WO2015007204A1 - 一种全钒液流电池及其运行方式 - Google Patents
一种全钒液流电池及其运行方式 Download PDFInfo
- Publication number
- WO2015007204A1 WO2015007204A1 PCT/CN2014/082235 CN2014082235W WO2015007204A1 WO 2015007204 A1 WO2015007204 A1 WO 2015007204A1 CN 2014082235 W CN2014082235 W CN 2014082235W WO 2015007204 A1 WO2015007204 A1 WO 2015007204A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- vanadium
- positive
- flow battery
- negative electrode
- Prior art date
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 71
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 5
- 239000001205 polyphosphate Substances 0.000 claims abstract description 5
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 4
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 4
- 235000021317 phosphate Nutrition 0.000 claims abstract description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 11
- 229910001456 vanadium ion Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the invention relates to an all-vanadium redox flow battery and an operation mode thereof, and belongs to the field of liquid flow batteries.
- an all-vanadium flow battery has advantages such as long cycle life, easy scale, quick response, free location, and the like, and has been in many large-scale solar energy storage. It has been successfully applied in wind power storage equipment and large emergency power supply systems and power system peak clipping and valley filling.
- the electrolyte is the key material and energy storage material of the vanadium battery. During the charging process, the electrolyte is driven by the left and right magnetic pump, and the positive and negative solution reacts through the ion conductive membrane as follows:
- V 5+ has a higher concentration (>1M).
- the positive solution is prone to precipitate V 2 O.
- the precipitation will block the gap structure of the electrode. , causing system paralysis and increasing battery maintenance costs. If cooling measures are taken, the cost and energy consumption of supporting facilities will not be underestimated.
- the electrolyte stability additives studied at home and abroad mainly include:
- alkali metal sulfate sodium sulfate, potassium sulfate, magnesium sulfate, etc.
- alkali metal salts there have been many reports on alkali metal salts in the literature, but it is necessary to add a certain amount (>2%, m/v) to have an effect, resulting in a solution.
- concentration of other metal ions is increasing, and there is no support for the application of stable charge and discharge data in the test level.
- Phosphoric acid and its salts have been reported as stabilizers for vanadium electrolytes, but the research on the low-temperature stability of the anodes after addition is still blank, and the storage stability test data under long-term extreme conditions have not been reported.
- European invention patent EP1143546 discloses an operation mode of an all-vanadium redox flow battery, which mentions that by adding a communication line to the upper end of the positive and negative electrode solution storage tank, the short-term capacity drop of the system caused by the mutual migration of the positive and negative electrode vanadium solutions is alleviated, but It does not avoid the irreversible capacity drop caused by the occurrence of hydrogen evolution side reactions, which has a limited improvement in the large attenuation of the discharge capacity caused by long-term operation of the system. Summary of the invention
- An all-vanadium redox flow battery comprising a positive electrode electrolyte and a negative electrode electrolyte, wherein the ratio of total vanadium in the positive electrode electrolyte to the negative electrode electrolyte is always positive: the negative electrode is 1: 1.5 ⁇ 1: 1.2, and the positive electrode electrolyte
- the negative electrode electrolyte contains additives, and the concentration of the additive is 0.01 mol/L to 0.5 mol/L.
- the additive is at least one selected from the group consisting of sulfuric acid, sulfate, phosphoric acid, phosphate, pyrophosphate, and polyphosphate.
- the total vanadium content of the electrolyte is the concentration of vanadium ions in the electrolyte X electrolyte volume; the ratio of total vanadium in the positive electrolyte and the negative electrolyte refers to the ratio of the total vanadium content of the positive electrolyte to the total vanadium of the negative electrolyte.
- the concentration of vanadium ions in the positive electrode electrolyte is the same as the concentration of vanadium ions in the negative electrode electrolyte; the vanadium ion concentration includes a sum of concentrations of vanadium ions of various valence states present in the electrolyte.
- the positive electrode electrolyte and the negative electrode electrolyte used in the all-vanadium redox flow battery are respectively stored in the positive and negative electrolyte storage tanks, and the total vanadium ratio of the positive electrode electrolyte and the negative electrode electrolyte is equal.
- the invention reduces the ratio of the V 2+ of the negative electrode solution to the total V n+ vanadium content of the negative electrode during the operation of the battery (SOC state), that is, the V 2+ in the negative electrode electrolyte is reduced by making the total vanadium content of the negative electrode larger than a certain ratio of the positive electrode. concentration.
