CN110534784B - Preparation method of high-energy-density low-cost alkaline flow battery system - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 239000011701 zinc Substances 0.000 claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 38
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- 239000012528 membrane Substances 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
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- 239000007788 liquid Substances 0.000 claims description 5
- 230000005588 protonation Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
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- 239000000463 material Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to the field of energy storage of alkaline redox flow batteries, in particular to a preparation method of an alkaline flow battery system with high energy density and low cost, which aims to solve the problems of low energy density, high cost and the like of the existing all-vanadium redox flow battery. The carbon felt is used as a positive electrode material of the flow battery, and the zinc sheet or the zinc plate is used as a negative electrode material of the flow battery. With permanganate (e.g., KMnO)4、NaMnO4Etc.) as a positive electrode electrolyte, with a strong base (such as: KOH, NaOH, etc.) as the negative electrolyte, and a perfluorinated sulfonic acid proton exchange membrane (such as: nafion117, Nafion212, etc.) as ion exchange membranes for flow batteries. Thus, an alkaline redox flow battery system having low cost and high energy density is obtained. The redox flow battery system developed by the invention has the advantages of high energy density, low cost, long cycle life and the like, and can be widely applied to the field of redox flow battery energy storage.
Description
The technical field is as follows:
the invention relates to the field of energy storage of alkaline redox flow batteries, in particular to a preparation method of an alkaline flow battery system with high energy density and low cost.
Background art:
the non-regenerability of fossil energy and the increasing demand for energy have led to a great need for new energy storage technologies to stably reserve new energy sources, such as: wind energy, solar energy, etc. Due to the advantages of flexible structure, long cycle life, safety, reliability and the like, the flow battery is one of the most promising energy storage candidates. Among the various conventional flow battery systems, all-vanadium flow batteries are effective in avoiding the problem of ion cross-contamination, but their relatively low energy density (25Wh/L) and prohibitive cost have presented significant obstacles to their commercialization. Although nonaqueous systems have a high open circuit voltage and a wide variety of active materials available, the low solubility and solution conductivity places significant limitations on the energy and power densities of such systems. In an aqueous system, the solubility of the active material is high, and the ion diffusion rate is high. Therefore, there is a great need to develop a new type of high energy density, low cost aqueous flow battery.
The invention content is as follows:
in order to overcome the defects of the prior art and break through the constraint of the traditional flow battery system, the invention aims to provide a preparation method of an alkaline flow battery system with high energy density and low cost, and solve the problems of low energy density, high cost and the like of the traditional flow battery. The energy storage battery with the cost far lower than that of the all-vanadium redox flow battery can be obtained by adopting the method, and has the advantages of high open-circuit voltage, high energy density, low cost, good stability and the like.
The technical scheme of the invention is as follows:
a preparation method of a high-energy-density low-cost alkaline flow battery system comprises the following steps and process conditions:
(1) preparing aqueous solutions of strong acid, strong base and oxidant in a beaker by using deionized water respectively;
(2) soaking a Nafion membrane in the oxidant aqueous solution obtained in the step (1) and cleaning at constant temperature;
(3) soaking the Nafion membrane obtained in the step (2) in deionized water, and carrying out constant-temperature water bath;
(4) soaking the Nafion membrane obtained in the step (3) in the strong acid aqueous solution obtained in the step (1) for constant-temperature protonation;
(5) soaking the Nafion membrane obtained in the step (4) in deionized water, and carrying out constant-temperature water bath;
(6) soaking the Nafion membrane obtained in the step (5) in the strong alkali aqueous solution obtained in the step (1) for constant-temperature ionization;
(7) washing the Nafion membrane obtained in the step (6) with deionized water until the pH value is 6-7, and then soaking the Nafion membrane into the deionized water to serve as an ion exchange membrane for later use;
(8) polishing a zinc plate with the thickness of 3-6 mm on abrasive paper, cleaning the zinc plate with absolute ethyl alcohol, and drying the zinc plate serving as a negative electrode material of the battery by using a blower;
(9) using a carbon felt with the thickness of 3-8 mm as a positive electrode material of the battery;
(10) taking the strong alkaline aqueous solution prepared in the step (1) as a negative electrode electrolyte of a battery;
(11) dissolving permanganate in the strong base aqueous solution prepared in the step (1) to prepare an alkaline aqueous solution of the permanganate, wherein the alkaline aqueous solution is used as a positive electrode electrolyte of the battery;
(12) and (4) assembling the key materials obtained in the steps (7), (8), (9), (10) and (11) into an alkaline redox flow battery system, and testing by using a battery testing system.
