1mol/L四价钒离子(二氧化钒)和2.5mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为100mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在85.2%,平均库仑效率92.6%,平均能量效率78.9%。Add 0.5mol/L divalent tin ion (stannous pyrophosphate) and 2.5mol/L sulfuric acid electrolyte to the negative electrode liquid storage tank of the single battery as the negative electrode electrolyte, and add 1mol/L tetravalent tin ion to the positive electrode liquid storage tank of the single battery Vanadium ions (vanadium dioxide) and 2.5mol/L sulfuric acid electrolyte are used as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 100mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 85.2%, the average coulombic efficiency is 92.6%, and the average energy efficiency is 78.9%.

实施例6Example 6

向单电池负极储液罐中加入0.5mol/L二价锡离子(硫酸亚锡)和2.5mol/L硫酸电解液作为负极电解液,向单电池正极储液罐中加入1mol/L四价钒离子(硫酸氧钒)和2.5mol/L硫酸电解液作为正极电解液。石墨毡为电极材料,阳离子交换膜为隔膜,对电池进行充放电测试。其中,充放电电流密度为160mA/cm2,充电电压为1.5V,放电电压为1.1V。经过多次充放电测试,平均电压效率为在77.5%,平均库仑效率92.1%,平均能量效率71.4%。Add 0.5mol/L divalent tin ion (stannous sulfate) and 2.5mol/L sulfuric acid electrolyte to the negative electrode liquid storage tank of the single cell as the negative electrode electrolyte, and add 1mol/L tetravalent vanadium to the positive electrode liquid storage tank of the single cell Ion (vanadyl sulfate) and 2.5mol/L sulfuric acid electrolyte as positive electrolyte. Graphite felt is used as the electrode material, and the cation exchange membrane is used as the diaphragm, and the battery is charged and discharged. Wherein, the charging and discharging current density is 160mA/cm 2 , the charging voltage is 1.5V, and the discharging voltage is 1.1V. After multiple charge and discharge tests, the average voltage efficiency is 77.5%, the average coulombic efficiency is 92.1%, and the average energy efficiency is 71.4%.

Claims (6)

1. flow battery, it is characterized in that, the monocell of this flow battery is provided with positive pole, anodal fluid reservoir, negative pole, negative pole fluid reservoir, positive and negative electrode is separated by barrier film, in the anodal fluid reservoir anode electrolyte is housed, anode electrolyte is the acid solution that contains vanadium, and anodal fluid reservoir consists of the loop by pipeline via liquid pump access positive pole; Negative electricity solution liquid is housed in the negative pole fluid reservoir, and negative pole electrolyte is stanniferous acid solution, and the negative pole fluid reservoir consists of the loop by pipeline via liquid pump access negative pole;
Negative pole electrolyte is comprised of the negative electrode active material aqueous solution and acidic electrolysis bath, and anode electrolyte is comprised of the positive active material aqueous solution and acidic electrolysis bath;
The flow battery positive active material is tetravalent vanadium compound, and the electrode reaction that positive active material occurs is VO 2 +/ VO 2+The flow battery negative electrode active material is the Bivalent Tin compound, and the electrode reaction that negative electrode active material occurs is Sn 2+/ Sn;
The concentration range of the negative electrode active material aqueous solution is 0.01mol/L~2mol/L; The concentration range of the positive active material aqueous solution is 0.01mol/L~4mol/L; The concentration range of described acidic electrolysis bath is 0.1mol/L~5mol/L.
2. according to flow battery claimed in claim 1, it is characterized in that, organize monocell more and be connected into pile.
3. according to flow battery claimed in claim 1, it is characterized in that, in the stanniferous acid solution, active material is stannous oxide, stannous hydroxide, stannous chloride, stannous sulfide, stannous pyrophosphate, stannous sulfate, the inferior tin of alkyl sulfonic acid or stannous fluoride.
4. according to flow battery claimed in claim 1, it is characterized in that, contain in the acid solution of vanadium, active material is vanadium dioxide or vanadic sulfate.
5. according to flow battery claimed in claim 1, it is characterized in that, in the described acidic electrolysis bath acid composition be following one or more: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid.
6. according to flow battery claimed in claim 1, it is characterized in that, barrier film adopts cation-exchange membrane.
CN2009100134486A 2009-08-27 2009-08-27 Liquid flow battery Expired - Fee Related CN101997129B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100134486A CN101997129B (en) 2009-08-27 2009-08-27 Liquid flow battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100134486A CN101997129B (en) 2009-08-27 2009-08-27 Liquid flow battery

Publications (2)

Publication Number Publication Date
CN101997129A CN101997129A (en) 2011-03-30
CN101997129B true CN101997129B (en) 2013-09-18

Family

ID=43786961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100134486A Expired - Fee Related CN101997129B (en) 2009-08-27 2009-08-27 Liquid flow battery

Country Status (1)