- the volume ratio of the positive and negative electrodes can be controlled, and the volume ratio of the positive and negative electrolytes can be controlled during operation to minimize the hydrogen evolution reaction of the negative electrode to maintain the lower capacity decay rate of the system.
- the ratio of the total amount of vanadium in the negative electrode electrolyte can be achieved by transferring the positive electrode electrolyte into the negative electrode electrolyte, and the volume of the transferred electrolyte is determined by the positive and negative electrode vanadium ion concentrations and the volume of the positive and negative electrode solutions measured in real time.
- the V 5+ ratio of the positive electrode solution can reach 85% or more at the completion of charging (the normal state is about 60%).
- the concentration of 5+ is too high or the temperature exceeds 45 °C. Therefore, while controlling the total vanadium ratio of the system, an additive is added to the positive electrode electrolyte and the negative electrode electrolyte to suppress the precipitation of V 3+ in the negative electrode solution at a low temperature, and to suppress the V 5+ in the positive electrode solution at a high temperature. Precipitating to achieve an additive to stabilize the entire system.
- the additive of the all-vanadium redox flow battery of the present invention is at least one of sulfuric acid, sulfate, phosphoric acid, phosphate, pyrophosphate, polyphosphate, etc., wherein the cation is preferably Na+.
- the additive is preferably added to the positive electrode electrolyte and the negative electrode electrolyte according to the following addition method:
- Negative Electrolyte Solution Add an additive directly to the negative electrode electrolyte so that the concentration of the additive is 0.01 mol/L to 0.5 mol/L. After the addition, stir until all the solution is dissolved.
- Positive Electrode Solution The additive is first diluted with water (additive: water: 1:1 to 1:4), and the diluted additive is added to the positive electrode electrolyte.
- the additive can be added at any temperature between -15 ° C and 55 ° C.
- the polyphosphate is added in an amount of 0.01 mol/L to 0.5 mol/L based on the concentration of the monomer salt in the electrolyte.
- the ratio of total vanadium in the positive electrode electrolyte and the negative electrode electrolyte is always kept as positive electrode: the negative electrode is 1: 1.3 ⁇ 1: 1.2.
- the all-vanadium redox flow battery of the present invention is a phosphoric acid or a phosphate.
- the concentration of the additive of the all-vanadium redox flow battery of the present invention is preferably 0.04 to 0.20 mol/L, more preferably 0.20 mol/L.
- the ratio of total vanadium in the positive electrode electrolyte and the negative electrode electrolyte is always positive: the negative electrode is 1:1.5 ⁇ 1: 1.2, and the charge and discharge voltage of the all-vanadium flow battery is between 0.9V and 1.58V. .
- the ratio of total vanadium in the positive electrode electrolyte and the negative electrode electrolyte is always positive: the negative electrode is 1: 1.3 ⁇ 1: 1.2, and the charge and discharge voltage range of the all-vanadium flow battery is 0.9V ⁇ 1.58V. between.
- the operation mode of the all-vanadium redox flow battery system of the present invention is preferably the charge and discharge operating temperature of the all-vanadium redox flow battery The degree is 0 ° C ⁇ 5 (TC, stored at -20 ° C ⁇ 0 ° C under full charge).
- the above-mentioned flow battery with different total vanadium distribution modes of positive and negative electrodes avoids the system capacity attenuation, and the total discharge capacity (solution utilization rate) of the system is partially affected (depending on the total vanadium ratio, and the initial positive and negative electrodes) Compared with the equivalent solution, the total discharge capacity has a decrease of about 20%. Therefore, the operation mode of expanding the charge and discharge voltage range is adopted for this phenomenon, and the conventional charge and discharge voltage is 1.0V ⁇ 1.55V, which is extended to 0.9V ⁇ 1.58. V, thereby making up for the problem of a decrease in the utilization rate of the electrolyte due to the difference in the total vanadium content of the positive and negative electrodes.
- the invention proposes a novel operation mode of an all-vanadium redox flow battery, that is, different total vanadium content of the positive and negative electrodes, changing the voltage range, and using phosphoric acid additives.
- the method can maintain high energy density operation while greatly reducing the irreversible decay of the discharge energy caused by the hydrogen evolution side reaction.
- the operation mode is simple and easy, does not increase any cost, and greatly improves the utilization rate of the vanadium electrolyte, improves the battery performance, and is suitable for industrialization promotion.
- Example 1 is a graph showing the capacity change of a liquid flow battery of Example 2.
