CN113707927A - High volume capacity flow battery system - Google Patents
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- 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
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- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
The invention discloses a high-volume capacity flow battery system, wherein positive active substances are two ferricyanides, two to three ferrocyanides or two to four [ DCNQI ] s with different cations]2X; when the positive active substance is ferricyanide or ferrocyanide with different cations, the anion concentration is 1.1-1.6 mol/L; the positive active material is [ DCNQI ] with different cations]2When X is higher, the anion concentration is 0.2-0.4 mol/L; the anode electrolyte liquid storage tank is internally provided with a solid energy storage material, and the solid energy storage material consists of one or two of Prussian blue and Prussian white. The high-volume-capacity flow battery system provided by the invention adopts a hetero-ionic effect and a same-potential Nernst potential to drive an oxidation-reduction targeted reaction to jointly improve the volume capacity of the full battery of the flow battery, and simultaneously, the cycle stability of the full battery of the flow battery is more stabilized, so that the full battery has an ultra-long cycle life.
Description
Technical Field
The invention belongs to the technical field of redox targeting reaction flow batteries, in particular to the field of redox targeting iron-sulfur flow batteries based on Nernst potential driving, and particularly relates to a high-volume-capacity flow battery system.
Background
Renewable new energy power generation is well paid attention to the power industry because of cleanness and sustainability, but due to the characteristics of discontinuity and instability, the renewable new energy power generation can cause impact damage to a power grid when being directly connected to the power grid, and the problem can be effectively solved by the energy storage device equipped for the renewable new energy power generation. The flow battery is a large-scale energy storage device with the most development prospect at present due to the advantages of high safety performance, capacity and power separation, flexible structural design, strong expandability, high response speed and the like.
The currently developed flow battery is an all-vanadium flow battery, but the all-vanadium flow battery has the problems of high cost, low volume capacity and the like, and the low volume capacity is an important reason for hindering the development of the flow battery. In recent years, ferricyanide has been widely studied because of its high reversibility and cycle stability, but an iron-sulfur-based flow battery using ferricyanide as an active material is limited by the solubility of ferricyanide, so that the full battery capacity is at a disadvantage.
The volume capacity of the positive and negative electrode sides of the redox flow battery depends on the solubility of an active substance in electrolyte, the volume capacity of the redox flow battery is low due to the fact that the active substance in the positive and negative electrolyte is limited by the solubility of the active substance, and in order to improve the solubility of the active substance in the positive and negative electrolyte of the redox flow battery, a method for improving the solubility of vanadyl sulfate of the vanadium redox flow battery by using mixed acid is adopted in the prior art, but the mixed acid is strong in corrosivity, high in requirement on devices, high in cost and short in service life; there is a method of increasing volume capacity by using solid suspension, but the solid suspension needs to be added with conductive additive, the reaction rate is slow, the viscosity of the suspension is high, the damage to the pump is large, and the service life of the battery is short; there are methods for developing high-solubility organic molecules to increase the volume capacity of a flow battery, but the stability of the organic molecules is poor, which causes the problem of poor battery cycle performance, and the cost of the organic molecules is high, and most of the organic molecules are dissolved in organic solvents, which are flammable and have poor safety. At present, the technology of adding solid energy storage materials into an electrolyte storage tank to increase the volume capacity of a single side is adopted. However, in the prior art, the pH of the solution is adjusted to ensure that the potential of the active substance is the same as that of the solid material, but the corrosivity of the solution is undoubtedly increased, or a plurality of active substances are added into the electrolyte to realize the oxidation reduction of the solid material, but the complexity of the reaction is increased, the voltage efficiency is reduced, and the cycling stability is reduced.
The specific surface area of the solid energy storage material used for energy storage is small, and the solid energy storage material cannot be in complete contact with a solution, so that the utilization rate of the solid energy storage material is about 40-60%, namely 40-60% of the theoretical capacity of the solid material.
In summary, the volume capacity of the flow battery is difficult to realize qualitative leap due to the limitation of the prior art barrier, so that the development speed and wide and rapid application of the flow battery are limited, and the need of innovative technology is urgently awaited, so that the volume capacity of the flow battery is rapidly and effectively improved and the further development of the flow battery is promoted under the condition of ensuring the high performance of the flow battery.
Disclosure of Invention
In order to achieve the above purpose, an embodiment of the present invention provides a high volume capacity flow battery system, and the volume capacity of a full battery of a flow battery is improved by using a hetero-ionic effect and a potentiostat to drive an oxidation-reduction targeting reaction, and simultaneously, the cycle stability of the full battery of the flow battery is more stabilized, so that the full battery has an ultra-long cycle life, and the problems of high cost and low volume capacity of the flow battery in the prior art are solved.
