WO2016078492A1 - 一种醌多卤化物液流电池 - Google Patents

一种醌多卤化物液流电池 Download PDF

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WO2016078492A1
WO2016078492A1 PCT/CN2015/092059 CN2015092059W WO2016078492A1 WO 2016078492 A1 WO2016078492 A1 WO 2016078492A1 CN 2015092059 W CN2015092059 W CN 2015092059W WO 2016078492 A1 WO2016078492 A1 WO 2016078492A1
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negative electrode
flow battery
electrolyte
ruthenium
positive electrode
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PCT/CN2015/092059
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English (en)
French (fr)
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张华民
赖勤志
李先锋
程元徽
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中国科学院大连化学物理研究所
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Priority to US15/302,440 priority Critical patent/US10446867B2/en
Priority to AU2015349218A priority patent/AU2015349218B2/en
Priority to JP2016566261A priority patent/JP6247778B2/ja
Priority to EP15861860.3A priority patent/EP3223354B1/en
Publication of WO2016078492A1 publication Critical patent/WO2016078492A1/zh

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • 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
    • Y02E60/10—Energy storage using 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 present invention relates to a flow battery system.
  • the well-developed flow battery system mainly includes two kinds of vanadium redox flow batteries and zinc bromine flow batteries.
  • the all-vanadium flow battery realizes the reversible conversion of electrical energy and chemical energy by electrochemical reaction of vanadium ions of different valence states on the inert electrode in the electrolyte.
  • the positive electrode is a VO 2+ /VO 2 + electric pair
  • the negative electrode is a V 2+ /V 3 + electric pair
  • the sulfuric acid is a supporting electrolyte. Because the vanadium ions of different valence states are on both sides of the positive and negative electrodes, the contamination of the electrolyte by the ions is avoided, which affects the performance and life of the battery.
  • the vanadium electrolyte solution can be regenerated, further improving the life of the battery system and reducing operating costs.
  • the electrolyte cost of the vanadium redox flow battery and the cost of the proton exchange membrane are high, and there is still a certain degree of cross-contamination problem between the positive and negative electrodes.
  • the positive and negative half-cells of the zinc-bromine flow battery are separated by a separator, and the electrolyte on both sides is a ZnBr 2 solution. Under the action of the power pump, the electrolyte circulates in a closed loop formed by the liquid storage tank and the battery.
  • the main problem with zinc-bromine flow batteries is that bromine contamination cannot be solved.
  • the ruthenium bromine flow battery has been reported in the literature, but since the proton exchange membrane is used in the literature and sulfuric acid is used as the supporting electrolyte, the cost and the battery voltage are both low.
  • the invention uses a porous membrane and uses hydrochloric acid as a supporting electrolyte, and the cost is obtained. Reduced, the voltage is increased.
  • the utility model relates to a ⁇ multi-halide liquid flow battery system, comprising: a positive and negative electrode end plate, a positive electrode, a porous diaphragm, a negative electrode, a liquid storage tank, a pipeline and a pump.
  • the positive and negative electrodes are composed of a current collector and a positive and negative electrode catalytic material; during charging and discharging, the electrolyte is transported from the liquid storage tank to the positive and negative electrodes via a pump, and the redox reaction of bromine and bromine is generated in the positive electrode, and the ruthenium and ruthenium are oxidized in the negative electrode. Reduction reaction.
  • the specific technical solution of the present invention is as follows:
  • the utility model relates to a ⁇ multi-halide flow battery, which is composed of a battery module, an electrolyte liquid storage tank filled with a positive electrode electrolyte, a negative liquid storage tank filled with a negative electrode electrolyte, a circulation pump and a circulation pipeline;
  • the two cells are connected in series by two or more cells, and the single cell includes a positive electrode, a separator and a negative electrode, the positive electrode electrolyte is a mixed solution of hydrochloric acid and sodium bromide, and the negative electrode electrolyte is a mixed solution of hydrochloric acid and hydrazine.
  • the positive electrode electrolyte is a mixed solution of a concentration of 0.5-2 M hydrochloric acid and a concentration of 0.5-2 M sodium bromide.
  • the negative electrode electrolyte is a mixed solution having a concentration of 0.5 to 2 M hydrochloric acid and a concentration of 0.5 to 1 M.
