CN111200152A - A kind of formula and process of all-vanadium redox flow battery electrolyte - Google Patents
A kind of formula and process of all-vanadium redox flow battery electrolyte Download PDFInfo
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- CN111200152A CN111200152A CN201811378534.2A CN201811378534A CN111200152A CN 111200152 A CN111200152 A CN 111200152A CN 201811378534 A CN201811378534 A CN 201811378534A CN 111200152 A CN111200152 A CN 111200152A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 94
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000009472 formulation Methods 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000012535 impurity Substances 0.000 claims description 20
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical group [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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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
- Y02E60/50—Fuel cells
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Abstract
本发明属于电解液配方领域，公开了一种全钒液流电池电解液的配方及工艺。通过对原料钒中影响电解液电阻的元素含量进行限制，当含这些元素的钒原料完全溶解形成电解液后，对相应元素含量上限进行控制，给出系统长时间安全运行的元素含量区间。相比现有技术的电解液系统，本发明的配方使系统效率仍能维持较高水平，同时有效降低电解液成本。The invention belongs to the field of electrolyte formulations, and discloses a formulation and a process of an all-vanadium redox flow battery electrolyte. By limiting the content of the elements in the raw vanadium that affect the resistance of the electrolyte, when the vanadium raw material containing these elements is completely dissolved to form the electrolyte, the upper limit of the corresponding element content is controlled, and the element content range for the long-term safe operation of the system is given. Compared with the electrolyte system of the prior art, the formula of the present invention can still maintain a high level of system efficiency, and at the same time effectively reduce the cost of the electrolyte.
Description
Technical Field
The invention belongs to the field of electrolyte formulas, and particularly relates to a formula and a process of an all-vanadium redox flow battery electrolyte.
Background
In the prior art, the performance of the battery is usually improved by adding reactive metal ions, but researches show that the performance of the battery system and the like can be adversely affected after partial reactive metal ions are introduced into the battery system by mistake, and for impurity ions except vanadium, the conductive resistance of the vanadium electrolyte is increased through different action mechanisms (forming non-conductive substances), so that the internal resistance of the electrolyte is increased, and the charging and discharging efficiency is reduced. The phenomenon that part of impurity ions influence the internal resistance of the vanadium electrolyte is reported in the literature, but the relevant literature about the limitation of the upper limit of the elements is not described.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a formula and a process of an all-vanadium redox flow battery electrolyte, and various performance indexes of a battery system are ensured on the basis of reducing the production cost of the electrolyte. After the indexes of the impurity elements are released, compared with the electrolyte with the corresponding elements exceeding the standard, the efficiency of the battery is obviously improved; compared with the existing high-purity electrolyte, the production cost of the electrolyte is greatly reduced.
The above purpose of the invention is realized by the following technical scheme:
the content of elements influencing internal resistance in the raw material vanadium is limited, and after the vanadium raw material containing corresponding elements is completely dissolved to form electrolyte, the corresponding ion content of the vanadium raw material is satisfied:
contains any one or more than one of the following elements (1) to (7), and when each element is present alone, the following elements are satisfied:
the content unit of the listed elements is as follows: mg/L;
(1) main group IA: comprises Li, Na, K and Rb, wherein any element is less than or equal to 200mg/L, and Li + Na + K + Rb is less than or equal to 800 mg/L;
(2) main group IIA: comprises Be, Mg, Ca, Sr and Ba, wherein any element is less than or equal to 60Mg/L, and Be + Mg + Ca + Sr + Ba is less than or equal to 300 Mg/L;
(3) group IIIA: comprises B, Al and Ga, wherein any element is less than or equal to 150mg/L, and B + Al + Ga is less than or equal to 600 mg/L;
(4) main group IVA: comprises organic total C elements, the organic total C is less than or equal to 500mg/L, and the total molecular mass of the organic total C elements is calculated according to the total molecular mass of the organic total C elements containing the C functional groups;
(5) subgroup IVB: comprises Ti, wherein Ti is less than or equal to 100 mg/L;
(6) group IIB: comprises Zn, Cd and Hg, wherein any element is less than or equal to 30mg/L, and Zn + Cd + Hg is less than or equal to 100 mg/L;
(7) subgroup VIII: comprises Ni, Co and Fe, wherein any element is less than or equal to 30mg/L, and Ni + Co + Fe is less than or equal to 100 mg/L; any other element of the family is less than or equal to 1 mg/L;
the electrolyte is any one of the parameters of sulfuric acid system electrolyte and HCl system electrolyte and the mixed acid system electrolyte.