The technical scheme adopted by the invention is that in the high-volume-capacity flow battery system, a positive electrolyte is stored in a positive electrolyte storage tank, a positive active substance is added into the positive electrolyte, a negative electrolyte is stored in a negative electrolyte storage tank, a negative active substance is added into the negative electrolyte, and the positive active substance is two ferricyanides, two to three ferrocyanides or two to four [ DCNQI ] s with different cations]2X; ferricyanide includes potassium ferricyanide or ammonium ferricyanide; the ferrocyanide comprises potassium ferrocyanide, sodium ferrocyanide or ammonium ferrocyanide; the [ DCNQI ]]2X comprises [ DCNQI]2Na、[DCNQI]2K、[DCNQI]2Li or [ DCNQI ]]2NH4(ii) a When the positive active substance is two ferricyanides and two to three ferrocyanides with different cations, the anion concentration range of the positive active substance is 1.1mol/L to 1.6 mol/L; the positive active substance is two to four kinds of [ DCNQI ] with different cations]2When X is higher, the anion concentration range of the positive active material is 0.2-0.4 mol/L;the negative active material is selected from potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, [ DCNQI ]]2Any one or more of X, wherein the concentration range of the negative active material is 0.1-12 mol/L; the supporting electrolyte in the positive electrolyte or the negative electrolyte comprises LiCl and Li2SO4、LiNO3、LiOH、KCl、K2SO4、KNO3、KOH、NaCl、Na2SO4、NaNO3、NaOH、NH4Cl、(NH4)2SO4、Bu4NClO4Any one or more of; and a solid energy storage material is arranged in the anode electrolyte liquid storage tank, and the solid energy storage material consists of one or two of Prussian blue and Prussian white.
Furthermore, the solid energy storage material is prepared from a solid energy storage substance by a pouring method or an electrostatic spinning method.
Further, the sum of the concentrations of the supporting electrolyte in the positive electrode electrolyte or the negative electrode electrolyte is 0.2mol/L to 4 mol/L.
Furthermore, the cation species of the supporting electrolyte in the positive electrode electrolyte solution is 1 to 4 species, and the cation species of the supporting electrolyte in the negative electrode electrolyte solution is one species.
Further, when two cations are present in the positive electrode electrolyte, the molar ratio of the two cations is (1-3): (1-3); when three cations exist in the positive electrode electrolyte, the molar ratio of the three cations is (1-3): (1-3): (1-3); when four cations are present in the positive electrode electrolyte, the molar ratio of the four cations is (1-3): (1-3): (1-3): (1-3).
Further, the solid energy storage material is prepared by an electrostatic spinning method, and comprises the following steps:
s1, dissolving a high molecular polymer in an organic solvent to obtain a high molecular polymer solution;
the high molecular polymer is polyvinylidene fluoride with the number average molecular weight of 10-100 ten thousand; the organic solvent comprises any one or two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone; the mass volume ratio of the high molecular polymer to the organic solvent is 1 g: 2 mL-5 mL;
s2, adding a solid energy storage substance into the high molecular polymer solution to obtain an electrostatic spinning solution; the mass ratio of the solid energy storage substance to the high molecular polymer S1 is (1: 9) - (9: 1);
and S3, carrying out electrostatic spinning treatment on the electrostatic spinning solution, and pressing and drying the obtained disordered jet-shaped fiber material to obtain the solid energy storage material.
Further, in S3, the electrostatic spinning process specifically includes: injecting the electrostatic spinning solution into an injector, wherein the capacity of the injector is 10-20 mL, the electrostatic spinning solution in the injector is sprayed onto a receiving plate in a high-pressure disordered manner, the distance from a needle head of the injector to the receiving plate is 10-25 cm, the spraying rate is 0.5-3 mL/h, the voltage is set to be 10-30 kV, the spinning temperature is controlled to be 20-70 ℃, the air humidity is 20-60%, the receiving plate is aluminum foil paper or copper plate, and a disordered spraying-shaped fiber material is formed on the receiving plate.
The invention has the beneficial effects that:
(1) according to the embodiment of the invention, the volume capacity of the full cell of the flow cell is improved by adopting the hetero-ionic effect and the same-potential Nernst potential to drive the redox targeting reaction, and meanwhile, the cycle stability of the full cell of the flow cell is more stabilized, so that the full cell has an ultra-long cycle life.
