CN114497665A - Method for reducing capacity attenuation of vanadium battery - Google Patents
Method for reducing capacity attenuation of vanadium battery Download PDFInfo
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- CN114497665A CN114497665A CN202210049238.8A CN202210049238A CN114497665A CN 114497665 A CN114497665 A CN 114497665A CN 202210049238 A CN202210049238 A CN 202210049238A CN 114497665 A CN114497665 A CN 114497665A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 84
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 179
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 230000002708 enhancing effect Effects 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229940041260 vanadyl sulfate Drugs 0.000 claims abstract description 25
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims abstract description 25
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001720 carbohydrates Chemical class 0.000 claims description 22
- 239000008139 complexing agent Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- LHAOFBCHXGZGOR-NAVBLJQLSA-N alpha-D-Manp-(1->3)-alpha-D-Manp-(1->2)-alpha-D-Manp Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@H](O)[C@H]1O[C@@H]1[C@@H](O)[C@@H](O[C@@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@@H](CO)O1 LHAOFBCHXGZGOR-NAVBLJQLSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 3
- FBJQEBRMDXPWNX-CFCQXFMMSA-N beta-D-Glcp-(1->6)-beta-D-Glcp-(1->6)-beta-D-Glcp Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC[C@@H]2[C@H]([C@H](O)[C@@H](O)[C@H](O)O2)O)O1 FBJQEBRMDXPWNX-CFCQXFMMSA-N 0.000 claims description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000008101 lactose Substances 0.000 claims description 3
- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- 238000005562 fading Methods 0.000 claims 3
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
Abstract
The invention relates to a method for reducing capacity attenuation of a vanadium battery. The technical scheme is as follows: mixing sulfuric acid, vanadyl sulfate and deionized water to obtain electrolyte I; respectively placing two parts of electrolyte I with the same volume in an anode chamber and a cathode chamber of an electrolytic cell; electrolyzing the electrolyte to reach the vanadium valence state of 3.5 in a constant current manner in the condition that the current is 1-3A until the vanadium valence state of the electrolyte in the positive electrode chamber and the vanadium valence state of the electrolyte in the negative electrode chamber are both obtained, and obtaining electrolyte II and electrolyte III; adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of vanadium ions to the composite permeation enhancing solute in the electrolyte II of (10-30) to 1, and stirring to obtain an electrolyte IV; putting the electrolyte III and the electrolyte IV into corresponding positive electrolyte storage tanks and negative electrolyte storage tanks, and respectively connecting the positive ends and the negative ends of the vanadium cell stacks correspondingly, wherein the voltage of the vanadium cell is 0.65-1.65V, and the current density of the vanadium cell is 40-120 mA/cm2The operation is carried out. The method has low cost and simple process, and can obviously reduce the capacity attenuation of the vanadium battery and improve the battery efficiency of the vanadium battery.
Description
Technical Field
The invention belongs to the technical field of all-vanadium redox flow batteries. In particular to a method for reducing the capacity attenuation of a vanadium battery.
Background
The core materials of the all-vanadium redox flow battery mainly comprise electrolyte, an ion exchange membrane and an electrode. The electrolyte solutions are classified into a positive electrode electrolyte solution containing v (v) and v (iv) as active materials and a negative electrode electrolyte solution containing v (iii) and v (ii) as active materials. The ion exchange membrane is responsible for isolating electrolytes on two sides to prevent the cross contamination of the electrolytes and simultaneously ensure H+By maintaining the electrolyte electrically neutral. The electrodes being subjected to an electrochemical reactionThe electrons are transferred to form current, so that the conversion between electric energy and chemical energy is realized. The low utilization rate of active substances caused by transmembrane permeation of vanadium ions and poor interfacial reaction activity of electrolyte and electrodes can unbalance the valence state and concentration of the electrolyte on two sides, so that the capacity of the vanadium battery is reduced, and the cycle life is shortened.