Further, when elements of main group IA and main group IVA are simultaneously present, the following requirements should be satisfied: li + Na + K + Rb + total organic C elements are less than or equal to 1000mg/L, and any element is less than or equal to 200 mg/L;
further, when both group IIA and group IIIA elements are present, the following requirements should be satisfied: be + Mg + Ca + Sr + Ba + B + Al + Ga is less than or equal to 700Mg/L, and any element is less than or equal to 80 Mg/L;
further, when elements of subgroups IVB, IIB and VIII are present simultaneously, the following requirements should be satisfied: ti + Zn + Cd + Hg + Ni + Co + Fe is less than or equal to 300mg/L, and any element is less than or equal to 25 mg/L;
wherein the requirements for the electrolyte system are as follows:
sulfuric acid system electrolyte parameters: unless otherwise specified, the concentration of free sulfuric acid is more than 1mol/L and less than 4mol/L, and the concentration of vanadium ions is more than 1mol/L and less than 3 mol/L;
HCl system electrolyte parameters: unless otherwise specified, the concentration of free hydrochloric acid is more than 5mol/L and less than 11mol/L, and the concentration of vanadium ions is more than 2mol/L and less than 4 mol/L;
electrolyte parameters of the mixed acid system: unless otherwise specified, the concentration of free hydrochloric acid is 5mol/L or more and 11mol/L or less, the concentration of vanadium ions is 2mol/L or more and 4mol/L or less, and the concentration of free sulfuric acid is 0.1mol/L or more and 3mol/L or less;
the specific operation is as follows: such as: preparing 1L, 2mol/L vanadium electrolyteA total of 95% of V is required2O5187.63g of vanadium raw material, but when the raw material contained 0.32% sodium sulfate, the raw material was completely dissolved to form a vanadium electrolyte solution containing Na+200mg/L, so if the electrolyte product Na is controlled+<200mg/L, the raw material with the sodium sulfate content of less than 0.32 percent is selected.
The process control method of the invention is as shown in figure 1, the raw materials are adjusted and prepared according to the process control method, and the electrolyte of the all-vanadium redox flow battery is prepared on the basis of the element content required by the formula;
the production process of the electrolyte is divided into the following two methods: calcination reduction and electrolysis, and chemical reduction and electrolysis.
(I) calcination reduction + electrolysis method
1) According to the standard of the amplified element content in the technical scheme of the invention, the raw material of ammonium metavanadate with vanadium purity of 95% is selected.
2) Adding ammonium metavanadate as raw material into a reaction furnace, and adding reducing substance (NH)3) Calcining at the high temperature of 500-900 ℃ for reduction reaction, wherein the product is vanadium (V) tetraoxide2O4) Powder, water, nitrogen and the like, cooling the reaction materials in the furnace to below 50 ℃, washing and filtering the reaction products for the first time, and filtering out insoluble silt or washing away part of soluble salts and the like;
3)V2O4adding the powder into an acid-proof reaction kettle containing 10-15 wt% sulfuric acid or 20-25 wt% hydrochloric acid, mixing, heating, stirring, reacting for about 30 min, filtering for the second time to obtain VOSO containing 10 wt% sulfuric acid4Or HCl concentration 25-30 wt% VOCl2An aqueous hydrochloric acid solution;
4) the prepared electrolyte with the valence of 4 or more than 3.5 is pumped into a negative storage tank of an electrolysis system, and the electrolysis current (80 mA/cm) is set2) Carrying out electrolytic reduction to obtain a sulfuric acid or hydrochloric acid electrolyte finished product with a valence state of 3.5 (the vanadium ions with the valence of 3 and 4 respectively account for 50% of molar concentration).
The process of adding complexing agent or precipitant to remove impurity ions is omitted in the conventional process (because a certain amount of impurity ions are allowed to exist according to the process requirement).
(II) chemical reduction + electrolysis method
When the vanadium raw material is powdery V2O5In the process, the raw materials are selected according to the standard of amplified element content in the technical scheme of the invention, and the purity of vanadium is 95 percent.