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the following steps of (1), preparing a strong acid aqueous solution with the molar concentration of 0.5-2M, a strong alkali aqueous solution with the molar concentration of 0.5-2M, and an oxidant aqueous solution with the molar concentration of 0.5-2M; the strong acid is HCl or HNO3、H2SO4The adopted strong base is one of KOH and NaOH, and the adopted oxidant is H2SO4/HNO3(V/V＝3:1)、H2O2、HNO3One kind of (1).
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the step (2), wherein the cleaning temperature is 50-120 ℃, and the cleaning time is 30-80 min.
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the step (3), wherein the water bath temperature is 60-100 ℃, and the water bath time is 40-80 min.
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the step (4), wherein the protonation temperature is 50-120 ℃, and the time is 30-80 min.
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the step (5), wherein the water bath temperature is 60-100 ℃, and the water bath time is 40-80 min.
The preparation method of the high-energy-density low-cost alkaline flow battery system comprises the step (6), wherein the ionization temperature is 50-120 ℃, and the time is 30-80 min.
In the preparation method of the high-energy-density low-cost alkaline flow battery system, in the step (8), the thickness of the zinc plate is 4-5 mm, and the mass fraction of absolute ethyl alcohol is 65-98% in 120-mesh sand paper.
According to the preparation method of the high-energy-density low-cost alkaline flow battery system, in the step (10), the molar concentration of a negative electrode electrolyte is 2-6M.
In the preparation method of the high-energy-density low-cost alkaline flow battery system, in the step (11), the active substance of the positive electrolyte is variable-valence permanganate ions, the molar concentration of the prepared alkaline aqueous solution of permanganate is 0.1-5M, and the permanganate is KMnO4Or NaMnO4。
The design idea of the invention is as follows:
compared with vanadium battery electrolyte, the permanganate active substance has the advantages of extremely high solubility, proper potential, lower cost, excellent reversibility, electrochemical performance and the like under an alkaline condition. With monomers, there is no such synergistic mechanism. According to the invention, the permanganate anode electrolyte with good stability and low cost is prepared by adding a large amount of strong base. Compared with the expensive vanadium battery electrolyte, the preparation method of the low-cost alkaline flow battery system can be obtained by applying the vanadium battery electrolyte to the flow battery of the alkaline permanganate-zinc plate system. After the Nafion membrane (perfluorinated sulfonic acid proton exchange membrane) is subjected to water bath ionization treatment, Nafion-H+Conversion of the membrane to Nafion-Na+The membrane can ensure that the normal transmission of specific ions forms a closed loop in the battery. Meanwhile, the good chemical stability of the Nafion membrane can ensure stable cycle performance and prolong the service life of the battery. Under alkaline conditions, the zinc with higher negative electrode potential enables the battery to have extremely high open-circuit voltage, and further, an ultra-high energy density can be obtained. Therefore, the alkaline system electrolyte has economic advantages and excellent electrochemical performance, is beneficial to guiding the research and development of low-cost flow batteries, and further promotes the industrial process of energy storage in the field of flow batteries.
Compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
1. the invention selects the carbon felt as the anode material, the zinc plate as the cathode material, and the aqueous solution of permanganate and strong base as the anode and cathode electrolyte, successfully assembles the alkaline flow battery system with high energy density and low cost, and the battery system has the advantages of good cycle performance, high energy density, low cost and the like.
2. The method has the advantages of easily available raw materials, low cost, simple and easy operation and suitability for large-scale development.
3. The whole preparation process has the characteristics of low equipment price, easily available raw materials, simple flow, convenient operation and other industrial practicability, and is beneficial to the commercial development of the propulsion flow battery.