- Figure 2 is a graph showing the capacity change of the liquid flow battery of Example 3.
- Fig. 3 is a graph showing the capacity change of the flow battery of the fourth embodiment. detailed description
- Example 1 The stability of phosphoric acid and its salt additives was tested at high and low temperatures.
- Examples 2 to 4 The batteries used in the test were respectively Nafionl type l5 ion membranes, and the current density was
- V 5+ pentavalent vanadium electrolyte with vanadium ion concentration of 1.66M and 1.83M, sealed in 10mL plastic In the heart tube. Phosphoric acid was added in a concentration of 0.05 M to 0.3 M, and a control test was carried out. The solution was observed in a water bath at 40 ° C and 50 ° C. The test results are shown in Table 1 below.
- Example 3 The test parameters and test results are shown in the table below.
- the capacity change curve is shown in Figure 2:
- Example 4 The test parameters and test results are shown in the table below.
- the capacity change curve is shown in Figure 3: Item Total vanadium 6:7 ratio (positive/negative) Total vanadium ratio 1 : 1 (positive / negative) Solution temperature 40 °C
Abstract
一种全钒液流电池及其运行方式，属于液流电池领域。该全钒液流电池，包括正极电解液和负极电解液，所述正极电解液与负极电解液中总钒比例始终保持为正极：负极为1:1.5〜1:1.2，且正极电解液与负极电解液中均含有添加剂，添加剂的浓度为0.01mol/L〜0.5mol/L，其中，所述添加剂选自硫酸、硫酸盐、磷酸、磷酸盐、焦磷酸盐、多聚磷酸盐中的至少一种。该全钒液流电池既可以保持高的能量密度运行，同时又可大大降低析氢副反应造成的放电能量的不可逆衰减。
Description
说 明 书 一种全钒液流电池及其运行方式
技术领域
本发明涉及一种全钒液流电池及其运行方式， 属于液流电池领域。
背景技术 作为新型绿色二次蓄电池， 全钒液流电池 （VFB)拥有循环寿命长、 容易规模化、 快速响应、 选址自由等其他电池系统所难以比拟的优势， 且已经在众多大型太阳能储 能和风电储能设备及大型应急电源系统及电力系统削峰填谷中成功应用。
电解液是钒电池的关键材料和储能物质， 充电过程中电解液在左右磁力泵驱动下， 正 负极溶液通过离子传导膜发生如下反应：
正极反应： VO2++H2O→VO2 ++2H++e— E0=1.00V (1)
负极反应： V3++e-→V2+ E0=-0.26V (2)
析氢反应：
而当充电到一定程度的时候，负极 V2+达到一定浓度开始与电解液中的 H+发生析氢 反应：
V2++ H+→V3++ H2† (3 )
而此反应直接导致负极参与放电的 V2+总量减少， 相应系统的放电容量减少， 随着 系统运行， 析氢副反应不断累积导致正负极价态失衡， 将严重影响系统的使用效率， 同时氢气的生成也给环境带来危险。 以上问题已经成为钒电池进入实用化阶段亟待解 决的技术瓶颈。
运行安全性（添加剂)：
正极溶液的充电完毕时 V5+具有较高的浓度 （>1M)， 在此情况下， 系统超过 40°C 运行时， 正极溶液极易出现沉淀 V2O"。沉淀将使电极空隙结构堵塞， 造成系统瘫痪， 加大电池维修成本。 如果采取降温措施， 则配备换热系统带来配套设施成本和能耗不 可低估。
此时通过在正负极溶液中加入一定量添加剂来改善正极电解液在 40°C以上的运行 稳定性， 是必须解决的问题之一。
近几年国内外研究的电解液稳定性添加剂主要有：
1 ) 有机小分子类， 如甘油， 醇类， 有机酸， 有机脲等， 研究发现这些机物分子 在正极溶液中均能与 V5+发生氧化还原反应， 将 V5+还原为 V4+， 本身被氧化为 CO2和
水， 失去稳定 v5+离子的能力；
2 ) 碱金属硫酸盐， 硫酸钠， 硫酸钾， 硫酸镁等； 文献中已有不少关于碱金属盐 的报道， 但需添加一定量（>2%， m/v)才有效果， 造成溶液中其他金属离子浓度升高， 且目前尚无其中试级稳定充放电应用数据的支持。