1) The production method of reduction and electrolysis is adopted. The production process comprises the following steps: according to the requirement of vanadium concentration in the finished product, the vanadium concentration is changed to V2O5Adding 10-15% sulfuric acid or 20-25% hydrochloric acid into the material, stirring to partially dissolve, and stirring for 60 min;
2) then according to the ratio of 5-valent vanadium ion (VO)2 +) Is completely reduced into (VO)2+) The required amount of reducing agent is calculated and added with reducing agents such as oxalic acid, ethanol, saccharides and the like (SO can be directly introduced)2Gas), making 5-valent vanadium ions (VO) partially dissolved in 1)2 +) Reduced to 4-valent vanadium ions (VO)2+) And finally promote V2O5All dissolve and reduce into 4-valent vanadium ions (VO)2+)；
3) Insoluble matter (silt, etc.) is removed by filtration, and then reduced to vanadium ion (VO) having a valence of 42+) Introducing the solution into a cathode storage tank of an electrolysis system for electrolytic reduction, and setting the electrolytic current density to be 80mA/cm according to the electrode area of the electrolysis system2Until the cathode electrolyte reaches 3.5 (the vanadium ions with 3 valence and 4 valence respectively account for 50% of molar concentration);
4) and filtering again to remove insoluble impurities (scraps, polymers and the like) in the solution to obtain a finished product of the sulfuric acid or hydrochloric acid electrolyte.
The process of adding complexing agent or precipitant to remove impurity ions is omitted in the conventional process (because a certain amount of impurity ions are allowed to exist according to the process requirement).
Proper release of part of impurity ions does not affect various parameters of the electrolyte, but the impurity ions directly affect the conductivity of the electrolyte when reaching a certain upper concentration limit, and further affect the efficiency of a battery system. The invention controls the influence of the impurities on the performance of the all-vanadium redox flow battery by controlling the upper limit of the content of the impurity elements.
The existing all-vanadium electrolyte requires high purity (> 99%) of raw material vanadium, which causes the cost of the electrolyte to be high. Allowing certain elements to be present in certain concentrations can reduce the overall cost of the electrolyte without affecting the solution properties.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the existing high-purity electrolyte system, after related impurity elements are increased to a certain degree, the system efficiency is still maintained at a higher level, and the system still operates normally;
2. compared with the existing electrolyte system which is excessively released and contains the above elements, the voltage efficiency is improved by more than 1 percent;
3. the method can effectively control the content of impurity elements participating in electrode reaction, improve the performance of a battery system, prolong the service life of equipment such as battery resistance and the like, effectively reduce the cost of the electrolyte, reduce the purchase cost of electrolyte raw materials by more than 20 percent, and reduce the production cost of the electrolyte by about 15 percent.
Drawings
FIG. 1 is a flow chart of the calcination reduction electrolysis process control of the present invention.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
The total impurity content of the high purity electrolyte described in the comparative example is required to be <100 mg/L. Specifically, each element is required to be <5 mg/L.
Examples 1-4 are all compared to comparative example 1; wherein the experimental conditions of examples 1-4 are the same as those of comparative example 1; the conditions of the scale of the galvanic pile, the charging and discharging modes, the running time and the like are the same;
example 5 comparative example 2; wherein the experimental conditions of example 5 are the same as those of comparative example 2; the conditions of the scale of the galvanic pile, the charging and discharging modes, the running time and the like are the same;
example 6 comparative example 3; wherein the experimental conditions of example 6 are the same as those of comparative example 3; the conditions of the scale of the galvanic pile, the charging and discharging modes, the running time and the like are the same;
in the examples, the single element in the VIII subgroup is Ni, Co, Fe.
Comparative example 1
Experimental samples: the existing sulfuric acid system is high-purity electrolyte;
scale of galvanic pile: 2kW, charge and discharge mode: CC, operation time length: 50 cycles;
the experimental results are as follows:
average efficiency of the stack: CE: 94.5%, VE: 84.5%, EE: 79.9 percent;
resistivity: 4.10 omega cm.
Comparative example 2
Experimental samples: the existing hydrochloric acid system is high-purity electrolyte;
scale of galvanic pile: 2kW, charge and discharge mode: CC, operation time length: 50 cycles;
the experimental results are as follows:
average efficiency of the stack: CE: 95%, VE: 84.9%, EE: 80.7 percent;
resistivity: 4.55 omega cm.
Comparative example 3
Experimental samples: the existing mixed acid system is high-purity electrolyte;
scale of galvanic pile: 2kW, charge and discharge mode: CC, operation time length: 50 cycles;
the experimental results are as follows:
average efficiency of the stack: CE: 94.5%, VE: 84.8%, EE: 80.1 percent;
resistivity: 4.44 Ω.