When the capacity of the vanadium redox battery is lost to a certain degree, the capacity is recovered by remixing unbalanced positive and negative electrolytes mostly, but the maintenance cost is high. The patent technology of 'an all vanadium redox flow battery capacity recovery method' (CN106876814A) is characterized in that ammonium ferrous sulfate is added into a positive electrolyte in any charge and discharge process, and accumulated pentavalent vanadium is reduced into tetravalent vanadium to recover the capacity; the patent technology of 'a method for recovering the capacity of an all-vanadium redox flow battery' (CN105702995A) is to introduce oxidizing gas into a negative electrode electrolyte after long-term operation and oxidize excessive divalent vanadium of a negative electrode into trivalent vanadium so as to recover the capacity of the battery. In the two patent technologies, partial capacity can be recovered by balancing the vanadium valence state of the electrolyte, but the process is complex, and the capacity attenuation in the circulating process is not improved.
The patent technology of 'an all-vanadium redox flow battery cathode electrolyte and a method for reducing cathode vanadium ion migration' (CN11313071A) is characterized in that complexing agents such as oxalic acid are added into the cathode electrolyte, the complexing agents are combined with vanadium ions to increase the ionic radius of the vanadium ions, transmembrane permeation of the vanadium ions in the cathode electrolyte is reduced, and the battery performance is improved; the patent of' a method for reducing capacity attenuation of a vanadium battery (CN104900898A) is a technology that a positive osmosis driving liquid additive is added into a negative electrode electrolyte at a low side of electrolyte osmotic pressure drop, so that transmembrane crossing of vanadium ions from a negative electrode to a positive electrode is inhibited. In the two patent technologies, the capacity attenuation is slowed down by reducing the transmembrane permeation of vanadium ions in the negative electrolyte, but the electrochemical performance of the negative electrolyte is not improved, and the battery efficiency is poor.
The patent of 'a preparation method of all vanadium redox flow battery electrolyte' (CN102637892A) is a technology, carbohydrate organic matters are added in positive and negative electrode electrolytes to improve the capacity and efficiency of the battery, but excessive carbohydrate organic matters can increase the viscosity of the electrolytes to cause the electrochemical performance of the electrolytes to be poor, and have adverse effect on the efficiency of the vanadium battery.
The patent technology of the vanadium battery, the negative electrolyte thereof and the method for improving the electrochemical activity thereof (CN106299437A) improves the electrochemical activity of the negative electrolyte by adding Sn phosphate into the negative electrolyte of the vanadium battery so as to improve the battery capacity. The interfacial activity between the electrolyte and the electrode is improved, but the required additives are expensive and the capacity fade due to transmembrane permeation of vanadium ions is not improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a method for reducing the capacity attenuation of a vanadium battery, which has low cost and simple process. The method can reduce the capacity attenuation of the vanadium battery and improve the battery efficiency of the vanadium battery.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of sulfuric acid to vanadyl sulfate of (2-5) to 1 to obtain a mixture.
The purity of the vanadyl sulfate is more than or equal to 98 percent.
And step two, adding deionized water into the mixture according to the solid-liquid ratio of vanadyl sulfate to deionized water of (0.20-0.85) to 1Kg/L, and stirring for 3-5 h at the temperature of 45-75 ℃ to obtain the electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing the electrolyte with a constant current until the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 under the condition that the current is 1-3A to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of the vanadium ions to the composite permeation enhancing solute in the electrolyte II of (10-30) to 1, mixing, and stirring for 0.5-1 h at normal temperature to obtain an electrolyte IV.
The composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is (0.1-5) to 1.
Putting the electrolyte III into a positive electrolyte storage tank, putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 40-120 mA/cm2Under the conditions of (1).
The acid-soluble saccharide is more than one of glucose, xylose, sucrose, lactose, mannotriose and gentiotriose.
The metal complexing agent is more than one of glycolic acid, nitrilotriacetic acid, ammonium citrate and ethylene diamine tetraacetic acid.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
1. according to the invention, the acid-soluble saccharide and the metal complexing agent are selected as the composite permeation enhancing solute, the raw materials are simple and easy to obtain, the process operation is simple, a small amount of the composite permeation enhancing solute is added into the negative electrolyte, the additional osmotic pressure is added to the negative electrolyte, the transmembrane permeation of vanadium ions from the negative electrolyte to the positive electrolyte in the charge-discharge cycle process is relatively inhibited, and the capacity attenuation of the vanadium battery is obviously reduced.