  • the positive and negative electrolytes contain 0.1-1M quaternary ammonium salt bromine elemental complexing agent, and the interaction between the bromine elemental complexing agent and the bromine element is used to generate a bromine elemental complex, so that the bromine elemental substance and the electrolyte Achieve phase separation to reduce the penetration of bromine.
  • the quaternary ammonium salt bromine elemental complexing agent is nitrogen bromide methyl ethyl pyrrolidine (MEP) or nitrogen bromide methyl ethyl morpholine (MEM).
  • the positive and negative materials are all activated carbon felts.
  • the separator is a porous membrane or a dense membrane.
  • the single cell includes a positive electrode end plate, a positive electrode, a separator, a negative electrode, and a negative electrode end plate.
  • this patent proposes the concept of a multi-halide halide flow battery, which improves the problem that the cost of the bismuth bromine flow battery is high and the battery voltage is low.
  • Example 1 is a cycle stability diagram of a battery of Example 1;
  • Fig. 3 is a graph showing the comparison of charge and discharge of the batteries of Example 1 and Comparative Example 1.
  • the batteries were assembled using a porous film unless otherwise specified.
  • Electrolyte configuration and battery assembly are Electrolyte configuration and battery assembly:
  • Positive electrode electrolyte 40 ml of 1 M HCl + 0.5 M solution of methyl bromide methyl ethyl pyrrolidine + 1 M sodium bromide solution; negative electrode electrolyte: 40 ml of 1 M HCl + 0.5 M solution of methyl bromide methyl ethyl pyrrolidine + 1 M solution
  • the single cells are sequentially a positive electrode end plate, a positive electrode 3 ⁇ 3 cm 2 , a carbon felt, a separator, a carbon felt, a negative electrode 3 ⁇ 3 cm 2 graphite plate, and a negative electrode end plate.
  • Electrolyte flow rate 5 ml/min; charge and discharge current density 20 mA/cm 2 ; battery cycle stability is shown in Fig. 1.
  • Electrolyte configuration and battery assembly are Electrolyte configuration and battery assembly:
  • Positive electrode electrolyte 40 ml of 0.5 M sulfuric acid + 1 M sodium bromide solution
  • negative electrode electrolyte 40 ml of 0.5 M sulfuric acid + 1 M barium solution single cell, positive electrode end plate, positive electrode 3x3 cm 2 , carbon felt, separator, carbon felt, negative electrode 3x3cm 2 graphite plate, negative end plate.
  • Electrolyte flow rate 5 ml/min; charge and discharge current density 20 mA/cm 2 ; battery cycle stability is shown in Fig. 2.
  • the ⁇ multi-halide liquid flow battery of the invention comprises: a positive and negative electrode end plate, a positive electrode, a porous separator, a negative electrode, a liquid storage tank, a pipeline, and a pump.
  • the positive and negative electrodes are composed of a current collector and a positive and negative electrode catalytic material; during charging and discharging, the electrolyte is transported from the liquid storage tank to the positive and negative electrodes via a pump, and the redox reaction of bromine and bromine is generated in the positive electrode, and the ruthenium and ruthenium are oxidized in the negative electrode. Reduction reaction.
  • the positive and negative electrolytes are all 40 ml; the single cells are sequentially positive electrode plates, positive electrodes 3 ⁇ 3 cm 2 , carbon felt, separator, carbon felt, negative electrode 3 ⁇ 3 cm 2 graphite plates, and negative electrode plates.
  • the electrolyte flow rate in the battery test was 5 ml/min; the charge and discharge current density was 20 mA/cm 2 ; and the battery performance is shown in Tables 1 and 2.
  • the battery performance tends to increase with the increase of the concentration of the positive hydrochloric acid.
  • the positive hydrochloric acid reaches 1.0 mol/L or more, the battery performance is basically unchanged.
  • the concentration of the positive sodium bromide increases, the battery performance gradually increases and tends to be stable.
  • the concentration of the positive hydrochloric acid and sodium bromide was selected to be 2. mol/L.
  • the concentration of the negative electrode hydrochloric acid is kept constant in accordance with the positive electrode, and finally 2 mol/L is selected, and the increase in the concentration of ruthenium is not advantageous for the improvement of the battery performance, and is preferably 0.5 mol/L.
  • the addition of MEP can significantly improve the performance of the battery, and has a better effect than MEM.
  • the excessive addition of the complexing agent causes an increase in cost.
  • it also causes a drop in battery performance.
  • the final preferred concentration is 0.5 mol/L.
  • the final optimized electrolyte conditions are the concentration parameters shown as number 7.