Example 1
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data and the operation results show that when the elements of the IA main group and the IVA main group are properly relaxed, the target electrolyte does not influence the internal resistance of the electrolyte, and the pile efficiency of the electrolyte is not different from that of a high-purity electrolyte pile, but when the impurity elements exceed the standard, the pile efficiency is reduced to a certain extent
Example 2
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data and the operation result show that when the elements of the main group IIA and the main group IIIA are properly relaxed, the target electrolyte does not influence the internal resistance of the electrolyte, and meanwhile, the efficiency of the galvanic pile is not different from that of a high-purity electrolyte galvanic pile, but when the impurity elements exceed the standard, the efficiency of the galvanic pile is reduced to a certain extent.
Example 3
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data show that when elements of IIB subgroup, IVB subgroup and VIII subgroup are properly relaxed, the elements of VIII subgroup include Ni, Co and Fe, the target electrolyte does not influence the internal resistance of the electrolyte, and the pile efficiency of the target electrolyte is not different from that of a high-purity electrolyte pile, but when the impurity elements exceed the standard, the pile efficiency is reduced to a certain extent.
Example 4
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data show that when the contents of all elements in the IA main group, the IIA main group, the IIIA main group, the IVA main group, the IIB sub-group, the IVB sub-group and the VIII sub-group meet the formula requirements of the invention, the target electrolyte does not influence the internal resistance of the electrolyte, and the galvanic pile efficiency of the electrolytic pile is not different from that of a high-purity electrolyte galvanic pile, but the galvanic pile efficiency is reduced to a certain extent after impurity elements exceed the standard.
Example 5
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data show that for the hydrochloric acid system electrolyte, when the contents of all elements in the main group IIA, the main group IIIA, the subgroup IIB, the subgroup IVB and the subgroup VIII meet the formula requirements of the invention, the target electrolyte does not influence the internal resistance of the electrolyte and the corresponding galvanic pile test, but when part of elements do not meet the formula requirements of the invention, the corresponding efficiency is greatly reduced.
Example 6
Vanadium electrolytes were prepared and run according to the sample contents in the following table, with the results shown in the following table:
the data show that for the mixed acid electrolyte, when the contents of all elements in the IA main group, the IIA main group, the IIIA main group, the IVA main group, the IIB sub-group, the IVB sub-group and the VIII sub-group meet the formula requirements of the invention, the target electrolyte does not influence the internal resistance of the electrolyte and the corresponding galvanic pile test, but when part of the elements do not meet the formula requirements of the invention, the corresponding efficiency is greatly reduced.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (8)
1. The formula of the electrolyte of the all-vanadium redox flow battery is characterized in that the content of elements influencing internal resistance in raw material vanadium is limited, and when the vanadium raw material containing corresponding elements is completely dissolved to form the electrolyte, the corresponding ion content of the electrolyte meets the following requirements:
contains any one or more than one of the following elements (1) to (7), and when each element is present alone, the following elements are satisfied:
the content unit of the listed elements is as follows: mg/L;
(1) main group IA: comprises Li, Na, K and Rb, wherein any element is less than or equal to 200mg/L, and Li + Na + K + Rb is less than or equal to 800 mg/L;
(2) main group IIA: comprises Be, Mg, Ca, Sr and Ba, wherein any element is less than or equal to 60Mg/L, and Be + Mg + Ca + Sr + Ba is less than or equal to 300 Mg/L;
(3) group IIIA: comprises B, Al and Ga, wherein any element is less than or equal to 150mg/L, and B + Al + Ga is less than or equal to 600 mg/L;
(4) main group IVA: comprises organic total C elements, the organic total C is less than or equal to 500mg/L, and the total molecular mass of the organic total C elements is calculated according to the total molecular mass of the organic total C elements containing the C functional groups;
(5) subgroup IVB: comprises Ti, wherein Ti is less than or equal to 100 mg/L;
(6) group IIB: comprises Zn, Cd and Hg, wherein any element is less than or equal to 30mg/L, and Zn + Cd + Hg is less than or equal to 100 mg/L;
(7) subgroup VIII: comprises Ni, Co and Fe, wherein any element is less than or equal to 30mg/L, and Ni + Co + Fe is less than or equal to 100 mg/L; any other element of the family is less than or equal to 1 mg/L;
the electrolyte is any one of the parameters of sulfuric acid system electrolyte and HCl system electrolyte and the mixed acid system electrolyte.