2. The beneficial functional groups carried by the composite permeation enhancing solute added into the vanadium battery cathode electrolyte can be attached to the surface of an electrode, so that the redox reaction generated in the charge-discharge process is promoted, the electrochemical performance of the cathode electrolyte can be effectively improved, and the battery efficiency of the vanadium battery is improved.
The vanadium battery of the invention, in which the composite permeation enhancing solute is added into the negative electrolyte, is tested by 30 cycles: the capacity retention rate is 48.42-64%, the coulombic efficiency is 93.9-96.20%, and the energy efficiency is 79.10-81.15%; the vanadium battery without the composite permeation enhancing solute added into the cathode electrolyte under the same condition as the invention is tested by 30 cycles: the capacity retention rate is 30.23-38.99%, the coulombic efficiency is 93.45-94.25%, and the energy efficiency is 78.3-78.77%.
Therefore, the method has low cost and simple process, can obviously reduce the capacity attenuation of the vanadium battery and can improve the battery efficiency of the vanadium battery.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
A method for reducing capacity attenuation of a vanadium battery. The method comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of sulfuric acid to vanadyl sulfate of (2-5) to 1 to obtain a mixture.
And step two, adding deionized water into the mixture according to the solid-liquid ratio of vanadyl sulfate to deionized water of (0.20-0.85) to 1Kg/L, and stirring for 3-5 h at the temperature of 45-75 ℃ to obtain the electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing the electrolyte with a constant current until the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 under the condition that the current is 1-3A to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of the vanadium ions to the composite permeation enhancing solute in the electrolyte II of (10-30) to 1, mixing, and stirring for 0.5-1 h at normal temperature to obtain an electrolyte IV.
The composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is (0.1-5) to 1.
Putting the electrolyte III into a positive electrolyte storage tank, putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 40-120 mA/cm2Under the conditions of (1).
In this embodiment:
the acid-soluble saccharide is more than one of glucose, xylose, sucrose, lactose, mannotriose and gentiotriose.
The metal complexing agent is more than one of glycolic acid, nitrilotriacetic acid, ammonium citrate and ethylene diamine tetraacetic acid.
The purity of the vanadyl sulfate is more than or equal to 98 percent.
The detailed description is omitted in the embodiments.
Example 1
A method for reducing capacity attenuation of a vanadium battery. The method of the embodiment comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of 2: 1 of sulfuric acid to vanadyl sulfate to obtain a mixture.
And step two, adding deionized water into the mixture according to the solid-to-liquid ratio of vanadyl sulfate to deionized water of 0.2: 1Kg/L, and stirring for 3 hours at the temperature of 45 ℃ to obtain electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing under a constant current condition that the current is 1A until the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of the vanadium ions to the composite permeation enhancing solute in the electrolyte II of 10: 1, mixing, and stirring for 0.5h at normal temperature to obtain the electrolyte IV.
The composite permeation-enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is 0.1: 1.
Putting the electrolyte III into a positive electrolyte storage tank and putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium cell stack, and the voltage of the cell is 0.65-1.65V and the current density is 40mA/cm2Under the conditions of (1).
The vanadium redox battery of the present example, in which the composite permeation enhancing solute was added to the negative electrolyte, was subjected to 30 cycles of testing: the capacity retention rate is 48.42-52.36%, the coulombic efficiency is 93.9-94.90%, and the energy efficiency is 79.10-79.4%; the vanadium redox battery without the composite permeation enhancing solute added to the negative electrolyte under the same conditions as in the present example was subjected to 30 cycle tests: the capacity retention rate was 30.23%, the coulombic efficiency was 93.45%, and the energy efficiency was 78.61%.
Example 2
A method for reducing capacity attenuation of a vanadium battery. The method comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of 3: 1 of sulfuric acid to vanadyl sulfate to obtain a mixture.