磷酸及其盐类作为钒电解液稳定剂已经有报道， 但其添加后的负极低温稳定性的 研究仍属空白， 且长期极端条件下的储存稳定试验数据还没有报道。
欧洲发明专利 EP1143546公开了一种全钒液流电池运行方式， 其中提到通过对正 负极溶液储罐上端增加联通管路， 来减缓正负极钒溶液相互迁移导致的系统短期容量 下降， 但其并不能避免析氢副反应的发生而导致的不可逆容量下降， 其对系统长期运 行导致的放电容量大幅衰减改善有限。 发明内容
本发明的目的是提供一种全钒液流电池。
一种全钒液流电池， 包括正极电解液和负极电解液， 所述正极电解液与负极电解 液中总钒比例始终保持为正极： 负极为 1: 1.5〜1: 1.2， 且正极电解液与负极电解液中均 含有添加剂， 添加剂的浓度为 0.01 mol/L〜0.5mol/L，
其中， 所述添加剂选自硫酸、 硫酸盐、 磷酸、 磷酸盐、 焦磷酸盐、 多聚磷酸盐中 的至少一种。
电解液的总钒量为电解液中钒离子的浓度 X电解液体积； 所述正极电解液与负极 电解液中总钒比例指正极电解液的总钒量与负极电解液的总钒量的比值； 所述正极电 解液中钒离子的浓度与负极电解液中钒离子的浓度相同； 所述钒离子浓度包括电解液 中所存在的各种价态的钒离子的浓度的总和。
现有技术中， 全钒液流电池中所用的正极电解液和负极电解液分别存储于正、 负 极电解液储罐中， 正极电解液和负极电解液的总钒比例相等。 正、 负极电解液均由 VOSO4、V2(SO4)3 按 1:0.5比例（即 V4+: V3+=l: l )配置而成， 而 V4+: H2SO4在 1: 1.5-1:2 之间。当充电到一定程度的时候， 负极 V2+浓度较高时与电解液中的 H+发生析氢反应。 析氢反应与溶液中 V2+浓度为正相关关系， 即 V2+浓度越高， H2产生速度越快。 因此， 本发明降低电池运行过程中负极溶液的 V2+占负极总 Vn+钒量的比例 （SOC状态）， 即 采取使负极总钒量大于正极一定比例的方式降低负极电解液中 V2+浓度。 实际操作中 可通过控制正负极初始溶液体积比，并在运行过程中始终控制正负极电解液的体积比， 使负极的析氢反应降到最低， 来维持系统较低的容量衰减速率。 另外， 运行过程中正
负极电解液钒总量的比例可通过将正极电解液转移到负极电解液中实现， 转移的电解 液的体积由实时测定的正负极钒离子浓度和正负极溶液的体积决定。
始终保持正极总钒与负极总钒量比例为 1: 1.5〜1: 1.2， 如果在运行多个循环后， 经 取样检测， 正极总钒量接近负极量时， 则通过联通阀将正极溶液导出一部分到负极， 保证正负极总钒量之比为 1: 1.5〜1: 1.2之间。
在采取上述措施的同时， 由于正极体积的相对减少， 使得正极溶液在充电完毕时 V5+比例可达 85%以上 （普通状态为 60%左右）， 在此情况下， 为避免正极溶液因 V5+浓 度过高或温度超过 45 °C运行出现沉淀。 因此， 在控制系统全钒比例的同时， 向正极电 解液和负极电解液中加入添加剂， 以抑制负极溶液中 V3+在低温状态下的析出， 及抑制 正极溶液中 V5+在高温下的析出， 实现一种添加剂稳定整个系统。
本发明所述全钒液流电池的添加剂为硫酸、 硫酸盐、 磷酸、 磷酸盐、 焦磷酸盐、 多聚磷酸盐中的至少一种等， 其中的阳离子优选为 Na+。
所述添加剂优选按下述添加方法加入正极电解液和负极电解液中：
负极电解液： 直接向负极电解液中加添加剂， 使添加剂的浓度为 0.01 mol/L〜0.5mol/L， 加入后搅拌， 至全部溶解混匀。
正极电解液： 首先将添加剂用水稀释（添加剂： 水为 1: 1〜1:4，）， 将稀释后的添加 剂加入至正极电解液中。
添加剂可以在 -15°C〜55°C之间的任何温度下加入。 其中， 多聚磷酸盐加入量按其 单体盐在电解液中的浓度为 0.01 mol/L〜0.5mol/L计。
本发明所述全钒液流电池优选所述正极电解液与负极电解液中总钒比例始终保持 为正极： 负极为 1: 1.3〜1: 1.2。
本发明所述全钒液流电池优选所述添加剂为磷酸或磷酸盐。
本发明所述全钒液流电池优选添加剂的浓度为 0.04〜0.20mol/L，进一步优选为 0.20 mol/L。
一种全钒液流电池系统的运行方式，
所述正极电解液与负极电解液中总钒比例始终保持为正极： 负极为 1: 1.5〜1: 1.2， 且所述全钒液流电池运行的充放电电压范围处于 0.9V〜1.58V之间。
进一步优选所述正极电解液与负极电解液中总钒比例始终保持为正极： 负极为 1: 1.3〜1: 1.2， 且所述全钒液流电池运行的充放电电压范围处于 0.9V〜1.58V之间。
本发明所述全钒液流电池系统的运行方式优选所述全钒液流电池的充放电运行温
度为 0°C〜5(TC， 满充电状态下 -20°C〜0°C储存。
上述给出的正负极不同总钒分配方式的液流电池， 在避免系统容量衰减的同时， 系统的总放电容量 （溶液利用率） 受到部分影响 （依据总钒比例不同， 与初始正负极 等量溶液相比， 总放电容量有 20%左右的下降）， 因此针对此现象采取了扩大充放电 电压范围的运行方式， 由常规的充放电压 1.0V〜1.55V， 拓展至 0.9V〜1.58V， 从而弥补 了正负极总钒量不同带来的电解液利用率下降的问题。
本发明的有益效果为：
本发明提出了一种新型的全钒液流电池运行方式， 即正负极不同总钒量、 改变电 压范围、 使用磷酸类添加剂。 该方法既可以保持高的能量密度运行， 同时又可大大降 低析氢副反应造成的放电能量的不可逆衰减。本运行方式简单易行， 不增加任何成本， 同时大大提高钒电解液的利用率， 提升电池性能， 适合工业化推广。