2. The formula of the electrolyte of the all-vanadium flow battery as claimed in claim 1, wherein the electrolyte system comprises the following components:
(1) sulfuric acid system electrolyte parameters: the concentration of free sulfuric acid is more than 1mol/L and less than 4mol/L, and the concentration of vanadium ions is more than 1mol/L and less than 3 mol/L;
(2) HCl system electrolyte parameters: the concentration of free hydrochloric acid is more than 5mol/L and less than 11mol/L, and the concentration of vanadium ions is more than 2mol/L and less than 4 mol/L;
(3) electrolyte parameters of the mixed acid system: the concentration of free hydrochloric acid is more than 5mol/L and less than 11mol/L, the concentration of vanadium ions is more than 2mol/L and less than 4mol/L, and the concentration of free sulfuric acid is more than 0.1mol/L and less than 3 mol/L.
3. The formula of the electrolyte of the all-vanadium flow battery according to claim 1, wherein when the elements of main group IA and main group IVA exist simultaneously, the following requirements are met: li + Na + K + Rb + total organic C elements are less than or equal to 1000mg/L, and any element is less than or equal to 200 mg/L.
4. The formula of the electrolyte of the all-vanadium redox flow battery according to claim 1, wherein when elements of main group IIA and main group IIIA exist simultaneously, the following requirements are met: be + Mg + Ca + Sr + Ba + B + Al + Ga is less than or equal to 700Mg/L, and any element is less than or equal to 80 Mg/L.
5. The formulation of an all vanadium flow battery electrolyte according to claim 1, wherein the presence of elements from sub-groups IVB, IIB and VIII satisfies the following requirements: ti + Zn + Cd + Hg + Ni + Co + Fe is less than or equal to 300mg/L, and any element is less than or equal to 25 mg/L.
6. The process for preparing the electrolyte of the all-vanadium redox flow battery according to the formula of claim 1, wherein the preparation process adopts any one of a calcination reduction + electrolysis method and a chemical reduction + electrolysis method.
7. The process as claimed in claim 6, wherein the calcination reduction + electrolysis method comprises the following steps:
1) selecting raw materials with the vanadium purity of 95 percent;
2) raw material metavanadateAdding ammonium into a reaction furnace, and adding a reducing substance NH3Calcining at the high temperature of 500 ℃ and 900 ℃ to carry out reduction reaction, wherein the product is V2O4Powder, water and nitrogen, cooling the reaction materials in the furnace to below 50 ℃, washing and filtering the reaction products for the first time, and filtering out insoluble silt or washing off part of soluble salts;
3)V2O4adding the powder into an acid-proof reaction kettle containing 10-15 wt% sulfuric acid or 20-25 wt% hydrochloric acid, mixing, heating, stirring, reacting for about 30 min, filtering for the second time to obtain VOSO containing 10 wt% sulfuric acid4Or HCl concentration 25-30 wt% VOCl2An aqueous hydrochloric acid solution;
4) the prepared electrolyte with the valence of 4 or more than 3.5 is pumped into a negative storage tank of an electrolysis system, and the electrolysis current is set to be 80mA/cm2Carrying out electrolytic reduction to obtain a finished product of sulfuric acid or hydrochloric acid electrolyte with the valence state of 3.5.
8. The process as claimed in claim 6, wherein the chemical reduction + electrolysis method comprises the following steps:
when the vanadium raw material is powdery V2O5Selecting raw materials with the vanadium purity of 95 percent;
1) according to the requirement of vanadium concentration in the finished product, the vanadium concentration is changed to V2O5Adding 10-15 wt% sulfuric acid or 20-25 wt% hydrochloric acid into the material, stirring to dissolve part of the material, and stirring for 60 min;
2) according to the VO2 +Complete reduction to VO2+The required dosage of the reducing agent is calculated, and the reducing agent is added to ensure that the VO is partially dissolved in the step 1)2 +Reducing and finally promoting V2O5All dissolved and reduced to VO2+；
3) Filtering to remove insoluble substances, and reducing to VO2+Introducing the solution into a cathode storage tank of an electrolysis system for electrolytic reduction, and setting the electrolytic current density to be 80mA/cm according to the electrode area of the electrolysis system2Until the cathode electrolyte reaches 3.5 price;
4) and filtering again to remove insoluble impurities in the solution to obtain a finished product of sulfuric acid or hydrochloric acid electrolyte.
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