CN117976951A - Negative electrode electrolyte of all-iron water-based flow battery - Google Patents
Negative electrode electrolyte of all-iron water-based flow battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims abstract description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 6
- LJDNMOCAQVXVKY-UHFFFAOYSA-N ethyl 2-[(2-ethoxy-2-oxoethyl)amino]acetate Chemical compound CCOC(=O)CNCC(=O)OCC LJDNMOCAQVXVKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 6
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 claims abstract description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 235000002639 sodium chloride Nutrition 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- BKUQKIUBBFUVBN-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;sodium Chemical compound [Na].OC(=O)CNCC(O)=O BKUQKIUBBFUVBN-UHFFFAOYSA-N 0.000 abstract description 2
- CLZHLAZNAFPJGE-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CNCC(O)=O CLZHLAZNAFPJGE-UHFFFAOYSA-N 0.000 abstract description 2
- 230000032895 transmembrane transport Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 7
- 239000011149 active material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- MWCFXRVLEYZWBD-UHFFFAOYSA-N tetralithium;iron(2+);hexacyanide Chemical compound [Li+].[Li+].[Li+].[Li+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] MWCFXRVLEYZWBD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
A negative electrolyte of a full-iron water-based flow battery relates to the technical field of flow battery energy storage. The electrolyte comprises a complex formed by ferric salt chemicals and chelating agents, supporting electrolyte and auxiliary electrolyte; the ferric salt chemical is selected from one or more of ferric sulfate, ferric nitrate, ferric chloride and ferric acetate, the chelating agent is selected from one or more of iminodiacetic acid (IDA) and derivative chemical thereof, the derivative chemical is selected from one or more of iminodiacetonitrile, iminodiacetic acid diethyl ester, iminodiacetic acid sodium and iminodiacetic acid disodium, and the concentration of the ferric salt chemical in the electrolyte is 0-2 mol/L; the chelating agent is 1.5-2.5 times of the mole number of the iron element. By adjusting the coordination environment, a suitable chelating agent is added to coordinate with Fe to form a ligand compound, so that the transmembrane transport of the active substance is reduced.
Description
Technical Field
The invention relates to the technical field of energy storage of flow batteries, in particular to a preparation method of novel water system all-iron flow battery negative electrode electrolyte.
Background
Along with the development of society and the enhancement of environmental awareness of people, reasonable utilization of clean energy has been paid attention to all countries of the world, so that the utilization and development of renewable energy sources such as solar energy, wind energy, tidal energy and the like are rapid. However, the intermittent nature and uncertainty of renewable energy sources limit their development, and there is a need to develop safe and efficient energy storage technologies to enable renewable energy sources to continuously and stably output electricity, thereby maximizing benefits. As the most potential large-scale chemical energy storage technology, the flow battery stores the electric energy generated by renewable energy sources in the form of chemical energy, and converts the chemical energy into electric energy for stable output when needed. In addition, flow batteries also have the characteristics of capacity infinity, design flexibility and high safety, and are considered to be the most promising large-scale energy storage technology.
The basic composition of the flow battery comprises an electrode, a bipolar plate, a diaphragm and an electrolyte storage tank. When the flow battery works, electrolyte is pumped into porous electrodes at two sides of the electric pile, the ion exchange membrane separates the positive and negative electrode cavities to prevent the phenomena of electrolyte mixing, ion mutual strings and the like, and electrochemical oxidation-reduction reaction of the battery occurs on the surfaces of the electrodes. The current commercial flow battery is an all-vanadium flow battery, but the electrolyte cost is high, so that the large-scale application of the flow battery is limited to a certain extent. The iron-chromium flow battery is the first flow battery in the historic sense, has low cost and rich resources, is one of the most cost-effective energy storage systems, but has the characteristics of easy deactivation, weak circularity and the like due to the low redox activity of the cathode Cr 3+/Cr2+. Among iron complexes having redox activity, ferrocyanide is considered to be the most commonly used proton-type redox active material for the positive electrode redox active material because of its low cost, non-toxicity and cyclic stability under neutral or alkaline conditions. On the negative electrode side, a different complex is generally used to adjust the coordination environment of Fe 3+/Fe2+, change the oxidation-reduction potential and improve the stability of the active material. At present, most of developed ligands operate in a strong alkaline environment, the stability of the battery has strong pH dependency, the corrosion protection requirement on equipment is higher under strong alkalinity, and the overall operation cost of the flow battery is improved. Therefore, developing a negative electrode electrolyte that operates stably in a neutral, weakly alkaline environment is also one of the important paths for improving the practicality of all-iron flow batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art of an all-iron flow battery and provides a novel water system all-iron flow battery negative electrode electrolyte in neutral and weak alkaline environments. The method adds proper chelating agent and adjusts coordination environment to coordinate with Fe 3+/Fe2+ to form ligand compound, so as to reduce the trans-membrane transportation of active substances, ensure the stability of electrolyte to be improved with lower cost, and further improve the service life of the battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The novel all-iron water-based flow battery negative electrode electrolyte is characterized in that: the electrolyte comprises a complex formed by ferric salt chemicals and chelating agents, supporting electrolyte and auxiliary electrolyte;