附图说明
图 1为实施例 2液流电池的容量变化曲线图；
图 2为实施例 3液流电池的容量变化曲线图；
图 3为实施例 4液流电池的容量变化曲线图。 具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明， 但不以 任何方式限制本发明。
实施例 1试验在高低温度下， 磷酸及其盐类添加剂的稳定作用。
实施例 2〜4 试验所用电池分别采用 Nafionl l5 型离子膜， 充放电流密度为
80mA/cm2的条件下， 小型 4w(48cm2电极面积)单电池和 1.5kw(875cm2/节， 15节)， 电 池堆在 25°C/40°C/45°C下测试本运行方式与普通运行方式的电池性能对比。 电解液中 钒离子的浓度均为 1.55M。 实施例 1 磷酸及其磷酸钠添加剂的静态储存实验 1.1正极溶液高温对比实验
钒离子浓度为 1.66M和 1.83M的纯五价钒 （V5+) 电解液， 于 10mL塑料密闭离
心管中。 添加磷酸， 含量为 0.05M〜0.3M， 并作对照试验， 于 40°C和 50°C的水浴中， 观察溶液状况， 试验结果见下表 1。
表 1 不同添加剂添加量对五价钒溶液的稳定作用 （析出天数)
由以上数据可以看出， 对于同一参数的电解液样品， 随着添加量不同， 其稳定时 间也不同）。
1.2低温储存试验：
同样方法在低温下考察了以上添加剂含量对三价钒溶液的低温稳定性的作用。 表 2 添加剂对三价钒在低温下的稳定作用 （析出天数） T=-20°C
添加添加剂对三价钒的低温稳定性影响作用是单向的， 即添加剂加入量越大， 低
温下稳定性越好。 实施例 2 试验参数与试验结果见下表， 容量变化曲线见图 1 :
实施例 3 试验参数与试验结果见下表， 容量变化曲线见图 2:
实施例 4 试验参数与试验结果见下表， 容量变化曲线见图 3 : 项目 总钒 6:7比例（正 /负） 总钒比例 1 : 1 (正 /负） 溶液温度 40 °C
磷酸 0.15M
电池型号 875cm2/节 /15节 （2kW)
充电 /放电截止电压 0.9 V/1.58V 1.0 V/1.55V 衰减率 （500循环） 7.5% 17.5% 能量密度（500循环平均） 18.5 wh/L 12.7 wh/L
Claims
1、 一种全钒液流电池， 包括正极电解液和负极电解液， 其特征在于：
所述正极电解液与负极电解液中总钒比例始终保持为正极： 负极为 1: 1.5〜1: 1.2， 且正极电解液与负极电解液中均含有添加剂， 添加剂的浓度为 0.01 mol/L〜0.5mol/L， 其中， 所述添加剂选自硫酸、 硫酸盐、 磷酸、 磷酸盐、 焦磷酸盐、 多聚磷酸盐中 的至少一种。
2、根据权利要求 1所述的电池， 其特征在于： 所述正极电解液与负极电解液中总 钒比例始终保持为正极： 负极为 1: 1.3〜1.2。
3、 根据权利要求 1所述的电池， 其特征在于： 所述添加剂为磷酸或磷酸盐。
4、 根据权利要求 1所述的电池， 其特征在于： 添加剂的浓度为 0.04〜0.2mol/L。
5、 一种全钒液流电池系统的运行方式， 其特征在于：
所述正极电解液与负极电解液中总钒比例始终保持为正极： 负极为 1: 1.5〜1: 1.2， 且所述全钒液流电池运行的充放电电压范围处于 0.9V〜1.58V之间。
6、 根据权利要求 5所述的运行方式， 其特征在于：
所述正极电解液与负极电解液中总钒比例始终保持为正极： 负极为 1: 1.3〜1.2， 且 所述全钒液流电池运行的充放电电压范围处于 0.9V〜1.58V之间。
7、根据权利要求 5或 6所述的运行方式， 其特征在于： 所述全钒液流电池的充放 电运行温度为 0°C〜50°C， 满充电状态下 -20°C〜45°C储存。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14825952.6A EP3024080B1 (en) | 2013-07-17 | 2014-07-15 | All-vanadium redox flow battery and operation method thereof |
| JP2016526430A JP6231202B2 (ja) | 2013-07-17 | 2014-07-15 | 全バナジウムレドックスフロー電池及びその運転方法 |
| AU2014292587A AU2014292587B2 (en) | 2013-07-17 | 2014-07-15 | All-vanadium redox flow battery and operation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310301519.9 | 2013-07-17 | ||
| CN201310301519.9A CN103367785B (zh) | 2013-07-17 | 2013-07-17 | 一种全钒液流电池及其运行方式 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015007204A1 true WO2015007204A1 (zh) | 2015-01-22 |
Family