And step two, adding deionized water into the mixture according to the solid-to-liquid ratio of vanadyl sulfate to deionized water of 0.45: 1Kg/L, and stirring for 4 hours at the temperature of 60 ℃ to obtain electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing under a constant current condition that the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of the vanadium ions to the composite permeation enhancing solute in the electrolyte II of 15: 1, mixing, and stirring for 0.65h at normal temperature to obtain the electrolyte IV.
The composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is 2.5: 1.
Putting the electrolyte III into a positive electrolyte storage tank, putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 70mA/cm2Under the conditions of (1).
The vanadium redox battery of the embodiment in which the composite permeation enhancing solute is added to the negative electrolyte is tested for 30 cycles: the capacity retention rate is 50.23-54.68%, the coulombic efficiency is 94.68-95.3%, and the energy efficiency is 78.9-79.52%; the vanadium redox battery without the composite permeation enhancing solute added to the negative electrolyte under the same conditions as in the present example was subjected to 30 cycle tests: the capacity retention was 35.1%, the coulombic efficiency was 93.68%, and the energy efficiency was 78.77%.
Example 3
A method for reducing capacity attenuation of a vanadium battery. The method comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of 4: 1 of sulfuric acid to vanadyl sulfate to obtain a mixture.
And step two, adding deionized water into the mixture according to the solid-to-liquid ratio of vanadyl sulfate to deionized water of 0.65: 1Kg/L, and stirring for 5 hours at 80 ℃ to obtain electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing under a constant current condition that the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of vanadium ions to the composite permeation enhancing solute in the electrolyte II of 25: 1, mixing, and stirring for 0.85h at normal temperature to obtain the electrolyte IV.
The composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is 3.5: 1.
Putting the electrolyte III into a positive electrolyte storage tank, putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 100mA/cm2Is carried under the condition ofAnd (6) rows.
The vanadium redox battery of the present example, in which the composite permeation enhancing solute was added to the negative electrolyte, was subjected to 30 cycles of testing: the capacity retention rate is 53.76-58.36%, the coulombic efficiency is 94.95-95.70%, and the energy efficiency is 79.32-80.50%; the vanadium redox battery without the composite permeation enhancing solute added to the negative electrolyte under the same conditions as in the present example was subjected to 30 cycle tests: the capacity retention was 38.30%, the coulombic efficiency was 93.98%, and the energy efficiency was 78.50%.
Example 4
A method for reducing capacity attenuation of a vanadium battery. The method comprises the following specific steps:
step one, mixing sulfuric acid and vanadyl sulfate according to the molar ratio of 5: 1 of sulfuric acid to vanadyl sulfate to obtain a mixture.
And step two, adding deionized water into the mixture according to the solid-to-liquid ratio of vanadyl sulfate to deionized water of 0.85: 1Kg/L, and stirring for 4 hours at 95 ℃ to obtain electrolyte I.
Taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; and switching on a power supply, and electrolyzing under a constant current condition that the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 to obtain corresponding electrolyte II and electrolyte III.
And step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of the vanadium ions to the composite permeation enhancing solute in the electrolyte II being 30: 1, mixing, and stirring for 1h at normal temperature to obtain the electrolyte IV.
The composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is 5: 1.
Putting the electrolyte III into a positive electrolyte storage tank and the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 120mA/cm2Under the conditions of (1).
The vanadium redox battery of the present example, in which the composite permeation enhancing solute was added to the negative electrolyte, was subjected to 30 cycles of testing: the capacity retention rate is 57.69-64.00%, the coulombic efficiency is 95.45-96.20%, and the energy efficiency is 80.42-81.15%; the vanadium redox battery without the composite permeation enhancing solute added to the negative electrolyte under the same conditions as in the present example was subjected to 30 cycle tests: the capacity retention was 38.99%, the coulombic efficiency was 94.25%, and the energy efficiency was 78.20%.
The composite permeation enhancing solute described in examples 1 to 4 is formed by mixing an acid-soluble saccharide substance and a metal complexing agent, so that the composite permeation enhancing solute added to the negative electrode electrolyte is formed by more than two substances, and the performance of the composite permeation enhancing solute fluctuates within a certain range, and thus the vanadium battery added with the composite permeation enhancing solute to the negative electrode electrolyte in each example also has a 30-cycle test value range.