The ferric salt chemical is selected from one or more of ferric sulfate, ferric nitrate, ferric chloride and ferric acetate, the chelating agent is selected from one or more of iminodiacetic acid (IDA) and derivative chemical thereof, the derivative chemical is selected from one or more of iminodiacetonitrile, iminodiacetic acid diethyl ester, iminodiacetic acid sodium and iminodiacetic acid disodium, and the supporting electrolyte in the solution is selected from one or more of potassium carbonate, sodium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide; the auxiliary electrolyte is selected from one or more of potassium chloride, potassium nitrate, sodium chloride, ammonium chloride, potassium sulfate, sodium sulfate and ammonium sulfate;
The concentration of the ferric salt chemical in the electrolyte is 0-2 mol/L and is not 0, and the preferable range is 0.2-1.5 mol/L; the chelating agent is 1.5-2.5 times, preferably 2 times of the mole number of the iron element; the concentration of the supporting electrolyte is 0 to 10mol/L, preferably 0 to 6mol/L, and more preferably 1 to 4mol/L; the concentration of the auxiliary electrolyte is 0-3 mol/L; meanwhile, the pH range of the electrolyte is 7-12.
The preparation method of the negative electrode electrolyte of the all-iron flow battery is characterized by comprising the following process steps of:
step 1), introducing nitrogen into a reactor to exhaust air, adding a proper amount of supported electrolysis into deionized water, and fully stirring until the supported electrolysis is completely dissolved;
And 2) adding proper amount of ferric salt, chelating agent and auxiliary electrolyte into the supporting electrolyte solution obtained in the step 1, fully stirring until the ferric salt, the chelating agent and the auxiliary electrolyte are completely dissolved, fully and uniformly mixing, and standing for 6-48 hours for use.
The water-based all-iron flow battery is characterized by comprising the electrolyte as claimed in any one of the above claims, and the running temperature of the electrolyte is 10-70 ℃.
Compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
1. According to the invention, the iminodiacetic acid ligand is added to be complexed with the ferrous salt, so that the stability of the battery is improved by utilizing the large steric hindrance effect of the complex, and the competitiveness of the all-iron flow battery is enhanced.
2. The invention improves the stability of Fe 3+/Fe2+ under the mild pH condition, ensures that the solution is kept in a uniform state, has no ferric hydroxide precipitation, and effectively improves the running stability and the cycle life of the battery.
3. The invention has the advantages of low cost of raw materials, stable performance, simple and easy operation of the synthesis method, and suitability for large-scale energy storage technology.
In a word, the invention takes ferric salt and iminodiacetic acid ligand with cost advantage as raw materials to prepare the novel negative electrolyte of the all-iron flow battery. By adjusting the coordination environment, a suitable chelating agent is added to coordinate with Fe to form a ligand compound, so that the transmembrane transport of the active substance is reduced. The electrolyte preparation process is simple, and is beneficial to large-scale development and industrial production.
Drawings
FIG. 1 shows the cyclic voltammogram of example 1 in the range of 2 to 50 mV.s -1.
Fig. 2 is a charge-discharge capacity-cycle curve of example 1 over 300 cycles.
Fig. 3 is a charge and discharge efficiency versus cycle curve for 300 cycles of example 1.
Table 1 shows the average test results after 300 cycles of the battery of each example.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and are not intended to limit the actual scope of the present invention in any way.
The preparation method can be as follows:
Step 1), introducing nitrogen into a reactor to exhaust air, weighing a proper amount of supporting electrolyte, adding the supporting electrolyte, and then adding a proper amount of deionized water, and fully stirring for 0-3 h until the supporting electrolyte is completely dissolved; transferring the obtained uniform supporting electrolyte to a volumetric flask, and carrying out constant volume by deionized water at room temperature of 25 ℃;
And 2) adding a proper amount of the supporting electrolyte solution obtained in the step 1 into a reactor with inert gas atmosphere, adding a proper amount of the complex containing ferric salt and iminodiacetic acid or derivative salts thereof, fully stirring for 0-3 h until the complex is completely dissolved, transferring the obtained solution into a volumetric flask, carrying out constant volume by using the supporting electrolyte solution obtained in the step 1 at room temperature of 25 ℃, fully and uniformly mixing, and standing for 6-48 h for use.
