CN103326055A - Zinc cathode electrolyte applied to redox battery - Google Patents
Zinc cathode electrolyte applied to redox battery Download PDFInfo
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- CN103326055A CN103326055A CN201210429786XA CN201210429786A CN103326055A CN 103326055 A CN103326055 A CN 103326055A CN 201210429786X A CN201210429786X A CN 201210429786XA CN 201210429786 A CN201210429786 A CN 201210429786A CN 103326055 A CN103326055 A CN 103326055A
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Abstract
The invention discloses a zinc cathode electrolyte applied to a redox battery. The electrolyte contains divalent zinc ions as main active component and organic and inorganic additive components. The additive comprises bromine-containing quaternary ammonium salt, boric acid, borax, indium hydroxide and lead oxide. The additive mainly has the functions of adjusting pH, inhibiting hydrogen and improving the appearance of the zinc sediment. The zinc cathode electrolyte can be applied to zinc vanadium batteries, zinc cerium batteries, zinc iron batteries and various redox batteries taking zinc as a cathode active component.
Description
Technical Field
The invention relates to the technical field of electrochemical redox batteries, in particular to a negative electrode electrolyte applied to a redox battery. The acidic electrolyte mainly containing zinc ions contains various additives including bromine-containing quaternary ammonium salts, boric acid, borax, indium hydroxide and lead oxide, and improves the energy efficiency and the cycle performance of the battery by regulating the pH value, inhibiting hydrogen evolution, improving the zinc deposition morphology. The technology can be applied to various redox batteries which take zinc as an active substance, such as zinc-vanadium batteries, zinc-cerium batteries, zinc-iron batteries and the like.
Background
In the current energy field, renewable energy sources such as solar energy and wind energy are more and more concerned by people, and in order to realize the stability of power supply, an efficient large-scale energy storage technology needs to be developed. Secondary batteries are being researched and developed as an important energy storage technology, and are being gradually introduced into the market. Among them, a redox flow battery shows special advantages in large-scale storage of electric energy due to its technical features of large capacity, deep discharge, long cycle life, etc. Among the batteries, the all-vanadium redox flow battery becomes a development hotspot and is entering the market. However, the theoretical voltage of the all-vanadium flow battery is low (1.26V), and high energy density and power density are difficult to obtain.
The zinc has a very negative potential, and the electrode potential of the Zn (II)/Zn electric pair is-0.77V, so that the battery with the zinc as the negative electrode has higher theoretical voltage. Because the zinc raw material has wide sources and is convenient and easy to obtain, the zinc is widely used in primary batteries (such as zinc-manganese batteries, zinc-air batteries and the like) and secondary batteries (such as rechargeable zinc-manganese batteries, zinc-silver oxide batteries and the like). However, the zinc-based negative electrode batteries that have been commercialized are mainly alkaline primary batteries. This is because zinc electrodes have various technical problems such as dendrite growth and electrode deformation during charge and discharge cycles in an alkaline medium, and thus have been an obstacle to the development of secondary batteries. In recent years, secondary batteries using an acidic, neutral electrolyte solution, such as zinc-bromine flow batteries and zinc-vanadium flow batteries, have been developed, in which zinc is used as the negative electrode. Compared with the all-vanadium redox flow battery, the battery taking zinc as the cathode has rich source of source flow, higher battery voltage and low cost, and can be applied to large-scale energy storage batteries.
In acidic media, the dendrite, deformation problems of zinc cathodes are alleviated compared to alkaline electrolytes, but improvements are still needed. In addition, since hydrogen evolution reaction easily occurs in an acidic medium, self-discharge occurs, and current efficiency is lowered. These technical problems have hindered the industrial development of such batteries. Aiming at the problems, the invention combines a plurality of organic and inorganic additives to comprehensively play the roles of adjusting pH, inhibiting hydrogen and improving the appearance of zinc deposition. Thereby improving the electrochemical performance and cycle performance of the battery. The zinc cathode electrolyte can be applied to various redox batteries such as zinc vanadium batteries, zinc cerium batteries, zinc iron batteries and the like.