ID=49368652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2014/082235 WO2015007204A1 (zh) | 2013-07-17 | 2014-07-15 | 一种全钒液流电池及其运行方式 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3024080B1 (zh) |
| JP (1) | JP6231202B2 (zh) |
| CN (1) | CN103367785B (zh) |
| AU (1) | AU2014292587B2 (zh) |
| WO (1) | WO2015007204A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112447266A (zh) * | 2020-11-17 | 2021-03-05 | 武汉理工大学 | 一种考虑水分子迁移的全钒液流电池容量衰减建模方法 |
| CN114243073A (zh) * | 2021-12-09 | 2022-03-25 | 大连博融新材料有限公司 | 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用 |
| CN115064740A (zh) * | 2022-06-20 | 2022-09-16 | 大连融科储能装备有限公司 | 一种用于全钒液流储能系统实时监控可充放电量的方法 |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367785B (zh) * | 2013-07-17 | 2016-06-22 | 大连融科储能技术发展有限公司 | 一种全钒液流电池及其运行方式 |
| KR101558079B1 (ko) | 2014-02-20 | 2015-10-06 | 오씨아이 주식회사 | 레독스 흐름 전지 |
| CN105762395B (zh) * | 2014-12-16 | 2018-06-19 | 中国科学院大连化学物理研究所 | 一种含有复合添加剂的全钒液流电池正极电解液及其应用 |
| US10062918B2 (en) * | 2015-03-19 | 2018-08-28 | Primus Power Corporation | Flow battery electrolyte compositions containing a chelating agent and a metal plating enhancer |
| CN106299432A (zh) * | 2015-05-26 | 2017-01-04 | 中国科学院金属研究所 | 无机酸作为提高钒电解液浓度和稳定性添加剂的应用 |
| CN106997958A (zh) * | 2016-01-22 | 2017-08-01 | 大连融科储能技术发展有限公司 | 一种消除全钒液流电池电解液杂质影响的方法 |
| WO2017156679A1 (zh) | 2016-03-14 | 2017-09-21 | 大连融科储能技术发展有限公司 | 液流电池调控方法及其调控系统、液流电池 |
| CN107195932B (zh) * | 2016-03-14 | 2019-12-31 | 大连融科储能技术发展有限公司 | 液流电池容量稳定调控方法、系统及液流电池 |
| CN107204480B (zh) * | 2016-03-14 | 2020-04-24 | 大连融科储能技术发展有限公司 | 液流电池电解液参数确定方法及其系统、液流电池 |
| EP3435464A1 (de) * | 2017-07-28 | 2019-01-30 | Siemens Aktiengesellschaft | Redox-flow-batterie und verfahren zum betreiben einer redox-flow-batterie |
| KR20200039610A (ko) * | 2017-08-08 | 2020-04-16 | 스미토모덴키고교가부시키가이샤 | 레독스 플로우 전지의 운전 방법 |
| CN109669142B (zh) * | 2017-09-28 | 2021-12-31 | 大连融科储能技术发展有限公司 | 一种用于实时监测全钒液流电池钒迁移的方法及系统 |
| JP2021028866A (ja) * | 2017-12-19 | 2021-02-25 | 昭和電工株式会社 | 電解液およびレドックスフロー電池 |
| WO2019225050A1 (ja) * | 2018-05-21 | 2019-11-28 | パナソニックＩｐマネジメント株式会社 | フロー電池 |
| CN112216856B (zh) * | 2020-09-17 | 2022-05-13 | 大连博融新材料有限公司 | 一种高温下稳定的盐酸电解液、其制备方法及应用 |
| DE102022113934A1 (de) | 2022-06-02 | 2023-12-07 | Voith Patent Gmbh | Verfahren zum Entfernen von V2O5 Ablagerungen in einem Redox-Flow-Batteriemodul |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1143546A1 (en) | 1999-09-27 | 2001-10-10 | Kashima-Kita Electric Power Corporation | Redox flow battery |