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Abstract

醌多卤化物液流电池，正极电解液为盐酸与溴化钠的混合溶液，负极电解液为盐酸与蒽醌的混合溶液。改善了醌溴液流电池成本偏高，电池电压较低的问题。

Description

一种醌多卤化物液流电池 技术领域
本发明涉及一种液流电池系统。
背景技术
日前随着世界能源供应日趋短缺，人们开始对风能、太阳能等可再生能源的开发和利用广泛关注，但要保证太阳能、风能等可再生能源发电系统的稳定供电，就必须结合高效、廉价、安全可靠的储能技术与其配合，纵观各种储能技术，其中化学储能方式的液流储能电池以其独特的优势而成为目前最适宜大规模储能的蓄电池之一。
目前发展较好的液流电池体系主要有全钒液流电池及锌溴液流电池两种。全钒液流电池通过电解液中不同价态钒离子在惰性电极上的电化学反应来实现电能和化学能的可逆转化。正极为VO2+/VO2 +电对，负极为V2+/V3+电对，硫酸为支持电解质。因为正负极两侧是不同价态的钒离子，避免了离子互串对电解液的污染，影响电池的性能和寿命。另外，钒电解质溶液可以恢复再生，进一步提高了电池系统的寿命，降低运行成本。但是全钒液流电池电解液成本和质子交换膜成本较高、正负极仍存在一定程度的交叉污染问题。
锌溴液流电池正负半电池由隔膜分开，两侧电解液为ZnBr2溶液。在动力泵的作用下，电解液在储液罐和电池构成的闭合回路中进行循环流动。锌溴液流电池存在的主要问题为溴的污染无法解决。
醌溴液流电池在文献中已有报道，但是由于文献中使用质子交换膜，并且采用硫酸作为支持电解质，成本及电池电压均偏低，该发明使用多孔膜并使用盐酸作为支持电解质，成本得到了降低，电压得以提高。
发明内容
一种醌多卤化物液流电池系统，包括：正负极端板、正极、多孔隔膜、负极、储液罐、管路、泵。其中正负极由集流体和正负极催化材料组成；充放电时，电解液经由泵从储液罐输送至正、负极，正极发生溴与溴单质的氧化还原反应，负极发生醌与蒽醌的氧化还原反应。为实现上述目的，本发明的具体技术方案如下：
一种醌多卤化物液流电池，所述电池由电池模块、装有正极电解液的电解液储液罐、装有负极电解液的负极储液罐、循环泵、循环管路组成；电池模块由二节或三节以上单电池串联而成，单电池包括正极、隔膜、负极，正极电解液为盐酸与溴化钠的混合溶液，负极电解液为盐酸与蒽醌的混合溶液。
所述正极电解液为浓度0.5-2M盐酸和浓度0.5-2M溴化钠的混合溶液。所述负极电解液为浓度0.5-2M盐酸和浓度0.5-1M蒽醌的混合溶液。
所述正负极电解液中含有0.1-1M季铵盐类溴单质络合剂，利用溴单质络合剂与溴单质之间的相互作用，产生溴单质络合物，使得溴单质与电解液实现分相，达到降低溴单质渗透的作用。
所述季铵盐类溴单质络合剂为溴化氮甲基乙基吡咯烷(MEP)、溴化氮甲基乙基吗啉(MEM)。
正极和负极材料均为活性炭毡。
所述隔膜为多孔膜或致密膜。
单电池包括正极端板、正极、隔膜、负极、负极端板。
本发明的有益效果：
本专利通过技术改进，提出了醌多卤化物液流电池的概念，改善了醌溴液流电池成本偏高，电池电压较低的问题。
附图说明
图1为实施例1电池循环稳定性图；
图2为对比例1电池循环稳定性图；
图3为实施例1和对比例1电池充放电对比曲线图。
具体实施方式
实施例及对比例中，如无特殊说明，电池均采用多孔膜进行装配。
实施例1
电解液配置及电池组装：
正极电解液：40ml的1MHCl+0.5M溴化氮甲基乙基吡咯烷+1M溴化钠溶液；负极电解液：40ml的1MHCl+0.5M溴化氮甲基乙基吡咯烷+1M蒽醌溶液单电池依次正极端板、正极3x3cm2、碳毡、隔膜、碳毡、负极3x3cm2石墨板、负极端板。
电池测试：
电解液流速：5ml/min；充放电电流密度20mA/cm2；电池循环稳定性见图1。
对比例1
电解液配置及电池组装：
正极电解液：40ml的0.5M硫酸+1M溴化钠溶液；负极电解液：40ml的0.5M硫酸+1M蒽醌溶液单电池依次正极端板、正极3x3cm2、碳毡、隔膜、碳毡、负极3x3cm2石墨板、负极端板。