Disclosure of Invention
The invention aims to develop the zinc cathode electrolyte applied to the redox battery according to the defects. In the redox battery using zinc as the cathode, the zinc ion concentration of the electrolyte of the cathode and the acidity of the electrolyte directly influence the performance of the battery. The higher the zinc ion concentration, the higher the energy density of the battery; higher acidity is beneficial for increasing the electrode reaction rate and conductivity of the electrolyte, but may exacerbate hydrogen evolution. The main factors that degrade the battery performance are from the zinc negative electrode: the hydrogen evolution reaction leads to a reduction in current efficiency; the uneven electric field on the surface of the electrode causes dendrite to generate and develop; the product of the discharge process, zinc oxide, dissolves in the electrolyte and precipitates out of place during charging resulting in electrode deformation. Aiming at the problems, the technology of the invention obtains the stable electrolyte with high zinc ion concentration through higher sulfamic acid concentration, and simultaneously, organic and inorganic additives are added into the electrolyte to organically combine different components to play a synergistic effect, thereby obtaining the comprehensive effects of regulating pH, inhibiting hydrogen and improving the appearance of zinc deposition, and realizing excellent battery performance.
The main active component of the zinc cathode electrolyte applied to the redox battery is divalent (Zn (II)) zinc ions, the zinc cathode electrolyte contains organic and inorganic additives, and the additives comprise bromine-containing quaternary ammonium salts, boric acid, borax, indium hydroxide and lead oxide, and have the effects of regulating pH value, inhibiting hydrogen evolution, improving zinc deposition morphology and the like. According to the acid negative electrode electrolyte of the technology, the acid component is methanesulfonic acid, the acid concentration is 0.5-2.0mol/L, and the zinc ion concentration is 1.0-2.0mol/L.
Indium and lead are effective elements for increasing the overpotential for hydrogen evolution of the electrode. However, lead has a very low solubility in inorganic acids such as sulfuric acid and hydrochloric acid, and has a high solubility in methanesulfonic acid used in the present technique. The technology adds lead oxide into electrolyte, and combines the lead oxide with indium element. The total amount of indium hydroxide and lead oxide in the electrolyte is 0.1-5.0g/L, and excellent hydrogen inhibiting effect is obtained. During the charging process, indium and lead in the electrolyte are reduced, and the alloy is possibly formed with zinc of dendrites, so that the morphology is improved, and the formation and development of the dendrites are reduced.
In the technology, boric acid and borax are used as buffers and added into electrolyte to play a role in regulating the acidity of the electrolyte, and the total amount of the boric acid and the borax is 10-80/L. Good effect is obtained, which not only maintains the high conductivity of electrolysis under high acidity, but also is beneficial to reducing hydrogen evolution.
Bromine quaternary ammonium salt is added in the electrolysis, and the addition amount of the bromine quaternary ammonium salt in the electrolyte is 0.1-5.0g/L, which is beneficial to improving the appearance of the deposited zinc and improving the smoothness. Under the comprehensive action of all components of the electrolyte, the growth of dendritic crystals is inhibited, the deformation of the electrode is reduced, and the cycle performance of the electrode is improved.
The acidic zinc cathode electrolyte of the technology can be applied to various redox batteries which take zinc as an active substance, such as zinc-vanadium batteries, zinc-cerium batteries, zinc-iron batteries and the like.
Drawings
FIG. 1: the invention relates to a charge-discharge curve of a zinc-cerium battery without an additive in a zinc cathode electrolyte.
FIG. 2: the invention relates to a charge-discharge curve of a zinc-cerium battery with an additive added into a zinc cathode electrolyte.
FIG. 3: the invention relates to a charge-discharge curve of a zinc-cerium battery with an additive added into a zinc cathode electrolyte.
FIG. 4: the invention relates to a charge-discharge curve of a zinc-vanadium battery with an additive added into a zinc cathode electrolyte.
Detailed Description
The embodiment of the invention mainly comprises the steps of assembling the zinc-cerium battery and the zinc-vanadium battery by using the zinc cathode electrolyte, and carrying out charge and discharge tests. The present invention will be described in detail with reference to specific examples.