| JP2003157882A (ja) * | 2001-11-21 | 2003-05-30 | Sumitomo Electric Ind Ltd | レドックスフロー電池の運転方法 |
| CN101572319A (zh) * | 2009-06-18 | 2009-11-04 | 湖南维邦新能源有限公司 | 用于全钒液流电池的电解液及其制备方法、以及包括该电解液的全钒液流电池 |
| CN101635363A (zh) * | 2008-07-27 | 2010-01-27 | 比亚迪股份有限公司 | 一种全钒离子液流电池电解液及其制备方法及电池 |
| CN102881933A (zh) * | 2012-10-23 | 2013-01-16 | 北京金能世纪科技有限公司 | 全钒液流电池电解液 |
| CN103367785A (zh) * | 2013-07-17 | 2013-10-23 | 大连融科储能技术发展有限公司 | 一种全钒液流电池及其运行方式 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2815389A (en) * | 1987-12-10 | 1989-07-05 | Unisearch Limited | All-vanadium redox battery and additives |
| JP2994210B2 (ja) * | 1994-08-22 | 1999-12-27 | 住友電気工業株式会社 | バナジウム系レドックスフロー型電池の電解液 |
| JPH11339835A (ja) * | 1998-05-29 | 1999-12-10 | Kashimakita Kyodo Hatsuden Kk | レドックス電池 |
| JP2000012064A (ja) * | 1998-06-25 | 2000-01-14 | Sumitomo Electric Ind Ltd | バナジウムレドックス電池電解液およびそれを用いたバナジウムレドックス電池 |
| JP2001093560A (ja) * | 1999-09-27 | 2001-04-06 | Kashimakita Kyodo Hatsuden Kk | レドックスフロー電池 |
| CN102110836A (zh) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | 一种高稳定性的钒离子电解液 |
-
2013
- 2013-07-17 CN CN201310301519.9A patent/CN103367785B/zh active Active
-
2014
- 2014-07-15 AU AU2014292587A patent/AU2014292587B2/en active Active
- 2014-07-15 WO PCT/CN2014/082235 patent/WO2015007204A1/zh active Application Filing
- 2014-07-15 JP JP2016526430A patent/JP6231202B2/ja active Active
- 2014-07-15 EP EP14825952.6A patent/EP3024080B1/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1143546A1 (en) | 1999-09-27 | 2001-10-10 | Kashima-Kita Electric Power Corporation | Redox flow battery |
| JP2003157882A (ja) * | 2001-11-21 | 2003-05-30 | Sumitomo Electric Ind Ltd | レドックスフロー電池の運転方法 |
| CN101635363A (zh) * | 2008-07-27 | 2010-01-27 | 比亚迪股份有限公司 | 一种全钒离子液流电池电解液及其制备方法及电池 |
| CN101572319A (zh) * | 2009-06-18 | 2009-11-04 | 湖南维邦新能源有限公司 | 用于全钒液流电池的电解液及其制备方法、以及包括该电解液的全钒液流电池 |
| CN102881933A (zh) * | 2012-10-23 | 2013-01-16 | 北京金能世纪科技有限公司 | 全钒液流电池电解液 |
| CN103367785A (zh) * | 2013-07-17 | 2013-10-23 | 大连融科储能技术发展有限公司 | 一种全钒液流电池及其运行方式 |
Non-Patent Citations (1)
| Title |
|---|
| WANG, W.H. ET AL.: "Investigation of Ir-modified Carbon Felt as the Positive Electrode of an All-vanadium Redox Flow Battery.", ELECTROCHIMICA ACTA., vol. 52, 10 May 2007 (2007-05-10), pages 6756, XP022145539 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112447266A (zh) * | 2020-11-17 | 2021-03-05 | 武汉理工大学 | 一种考虑水分子迁移的全钒液流电池容量衰减建模方法 |