电池测试：
电解液流速：5ml/min；充放电电流密度20mA/cm2；电池循环稳定性见图2。
实施例1和对比例电池充放电对比曲线见图3。
本发明醌多卤化物液流电池，包括：正负极端板、正极、多孔隔膜、负极、储液罐、管路、泵。其中正负极由集流体和正负极催化材料组成；充放电时，电解液经由泵从储液罐输送至正、负极，正极发生溴与溴单质的氧化还原反应，负极发生醌与蒽醌的氧化还原反应。
由图2和图3可以看出：盐酸作为支持电解质的电池充电电压下降，放电电压升高，电池性能得到提升，且循环性能优于硫酸作为支持电解质。
在条件优选中，如无说明，正负极电解液均为40ml；单电池依次正极端板、正极3x3cm2、碳毡、隔膜、碳毡、负极3x3cm2石墨板、负极端板。电池测试中电解液流速：5ml/min；充放电电流密度20mA/cm2；电池性能见表1和2。
从优选结果中可以看出，随着正极盐酸浓度的升高，电池性能呈上升的趋势，在正极盐酸达到1.0mol/L以上时，电池性能基本不变。随着正极溴化钠浓度的提高，电池性能逐渐上升并趋于稳定。为了提高电池的能量密度，正极盐酸及溴化钠浓度选为2.mol/L。负极盐酸浓度为了保持与正极保持一致，最终选择2mol/L，而醌浓度的上升并不利于电池性能的提高，最终优选为0.5mol/L。通过对比可以看出MEP的加入可以显著提高电池的性能，相比MEM具有更好的效果。但是络合剂的加入过多一方面造成成本的上升。另一方面，也会导致电池性能的下降。最终优选浓度为0.5mol/L。
最终优化的电解液条件为编号为7所显示的各浓度参数。
表1
Figure PCTCN2015092059-appb-000001
表2
编号 库伦效率(100％) 电压效率(100％) 能量效率(100％)
1 96 83 80
2 96 85 82
3 96 84 81
4 96 86 83
5 96 85 82
6 96 85 82
7 97 86 83
8 98 83 81
9 94 85 80
10 96 85 82
11 97 80 78
12 99 81 80
13 99 80 79

Claims (8)

  1. 一种醌多卤化物液流电池，所述电池由电池模块、装有正极电解液的电解液储液罐、装有负极电解液的负极储液罐、循环泵、循环管路组成；电池模块由二节或三节以上单电池串联而成，单电池包括正极、隔膜、负极，其特征在于：正极电解液为盐酸与溴化钠的混合溶液，负极电解液为盐酸与蒽醌的混合溶液。
  2. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：所述正极电解液为浓度0.5-2M盐酸和浓度0.5-2M溴化钠的混合溶液。
  3. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：所述负极电解液为浓度0.5-2M盐酸和浓度0.5-1M蒽醌的混合溶液。
  4. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：所述正负极电解液中含有0.1-1M季铵盐类溴单质络合剂。
  5. 根据权利要求3所述的醌多卤化物液流电池，其特征在于：所述季铵盐类溴单质络合剂为溴化氮甲基乙基吡咯烷(MEP)、溴化氮甲基乙基吗啉(MEM)。
  6. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：正极和负极材料均为活性炭毡。
  7. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：所述隔膜为多孔膜或致密膜。
  8. 根据权利要求1所述的醌多卤化物液流电池，其特征在于：单电池包括正极端板、正极、隔膜、负极、负极端板。
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