Examples
Description of the drawings: in the examples described below, SA represents methanesulfonic acid.
Example 1, a zinc-cerium battery with negative electrode solution without additives.
(1) 100ml0.8mol/L Ce 2 (CO 3 ) 3 And 100ml1.0mol/L of Zn (SA) 2 。
Weighing 61.5g of methanesulfonic acid and Ce 2 (CO 3 ) 3 Prepared into 0.8mol/L Ce (SA) 3 +4.0mol/L of SA.
8.14g of ZnO and 38.40g of methylsulfonic acid were weighed outAcid, formulation 1.0mol/L Zn (SA) 2 . The positive and negative electrode cavities of the battery are separated by a cation exchange membrane. The positive and negative electrode materials are graphite felt and carbon-plastic composite material electrodes respectively, and the reaction area of the graphite felt and the electrodes is 4cm 2 . The anode solution is 0.8mol/LCe (SA) prepared in the step (1) 3 +4.0mol/LSA, and the anolyte is 1.0mol/LZn (SA) prepared in (2) 2 . The charging and discharging current is 120mA, and the charging time is 30min. The highest charging voltage of the battery is 3.18V, the highest discharging voltage is 1.92V, the discharging time of more than 1V in 1 cycle can reach 20min, the discharging time of more than 0.2V can reach 22.3min, and the coulombic efficiency is 74.2%. The charge and discharge performance is shown in fig. 1.
Example 2, a zinc-cerium battery with an additive in the negative electrode solution.
(1) The positive electrode electrolyte and the negative electrode electrolyte were the same as in example 1.
(2) The following additives were added to 100ml of the negative electrode solution:
weighing 2.0g of boric acid and 1.5g of borax;
-weighing 0.02g of indium hydroxide;
-weighing 0.02g of lead oxide;
0.5g of cetyltrimethylammonium bromide was taken.
Heating the mixture to dissolve the additive, and cooling the mixture to room temperature.
(3) Battery assembly and experimental parameter settings charge and discharge tests were performed as described in example 1. The highest charging voltage of the battery is 2.96V, the highest discharging voltage is 2.22V, more than 1V discharging time in 1 cycle can reach 27min, more than 0.2V discharging time can reach 27.5min, and the coulomb efficiency is 91.7%. The results show a significant improvement in battery performance after addition of the additive (compare with example 1). The charge and discharge performance is shown in fig. 2.
Example 3, a zinc-cerium battery with an additive in the negative electrode solution.
(1) The positive electrode electrolyte and the negative electrode electrolyte were the same as in example 1.
(2) To 100ml of the anolyte solution, additives were added as described in example 2. The amount of the additive is: 3.0g of boric acid, 2.5g of borax, 0.1g of indium hydroxide, 0.1g of lead oxide and 0.2g of tetrabutylammonium bromide.
(3) Battery assembly and experimental parameter settings charge and discharge tests were performed as described in example 1. The maximum charging voltage of the battery is 2.90V, the maximum discharging voltage is 2.17V, the discharging time of more than 1V in 1 cycle can reach 27.5min, the discharging time of more than 0.2V can reach 28min, and the coulombic efficiency is 93.8%. The charge and discharge performance is shown in fig. 3.
Example 4, zinc vanadium cell with negative electrode electrolyte containing additives.
(1) 100 mll 3.0mol/LVO (SA) 2 +3.0mol/LSA electrolyte
Weighing 27.3gV 2 O 5 And 86.5g of methanesulfonic acid in a 250ml beaker, adding a suitable amount of distilled water;
-introducing V 2 O 5 Mixing with methanesulfonic acid and adding a small amount of distilled water;
heating to maintain the temperature at 80-100 ℃, gradually adding oxalic acid until V 2 O 5 And after complete dissolution, adding distilled water to dissolve to 100ml to obtain the product.
(2) The same negative electrode solution was prepared as in example 2.
(3) Battery assembly and experimental parameter settings charge and discharge tests were performed as described in example 1. The highest charging voltage is 2.38V, the highest discharging voltage is 1.64V, the discharging time of more than 1V in 1 cycle can reach 27min, the discharging time of more than 0.2V can reach 29min, and the coulombic efficiency is 97.2%. The charge and discharge performance is shown in fig. 4.