(2) The embodiment of the invention popularizes the solid energy storage mode to the aqueous phase flow battery and the organic phase flow battery, utilizes the hetero-ion effect to synergistically improve the solubility of the active substance in the electrolyte, and utilizes the electrostatic spinning process to prepare the solid energy storage material with the ultrahigh specific surface area, so that the utilization rate of the solid energy storage material reaches more than 80%, and utilizes Nernst potential to drive the redox targeting reaction to realize solid energy storage, thereby breaking the solubility limit of the active substance in the electrolyte and further effectively improving the volume capacity of the positive electrode side.
(3) The solid material adopted by the embodiment of the invention is stored in the liquid storage tank and does not enter the inside of the electrode. However, the solid material is a self-made particle material, and trace powder inevitably enters the battery along with the electrolyte and adheres to the surface of the electrode, so that the small-sized trace solid material on the surface of the electrode has a catalytic effect on the active substance, the oxidation-reduction reaction rate of the active substance on the electrode is improved, and the power performance of the battery is improved.
(4) The active substances adopted by the embodiment of the invention have low cost, and the material friendliness of the neutral aqueous solution can effectively reduce the equipment input cost and the maintenance cost, thereby being beneficial to realizing industrialization and scale production by the technical scheme of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a high volume capacity flow battery system according to an embodiment of the invention.
Fig. 2 is a graph of the cycle performance of the flow battery system in example 2 of the present invention.
Fig. 3 is a rate performance graph of a flow battery system in example 2 of the invention.
Fig. 4 is a graph of the cycling performance of the flow battery system in example 9 of the present invention.
Fig. 5 is a graph of the cycling performance of the flow cell system of comparative example 1 of the invention.
Fig. 6 is a graph of capacity voltage of batteries of example 2 of the present invention and comparative example 1.
Fig. 7 is a graph of the cycling performance of the flow cell system of comparative example 3 of the present invention.
Fig. 8 is a graph comparing the volumetric capacity and voltage of flow battery systems of example 2, comparative example 1, and comparative example 3 of the present invention.
In the drawings: the device comprises a 1-flow battery unit, a 2-anode electrolyte storage tank, a 3-cathode electrolyte storage tank, a 4-anode circulating pump, a 5-cathode circulating pump, a 6-anode transmission pipeline, a 7-cathode transmission pipeline, a 1-1 anode half cell, a 1-2 diaphragm, a 1-3 cathode half cell, a 2-1 anode electrolyte storage tank liquid inlet, a 2-2 anode electrolyte storage tank liquid outlet, a 1-1-1 anode liquid outlet, a 1-1-2 anode liquid inlet, a 3-1 cathode electrolyte storage tank liquid inlet, a 3-2 cathode electrolyte storage tank liquid outlet, a 1-3-1 cathode liquid outlet and a 1-3-2 cathode liquid inlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A high volume capacity flow battery system comprises a single cell or a cell stack consisting of more than two single cells; as shown in fig. 1, the single cell comprises a flow cell unit 1, a positive electrolyte storage tank 2, a negative electrolyte storage tank 3, a positive circulating pump 4, a negative circulating pump 5, a positive transmission pipeline 6 and a negative transmission pipeline 7; the flow battery unit 1 sequentially comprises a positive electrode half battery 1-1, a diaphragm 1-2 and a negative electrode half battery 1-3; the positive electrolyte storage tank 2 stores positive electrolyte, and positive active substances are added into the positive electrolyte; the negative electrolyte storage tank 3 is stored with negative electrolyte, and negative active substances are added into the negative electrolyte; a solid energy storage material can be arranged in the anode electrolyte storage tank 2; the solid energy storage material is prepared from one or two solid energy storage substances of Prussian Blue (PB) and Prussian White (PW).
Prussian blue, i.e. ferric ferrocyanide, of the formula
Is a complex compound.
Prussian white is the reduced state of Prussian blue and has the chemical formula
Where X is a cation, Na is preferably used herein+、K+、NH4 +、Li+Any one of the above.
The top end of the anode electrolyte storage tank 2 is provided with an anode electrolyte storage tank inlet 2-1, and the bottom end is provided with an anode electrolyte storage tank outlet 2-2; the top end of the positive electrode half cell 1-1 is provided with a positive electrode liquid outlet 1-1-1, and the bottom end is provided with a positive electrode liquid inlet 1-1-2; a liquid outlet 2-2 of the positive electrolyte storage tank is connected with a positive circulating pump 4 through a positive transmission pipeline 6, and the positive circulating pump 4 is connected with a positive liquid inlet 1-1-2 through the positive transmission pipeline 6; the anode liquid outlet 1-1-1 is connected with the anode electrolyte liquid storage tank liquid inlet 2-1 through an anode transmission pipeline 6.