Country Link
CN (1) CN101997129B (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102244286B (en) * 2011-06-07 2014-10-15 中国东方电气集团有限公司 Flow battery system and repair device thereof
CN102856573A (en) * 2011-06-30 2013-01-02 中国科学院大连化学物理研究所 Zinc-vanadium redox flow energy storage battery
CN102447132A (en) * 2011-10-24 2012-05-09 吉林省晋吉锂电池有限公司 Semisolid flow lithium ion battery
CN102709579B (en) * 2012-04-05 2015-08-19 天津滨海储能技术有限公司 The preparation method of vanadium liquid
CN103928720A (en) * 2013-03-26 2014-07-16 摩尔动力(北京)技术股份有限公司 Method for prolonging working time length of liquid change storage battery
CN104518233A (en) * 2013-09-29 2015-04-15 中国科学院大连化学物理研究所 Chlorine-containing all-vanadium redox flow battery anode electrolyte
JP2017054631A (en) * 2015-09-08 2017-03-16 昭和電工株式会社 Electrolytic solution for redox flow battery, and redox flow battery
CN106299437A (en) * 2016-11-11 2017-01-04 攀钢集团攀枝花钢铁研究院有限公司 Vanadium cell and electrolyte liquid thereof and the method improving its electro-chemical activity
CN106328975A (en) * 2016-11-11 2017-01-11 攀钢集团攀枝花钢铁研究院有限公司 Full-vanadium oxidation reduction flow battery
JP7149280B2 (en) * 2017-09-14 2022-10-06 東洋エンジニアリング株式会社 redox flow battery
CN108199069B (en) * 2018-01-17 2020-09-29 大连博融新材料有限公司 Electrolyte for redox flow battery and preparation method thereof
CN109103484A (en) * 2018-08-29 2018-12-28 深圳大学 A kind of flow battery and preparation method thereof
CN110649304B (en) * 2019-09-25 2024-08-16 何国珍 Tin-iodic acid rechargeable battery
CN110993999A (en) * 2019-11-26 2020-04-10 中国科学院金属研究所 A kind of electrolyte containing additive for iron-chromium flow battery and its application
CN113707925A (en) * 2021-08-24 2021-11-26 复旦大学 Tin-manganese aqueous flow battery
CN117254074B (en) * 2023-11-20 2024-02-09 华中科技大学 An alkaline tin negative electrolyte and an alkaline tin-iron flow battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996064A (en) * 1975-08-22 1976-12-07 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrically rechargeable REDOX flow cell
CN1694282A (en) * 2005-04-22 2005-11-09 攀钢集团攀枝花钢铁研究院 Electrode for all-vanadium redox flow battery and preparation method thereof
CN201514973U (en) * 2009-08-27 2010-06-23 中国科学院金属研究所 A flow battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996064A (en) * 1975-08-22 1976-12-07 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrically rechargeable REDOX flow cell
CN1694282A (en) * 2005-04-22 2005-11-09 攀钢集团攀枝花钢铁研究院 Electrode for all-vanadium redox flow battery and preparation method thereof
CN201514973U (en) * 2009-08-27 2010-06-23 中国科学院金属研究所 A flow battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
D-G.OEI.Chemically regenerative redox fuel cells.《JOURNAL OF APPLIED ELECTROCHEMISTRY》.1982,第12卷(第1期),87-100.
D-G.OEI.Chemically regenerative redox fuel cells.《JOURNAL OF APPLIED ELECTROCHEMISTRY》.1982,第12卷(第1期),87-100. *

Also Published As

Publication number Publication date
CN101997129A (en) 2011-03-30

Similar Documents

Publication Publication Date Title
CN101997129B (en) Liquid flow battery
CN102479968B (en) Zinc / polyhalide energy storage cell
CN103000924B (en) Organic phase dual flow battery
CN207587857U (en) A kind of zinc-nickel single flow battery
CN105680082A (en) Long-lifetime zinc-bromine flow battery structure and electrolyte
CN118016944B (en) Water system iron-cerium flow battery
CN112786938B (en) Acid-base Hybrid High Voltage Aqueous Zinc Batteries and Zinc Flow Batteries with Dual Dissolution Deposition Reactions
CN201514973U (en) A flow battery
CN106549179B (en) An organic system lithium quinone flow battery
CN110867587A (en) A high-power and long-life neutral aqueous hybrid flow battery based on pyridylphenazine
CN100438190C (en) All-vanadium ion flow battery electrolyte and preparation method thereof
CN106532093A (en) Quinone metal redox couple flow cell system
CN102227029B (en) High-concentration vanadium electrolyte and preparation method thereof
CN112952212A (en) Aqueous manganese dioxide-metal secondary battery
CN105280943B (en) A kind of full manganese flow battery
CN102694143A (en) Air/vanadium redox flow battery
CN108390110A (en) A kind of lead-manganese secondary battery
WO2016078492A1 (en) Quinone polyhalide flow battery
CN105322186B (en) A kind of method for reducing all-vanadium flow battery activation polarization
CN107565151B (en) Regeneration method of electrode activity of all-vanadium redox flow battery
CN104300169A (en) Alkaline zinc vanadium flow battery
CN106129443B (en) A kind of novel keggin type cobalt wolframic acid flow battery
CN106450400A (en) All-vanadium redox flow battery
CN110071317A (en) A kind of tin bromine flow battery
CN104716385A (en) Vanadium manganese hybrid flow battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130918

Termination date: 20150827

EXPY Termination of patent right or utility model