Claims (6)
1. A zinc negative electrode electrolyte applied to a redox battery is characterized in that the main active component of the electrolyte is divalent (Zn (II)) zinc ions, and the electrolyte contains organic and inorganic additives. The additive comprises bromine-containing quaternary ammonium salt, boric acid, borax, indium hydroxide and lead oxide, and has the effects of regulating pH value, inhibiting hydrogen evolution, improving zinc deposition morphology and the like.
2. The zinc negative electrode electrolyte for a redox battery according to claim 1, wherein the acidic component is methanesulfonic acid, the acid concentration is 0.5 to 2.0mol/L, and the zinc ion concentration is 1.0 to 2.0mol/L.
3. The zinc negative electrode electrolyte bromine quaternary ammonium salt applied to the redox battery as claimed in claim 1, wherein the addition amount of the bromine quaternary ammonium salt in the electrolyte is 0.1-5.0g/L.
4. The zinc negative electrode electrolyte for a redox cell according to claim L wherein boric acid and borax are present as buffering agents, the total amount of boric acid and borax being 10-80/L.
5. The zinc negative electrolyte for a redox cell according to claim 1 wherein the additives indium hydroxide and lead oxide are primarily hydrogen inhibiting. The total amount of the indium hydroxide and the lead oxide is 0.1-5.0g/L.
6. The zinc negative electrode electrolyte applied to a redox battery according to claim 1, which can be applied to zinc vanadium batteries, zinc cerium batteries, zinc iron batteries and various redox batteries using zinc as an active material.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN104733785B (en) * | 2013-12-20 | 2017-11-07 | 苏州宝时得电动工具有限公司 | Battery |
| CN108199068A (en) * | 2018-01-09 | 2018-06-22 | 中国工程物理研究院电子工程研究所 | A kind of low temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
| CN109148952A (en) * | 2018-07-26 | 2019-01-04 | 华中科技大学 | A kind of electrolyte and its application and product |
| CN110391469A (en) * | 2018-04-19 | 2019-10-29 | 北京金羽新能科技有限公司 | A kind of water system ion battery electrolyte |
| WO2019208809A1 (en) * | 2018-04-27 | 2019-10-31 | 京セラ株式会社 | Flow cell, flow cell system, and control method |
| TWI678830B (en) * | 2017-05-24 | 2019-12-01 | 徐鎮 | The structure of oxalic acid battery |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN115838557A (en) * | 2022-09-23 | 2023-03-24 | 上海交通大学 | Preparation method of high-molecular functional coating for metal negative electrode |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104733785B (en) * | 2013-12-20 | 2017-11-07 | 苏州宝时得电动工具有限公司 | Battery |
| CN104752681A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Battery |
| CN104752754A (en) * | 2013-12-26 | 2015-07-01 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
| TWI678830B (en) * | 2017-05-24 | 2019-12-01 | 徐鎮 | The structure of oxalic acid battery |
| CN108199068A (en) * | 2018-01-09 | 2018-06-22 | 中国工程物理研究院电子工程研究所 | A kind of low temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
| CN108199068B (en) * | 2018-01-09 | 2020-05-05 | 中国工程物理研究院电子工程研究所 | Low-temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
| CN110391469A (en) * | 2018-04-19 | 2019-10-29 | 北京金羽新能科技有限公司 | A kind of water system ion battery electrolyte |
| WO2019208809A1 (en) * | 2018-04-27 | 2019-10-31 | 京セラ株式会社 | Flow cell, flow cell system, and control method |
| CN109148952A (en) * | 2018-07-26 | 2019-01-04 | 华中科技大学 | A kind of electrolyte and its application and product |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN115838557A (en) * | 2022-09-23 | 2023-03-24 | 上海交通大学 | Preparation method of high-molecular functional coating for metal negative electrode |
| CN115838557B (en) * | 2022-09-23 | 2023-12-08 | 上海交通大学 | Preparation method of high-molecular functional coating for metal negative electrode |
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