In a word, the invention adopts the carbon felt as the battery anode material, the zinc plate as the battery cathode material and the permanganate and strong base solution as the anode and cathode electrolyte of the battery, and provides the alkaline flow battery system with high energy density and low cost. The battery has the advantages of high open-circuit voltage, high efficiency, long cycle life, low cost and the like. The alkaline flow battery has the advantages of easily available raw materials, low cost, suitability for large-scale industrial development and low cost and high energy density.
Description of the drawings:
fig. 1 is a cyclic voltammogram of a permanganate-zinc plate flow battery.
Fig. 2 is a graph of the performance of a flow battery with 0.5M permanganate-zinc plates.
Fig. 3 is a graph of charge and discharge curves for a flow battery with 0.5M permanganate-zinc plates.
Fig. 4 is a graph of the performance of a flow battery with a 1M permanganate-zinc plate molar concentration.
The specific implementation mode is as follows:
in the specific implementation process, the carbon felt is used as the positive electrode material of the flow battery, and the zinc sheet or the zinc plate is used as the negative electrode material of the flow battery. With permanganate (e.g., KMnO)4、NaMnO4Etc.) as a positive electrode electrolyte, with a strong base (such as: KOH, NaOH, etc.) as the negative electrolyte, and a perfluorinated sulfonic acid proton exchange membrane (such as: nafion117, Nafion212, etc.) as ions for flow batteriesAnd (3) an exchange membrane. Thus, an alkaline redox flow battery system having low cost and high energy density is obtained.
The present invention will be further described with reference to examples.
Example 1:
in this example, the preparation method of the alkaline flow battery system was as follows:
an ionization process of a Nafion membrane (Nafion 212 is used in this embodiment), comprising the steps of:
(1) a Nafion membrane 7.5cm long and 5.5cm wide was placed in a molar concentration of 1M H2O2Washing in water solution at constant temperature of 80 deg.C for 1 h;
(2) placing the treated Nafion membrane in deionized water, and carrying out constant temperature treatment at 60 ℃ for 40min to obtain a clean Nafion membrane;
(3) protonating the clean Nafion membrane in hydrochloric acid water solution with the molar concentration of 1M at the constant temperature of 80 ℃ for 1 hour;
(4) placing the protonated Nafion membrane in deionized water, and carrying out constant temperature treatment at 60 ℃ for 40min to obtain a clean Nafion membrane;
(5) putting the cleaned Nafion membrane into a sodium hydroxide aqueous solution with the molar concentration of 1M, and ionizing for 1h at the constant temperature of 80 ℃;
(6) cooling the ionized Nafion membrane to room temperature, washing the Nafion membrane to be neutral by deionized water, and soaking the Nafion membrane in the deionized water to be used as an ion exchange membrane of the battery for later use;
2. preparing an electrode material:
(1) and (3) polishing a zinc plate with the thickness of 5mm on 120-mesh abrasive paper, cleaning the zinc plate with 75% of absolute ethyl alcohol by mass, and drying the zinc plate by using a blower to obtain the negative electrode material of the battery.
(2) A carbon felt 5mm thick was used as a negative electrode material of the battery.
3. Preparing an electrolyte:
(1) potassium permanganate is dissolved in sodium hydroxide aqueous solution with the molar concentration of 1M, after the potassium permanganate aqueous solution is completely dissolved, alkaline aqueous solution of potassium permanganate with the molar concentration of 0.5M is obtained, and the alkaline aqueous solution is sealed in an anode liquid storage tank and is used as anode electrolyte of a battery.
(2) And dissolving sodium hydroxide in deionized water to obtain sodium hydroxide solution with the molar concentration of 1M after the sodium hydroxide is completely dissolved, and sealing the sodium hydroxide solution in a negative electrode liquid storage tank to be used as a negative electrode electrolyte of the battery.
In this embodiment, a carbon felt is used as a positive electrode material of a flow battery, a zinc sheet is used as a negative electrode material of the flow battery, and an ionized Nafion membrane is adopted to assemble a flow battery of a potassium permanganate-zinc plate system. The flow battery of the potassium permanganate-zinc plate system assembled by adopting the alkaline aqueous solution of potassium permanganate as the anode electrolyte has high battery efficiency and excellent cycling stability.