Example 1:
In this embodiment, the main composition of the negative electrode electrolyte includes: ferric chloride and iminodiacetic acid are used as a complex, the supporting electrolyte is lithium hydroxide, the auxiliary electrolyte is sodium chloride, and the solvent is oxygen-free deionized water. Wherein the concentration of ferric chloride is 0.5mol/L, and the concentration of iminodiacetic acid is 1mol/L.
The preparation method of the negative electrode electrolyte comprises the following specific steps:
putting 24g of lithium hydroxide weighed in advance into a reactor, adding deionized water for dissolution, and then stirring for 0.5h; transferring the dissolved lithium hydroxide solution into a volumetric flask with the volume of 1L, and performing constant volume at room temperature to obtain a lithium hydroxide supporting electrolyte solution with the volume of 1mol/L, and standing for 24 hours for use.
135G of ferric chloride, 336g of iminodiacetic acid and 58g of sodium chloride are taken and put into a reactor, the supporting electrolyte solution prepared in the steps is poured into the reactor, then the reactor is stirred for 1h, the reactor is moved to a volumetric flask of 1L after being completely dissolved, the electrolyte solution obtained in the steps is used after being subjected to constant volume at room temperature, and the reactor is kept stand for 24 h.
The above negative electrode electrolyte was subjected to electrochemical test (the operating temperature was room temperature), and the results are shown in fig. 1. The cyclic voltammogram is scanned within the scanning speed of 2-50 mV.s -1, the linear relation between the scanning speed and the current density is regular, the oxidation-reduction current intensity is similar, and the reversibility is good.
In the battery test, the electrolyte of the positive electrode adopts 0.5mol/L lithium ferrocyanide and 1mol/L lithium hydroxide electrolyte.
And respectively adding the positive electrode electrolyte and the negative electrode electrolyte into a liquid storage tank corresponding to the flow battery. The flow battery system mainly comprises a battery, an anode liquid storage tank, an anode peristaltic pump, an anti-corrosion circulating pipeline and a battery test system. Wherein the battery assembly includes: aluminum end plates, polytetrafluoroethylene gaskets, collector plates, graphite bipolar plates, fluororubber gaskets, proton exchange membranes and graphite felt electrodes. The graphite felt electrode is 3cm multiplied by 3cm, and the proton exchange membrane is Nafion 117.
After the components are assembled, inert gas is used for circulating in the battery system, so that the deactivation of active substances and the deterioration of alkaline electrolyte are avoided. And then accessing a battery test system to start the test.
The assembled all-iron flow battery is subjected to 300 charge and discharge cycle tests, and the charge and discharge capacity curves of 300 cycles are shown in fig. 2, so that the capacity decay is faster and gradually stabilized.
Fig. 3 shows Coulombic Efficiency (CE), voltage Efficiency (VE), and Energy Efficiency (EE) at 300 cycles, the CE being close to 100% at 300 cycles, and the stability being good. The attenuation of EE and VE also tended to be slower over 300 cycles, showing excellent stability.
Example 2:
In this embodiment, the main composition of the negative electrode electrolyte includes: ferric nitrate, diethyl iminodiacetate as a complex, sodium hydroxide as a supporting electrolyte, sodium nitrate as an auxiliary electrolyte and oxygen-free deionized water as a solvent. Wherein, the concentration of ferric nitrate is 0.4mol/L, and the concentration of iminodiacetic acid diethyl ester is 0.8mol/L.
The preparation method of the negative electrode electrolyte comprises the following specific steps:
putting 8g of sodium hydroxide weighed in advance into a reactor, adding deionized water for dissolution, and then stirring for 0.5h; transferring the dissolved sodium hydroxide solution into a 250mL volumetric flask, and performing constant volume at room temperature to obtain 1mol/L sodium hydroxide supporting electrolyte solution, and standing for 24h for use.
24.1G of ferric nitrate, 336g of diethyl iminodiacetate and 17g of sodium nitrate are taken and put into a reactor, the supporting electrolyte solution prepared in the steps is poured into the reactor, then the reactor is stirred for 1h, the reactor is moved to a 250mL volumetric flask after being completely dissolved, the electrolyte solution obtained in the steps is used after being subjected to constant volume at room temperature, and the reactor is kept stand for 24 h.
The electrolyte of the positive electrode is mainly sodium ferrocyanide of 0.4mol/L and sodium hydroxide of 1 mol/L.
After the battery system was assembled, other reference conditions were the same as in example 1. Preventing the deactivation of active materials and the deterioration of alkaline electrolyte, and after the whole battery system is filled with inert gas. And accessing a battery test system to start the test.