| CN112447266B (zh) * | 2020-11-17 | 2024-04-05 | 武汉理工大学 | 一种考虑水分子迁移的全钒液流电池容量衰减建模方法 |
| CN114243073A (zh) * | 2021-12-09 | 2022-03-25 | 大连博融新材料有限公司 | 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用 |
| CN114243073B (zh) * | 2021-12-09 | 2023-11-28 | 大连融科储能集团股份有限公司 | 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用 |
| CN115064740A (zh) * | 2022-06-20 | 2022-09-16 | 大连融科储能装备有限公司 | 一种用于全钒液流储能系统实时监控可充放电量的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016527678A (ja) | 2016-09-08 |
| EP3024080A4 (en) | 2017-03-22 |
| AU2014292587A1 (en) | 2016-02-11 |
| CN103367785B (zh) | 2016-06-22 |
| JP6231202B2 (ja) | 2017-11-15 |
| CN103367785A (zh) | 2013-10-23 |
| EP3024080A1 (en) | 2016-05-25 |
| AU2014292587B2 (en) | 2016-12-22 |
| EP3024080B1 (en) | 2019-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015007204A1 (zh) | 一种全钒液流电池及其运行方式 | |
| CN101572319B (zh) | 用于全钒液流电池的电解液及其制备方法、以及包括该电解液的全钒液流电池 | |
| CN102354762A (zh) | 一种高纯度钒电池电解液的制备方法 | |
| CN109509901B (zh) | 一种碱性锌铁液流电池 | |
| WO2018103518A1 (zh) | 一种中性锌铁液流电池 | |
| CN204577513U (zh) | 一种利用地埋管进行全钒液流电池电解液温度控制的装置 | |
| CN102244285B (zh) | 一种高浓度锌钒氧化还原电池 | |
| CN102881931A (zh) | 一种含磷全钒液流电池正极电解液 | |
| CN102227029B (zh) | 高浓度钒电解液及其制备方法 | |
| CN109888350B (zh) | 一种中温型全钒液流电池的电解液 | |
| CN103904352B (zh) | 一种液流电池用锌电解液及其制备方法 | |
| CN102881932B (zh) | 一种含锰的钒液流电池电解液 | |
| CN104300169B (zh) | 一种碱性锌钒液流电池 | |
| CN101692500A (zh) | 制备全钒离子液流电池电解液的方法及所制备的电解液 | |
| CN108123159A (zh) | 一种提高全钒液流电池负极电解液稳定性的方法 | |
| US11605824B2 (en) | Zinc iodine flow battery | |
| CN105322207A (zh) | 一种含磷的杂多酸全钒液流电池正极电解液及其应用 | |
| WO2023082842A1 (zh) | 一种碱性负极电解液及其组装的碱性锌铁液流电池 | |
| CN115992357A (zh) | 一种全钒液流电池电解液的制备方法 | |
| CN106876814B (zh) | 一种全钒液流电池容量恢复方法 | |
| CN104852074A (zh) | 一种通过电解合成法制备全钒液流电池正极电解液的方法 | |
| CN109768309A (zh) | 一种负极电解液在全钒液流电池的应用 | |
| CN105762395B (zh) | 一种含有复合添加剂的全钒液流电池正极电解液及其应用 | |
| CN106450400A (zh) | 一种全钒氧化还原液流电池 | |
| CN104518228A (zh) | 一种全钒氧化还原液流电池调节方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14825952 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2016526430 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2014825952 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2014292587 Country of ref document: AU Date of ref document: 20140715 Kind code of ref document: A |