Compared with the prior art, the specific implementation mode has the following positive effects:
1. according to the specific embodiment, the acid-soluble saccharide and the metal complexing agent are selected as the composite permeation enhancing solute, the raw materials are simple and easy to obtain, the process operation is simple, a small amount of the composite permeation enhancing solute is added into the negative electrolyte, the additional osmotic pressure is added to the negative electrolyte, the transmembrane permeation of vanadium ions from the negative electrolyte to the positive electrolyte in the charge-discharge circulation process is relatively inhibited, and the capacity attenuation of the vanadium battery can be remarkably reduced.
2. The beneficial functional groups carried by the composite permeation enhancing solute added into the vanadium battery cathode electrolyte can be attached to the surface of an electrode, so that the redox reaction generated in the charge-discharge process is promoted, the electrochemical performance of the cathode electrolyte can be effectively improved, and the battery efficiency of the vanadium battery is improved.
The vanadium redox battery of the present embodiment, in which the composite permeation enhancing solute is added to the negative electrolyte, is tested for 30 cycles: the capacity retention rate is 48.42-64%, the coulombic efficiency is 93.9-96.20%, and the energy efficiency is 79.10-81.15%; the vanadium redox battery without the composite permeation enhancing solute added to the negative electrolyte under the same conditions as the present embodiment was subjected to 30 cycle tests: the capacity retention rate is 30.23-38.99%, the coulombic efficiency is 93.45-94.25%, and the energy efficiency is 78.3-78.77%.
Therefore, the method is low in cost and simple in process, and can remarkably reduce the capacity attenuation of the vanadium battery and improve the battery efficiency of the vanadium battery.
Claims (3)
1. A method for reducing capacity fading of a vanadium battery is characterized by comprising the following specific steps:
mixing sulfuric acid and vanadyl sulfate to obtain a mixture, wherein the molar ratio of the sulfuric acid to the vanadyl sulfate is (2-5) to 1;
the purity of the vanadyl sulfate is more than or equal to 98 percent;
step two, adding deionized water into the mixture according to the solid-liquid ratio of vanadyl sulfate to deionized water of (0.20-0.85) to 1Kg/L, and stirring for 3-5 h at the temperature of 45-75 ℃ to obtain electrolyte I;
taking two parts of the electrolyte I with the same volume, and respectively placing the two parts of the electrolyte I in an anode chamber and a cathode chamber of an electrolytic cell; switching on a power supply, and electrolyzing to obtain electrolyte II and electrolyte III by constant current until the vanadium valence state of the electrolyte in the positive electrode chamber is 3.5 and the vanadium valence state of the electrolyte in the negative electrode chamber is 3.5 under the condition that the current is 1-3A;
step four, adding the composite permeation enhancing solute into the electrolyte II according to the molar ratio of vanadium ions to the composite permeation enhancing solute in the electrolyte II of (10-30) to 1, mixing, and stirring for 0.5-1 h at normal temperature to obtain an electrolyte IV;
the composite permeation enhancing solute is formed by mixing acid-soluble saccharide substances and metal complexing agents, wherein: the molar ratio of the acid-soluble saccharide to the metal complexing agent is (0.1-5) to 1;
putting the electrolyte III into a positive electrolyte storage tank, putting the electrolyte IV into a negative electrolyte storage tank, wherein the positive electrolyte storage tank and the negative electrolyte storage tank are respectively and correspondingly connected with a positive end and a negative end of the vanadium battery pile, and the battery voltage is 0.65-1.65V and the current density is 40-120 mA/cm2Is run under the conditions of (1).
2. The method for reducing the capacity fading of the vanadium redox battery according to claim 1, wherein: the acid-soluble saccharide is more than one of glucose, xylose, sucrose, lactose, mannotriose and gentiotriose.
3. The method for reducing the capacity fading of the vanadium redox battery according to claim 1, wherein: the metal complexing agent is more than one of glycolic acid, nitrilotriacetic acid, ammonium citrate and ethylene diamine tetraacetic acid.
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