Example 3:
In this embodiment, the main composition of the negative electrode electrolyte includes: ferric sulfate, disodium iminodiacetate as a complex, lithium hydroxide as a supporting electrolyte, sodium sulfate as an auxiliary electrolyte and oxygen-free deionized water as a solvent. Wherein, the concentration of ferric sulfate is 0.8mol/L, and the concentration of ethylenediamine tetraacetic acid is 1.2mol/L.
The preparation method of the negative electrode electrolyte comprises the following specific steps:
Putting 72g of lithium hydroxide weighed in advance into a reactor, adding deionized water for dissolution, and then stirring for 1h; transferring the dissolved lithium hydroxide solution into a volumetric flask with the volume of 1L, and performing constant volume at room temperature to obtain a lithium hydroxide supporting electrolyte solution with the volume of 3mol/L, and standing for 24 hours for use.
160G of ferric sulfate, 350g of disodium iminodiacetate and 58g of sodium chloride are taken and put into a reactor, the supporting electrolyte solution prepared in the steps is poured into the reactor, then the reactor is stirred for 1h, the reactor is moved to a volumetric flask of 1L after being completely dissolved, the electrolyte solution obtained in the steps is used after being subjected to constant volume at room temperature, and the reactor is kept stand for 24 h.
The electrolyte of the positive electrode is mainly lithium ferrocyanide of 0.8mol/L and lithium hydroxide of 3 mol/L.
After the battery system was assembled, other reference conditions were the same as in example 1. Preventing the deactivation of active materials and the deterioration of alkaline electrolyte, and after the whole battery system is filled with inert gas. The battery test system was accessed and the test was started (operating temperature was room temperature).
Table 1 shows the average test results after 300 cycles of the battery of each example.
| Sample of | CE/％ | VE/％ | EE/％ |
| Example 1 | 98.2 | 62.1 | 66.9 |
| Example 2 | 96.6 | 58.7 | 56.7 |
| Example 3 | 94.0 | 60.9 | 57.2 |
。
Claims (9)
1. The negative electrode electrolyte of the all-iron water-based flow battery is characterized in that: the electrolyte comprises a complex formed by ferric salt chemicals and chelating agents, supporting electrolyte and auxiliary electrolyte; the chelating agent is selected from one or more of iminodiacetic acid (IDA) and derivatives thereof; meanwhile, the pH range of the electrolyte is 7-12.
2. The negative electrode electrolyte of the all-iron water-based flow battery according to claim 1, wherein the negative electrode electrolyte comprises the following components: the ferric salt chemical is selected from one or more of ferric sulfate, ferric nitrate, ferric chloride and ferric acetate.
3. The negative electrode electrolyte of the all-iron water-based flow battery according to claim 1, wherein the negative electrode electrolyte comprises the following components: the iminodiacetic acid (IDA) derivative chemical is selected from one or more of iminodiacetonitrile, diethyl iminodiacetate, sodium iminodiacetate and disodium iminodiacetate.
4. The negative electrode electrolyte of the all-iron water-based flow battery according to claim 1, wherein the negative electrode electrolyte comprises the following components: the supporting electrolyte in the solution is selected from one or more of potassium carbonate, sodium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide; the auxiliary electrolyte is selected from one or more of potassium chloride, potassium nitrate, sodium chloride, ammonium chloride, potassium sulfate, sodium sulfate and ammonium sulfate.
5. The negative electrode electrolyte of the all-iron water-based flow battery according to claim 1, wherein the negative electrode electrolyte comprises the following components: the concentration of the ferric salt chemical in the electrolyte is 0-2 mol/L and is not 0, and the preferable range is 0.2-1.5 mol/L; the chelating agent is 1.5-2.5 times, preferably 2 times, the mole number of the iron element.
6. The negative electrode electrolyte of the all-iron water-based flow battery according to claim 1, wherein the negative electrode electrolyte comprises the following components: the concentration of the supporting electrolyte is 0 to 10mol/L, preferably 0 to 6mol/L, and more preferably 1 to 4mol/L; the concentration of the auxiliary electrolyte is 0-3 mol/L.
7. The method for preparing the negative electrode electrolyte of the all-iron water-based flow battery as claimed in any one of claims 1 to 6, which is characterized by comprising the following process steps:
step 1), introducing nitrogen into a reactor to exhaust air, adding a proper amount of supported electrolysis into deionized water, and fully stirring until the supported electrolysis is completely dissolved;
And 2) adding proper amount of ferric salt, chelating agent and auxiliary electrolyte into the supporting electrolyte solution obtained in the step 1, fully stirring until the ferric salt, the chelating agent and the auxiliary electrolyte are completely dissolved, fully and uniformly mixing, and standing for 6-48 hours for use.
8. An aqueous all-iron flow battery comprising the all-iron flow battery negative electrode electrolyte of any one of claims 1-6.
9. The aqueous all-iron flow battery of claim 8, having an operating temperature of 10 to 70 ℃.
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