The performance index of this example is as follows: the discharge capacity of the flow battery of a potassium permanganate-zinc plate system assembled by taking an alkaline aqueous solution of potassium permanganate as a positive electrolyte is basically not attenuated after 100 cycles, the coulombic efficiency is up to 100 percent, and the energy efficiency is up to about 80.60 percent.
Example 2:
the difference from example 1 is that the electrolyte preparation:
(1) dissolving sodium permanganate in sodium hydroxide water solution with the molar concentration of 1.5M, obtaining alkaline water solution of the sodium permanganate with the molar concentration of 1M after the sodium permanganate is completely dissolved, sealing the alkaline water solution in an anode liquid storage tank, and using the alkaline water solution as anode electrolyte of the battery.
(2) And dissolving sodium hydroxide in deionized water to obtain a sodium hydroxide aqueous solution with the molar concentration of 1.5M after the sodium hydroxide is completely dissolved, and sealing the sodium hydroxide aqueous solution in a negative electrode liquid storage tank to be used as a negative electrode electrolyte of the battery after the sodium hydroxide is completely dissolved.
In the embodiment, a carbon felt is used as a positive electrode material of the flow battery, a zinc sheet is used as a negative electrode material of the flow battery, and the ionized Nafion membrane is adopted to assemble the flow battery with the sodium permanganate-zinc plate system. The flow battery of the sodium permanganate-zinc plate system assembled by adopting the alkaline aqueous solution of sodium permanganate as the anode electrolyte has high battery efficiency and excellent cycling stability.
The performance index of this example is as follows: the discharge capacity of the flow battery of the sodium permanganate-zinc plate system assembled by taking the alkaline aqueous solution of sodium permanganate as the positive electrolyte is basically not attenuated after 115 cycles, the coulombic efficiency is up to 100 percent, and the energy efficiency is up to about 86.43 percent.
As shown in fig. 1, it can be seen from the cycle method voltammogram of the potassium permanganate-zinc plate flow battery that the flow battery of the potassium permanganate-zinc plate system assembled by using the alkaline aqueous solution of potassium permanganate as the positive electrolyte has a voltage of 1.94V, and a high voltage is favorable for obtaining a flow battery with high energy density.
As shown in fig. 2, it can be seen from the performance diagram of the flow battery with 0.5M molar concentration of potassium permanganate-zinc plate that the flow battery with potassium permanganate-zinc plate system assembled by using the alkaline aqueous solution of potassium permanganate as the positive electrolyte has no attenuation of discharge capacity after 100 cycles, coulombic efficiency is as high as 100%, and energy efficiency is as high as about 80.60%.
As shown in fig. 3, it can be seen from the charge-discharge curve diagram of the flow battery with a molar concentration of 0.5M potassium permanganate-zinc plate that the flow battery with a potassium permanganate-zinc plate system assembled by using an alkaline aqueous solution of potassium permanganate as a positive electrolyte has a capacity retention rate of up to 94%, and the battery discharge capacity of the flow battery only declines by 15mAh after 100 cycles.
As shown in fig. 4, it can be seen from the performance diagram of the flow battery with 1M molar sodium permanganate-zinc plate that the flow battery with sodium permanganate-zinc plate system assembled by using alkaline aqueous solution of sodium permanganate as the positive electrolyte has almost no discharge capacity attenuation after 115 cycles, the coulombic efficiency is as high as 100%, and the energy efficiency is as high as about 86.43%.
From the above examples, it can be seen that the flow battery of the permanganate-zinc plate system assembled by using the alkaline aqueous solution of permanganate as the positive electrolyte has good cycle stability and high efficiency. The redox flow battery system developed by the invention has the advantages of high energy density, low cost, long cycle life and the like, and can be widely applied to the field of redox flow battery energy storage. Therefore, low cost and superior performance are advantageous for the commercial development of alkaline flow batteries.
Claims (7)
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