The top end of the negative electrolyte storage tank 3 is provided with a negative electrolyte storage tank inlet 3-1, and the bottom end is provided with a negative electrolyte storage tank outlet 3-2; a negative liquid outlet 1-3-1 is arranged at the top end of the negative half cell 1-3, and a negative liquid inlet 1-3-2 is arranged at the bottom end; a liquid outlet 3-2 of the negative electrolyte liquid storage tank is connected with a negative circulating pump 5 through a negative transmission pipeline 7, and the negative circulating pump 5 is connected with a negative liquid inlet 1-3-2 through the negative transmission pipeline 7; the negative electrode liquid outlet 1-3-1 is connected with the liquid inlet 3-1 of the negative electrode electrolyte liquid storage tank through a negative electrode transmission pipeline 7.
The supporting electrolyte in the positive electrolyte comprises LiCl and Li2SO4、LiNO3、LiOH、KCl、K2SO4、KNO3、KOH、NaCl、Na2SO4、NaNO3、NaOH、NH4Cl、(NH4)2SO4、Bu4NClO4(tetrabutylammonium perchlorate), in some preferred embodiments, the number of the cationic species of the supporting electrolyte in the positive electrode electrolyte is 1-4, the effect of improving the solubility of the positive electrode active material in the positive electrode electrolyte is not obvious after the number of the cationic species exceeds four, and the introduction of more than four cationic species has an influence on the circulation stability of the positive electrode electrolyte and increases the internal resistance of the battery; the sum of the concentrations of the supporting electrolytes in the positive electrode electrolyte is 0.2mol/L to 4 mol/L.
Supporting electrolysis in the negative electrolyteThe substance comprises LiCl and Li2SO4、LiNO3、LiOH、KCl、K2SO4、KNO3、KOH、NaCl、Na2SO4、NaNO3、NaOH、NH4Cl、(NH4)2SO4、Bu4NClO4Any one or more of the above, in some preferred embodiments, the cation species of the supporting electrolyte in the negative electrolyte solution is one, and a plurality of supporting electrolyte cations may be present in the negative electrolyte solution, which may be assembled into a battery and circulated, but the performance is not good; the sum of the concentrations of the supporting electrolytes in the negative electrode electrolyte is 0.2mol/L to 4 mol/L.
When the cation of the supporting electrolyte in the negative electrode electrolyte is one, the cation needs to be one of the cations of the supporting electrolyte in the positive electrode electrolyte.
The positive active substance in the positive electrolyte is two ferricyanides, two to three ferrocyanides or two to four [ DCNQI ] compounds with different cations]2X, effectively improving the solubility of the positive active substance in the positive electrolyte, wherein the ferricyanide comprises potassium ferricyanide or ammonium ferricyanide; ferrocyanide includes potassium ferrocyanide, sodium ferrocyanide or ammonium ferrocyanide; [ DCNQI]2X comprises [ DCNQI]2Na、[DCNQI]2K、[DCNQI]2Li or [ DCNQI ]]2NH4(ii) a When the positive active substance is two ferricyanides and two to three ferrocyanides with different cations, the anion concentration range of the positive active substance is 1.1mol/L to 1.6 mol/L; the positive active substance is two to four kinds of [ DCNQI ] with different cations]2When X is higher, the anion concentration range of the positive active material is 0.2-0.4 mol/L; the volume capacity can be synergistically improved by matching with the solid energy storage material; the volume capacity of the flow battery is high and low, so that the performance is good and bad. The volume capacity is the capacity that the battery can release per unit volume, and the unit is Ah/L.
In some preferred embodiments, (potassium ferrocyanide + sodium ferrocyanide) or ([ DCNQI]2Na+[DCNQI]2K) Due to K as the positive electrode active material+And Na+As the same masterTwo adjacent cations in the family are more similar in chemical properties, and have little influence on the performance of the flow battery.
[DCNQI]2X has a structural formula of
In the formula, DCNQI is N, N’-dicyanoquinoline diimine (C)8H4N4) X represents a cation, including Na+、K+、NH4 +、Li+Any one of the above.
In the process of charging and discharging of the flow battery system, the oxidation state and the reduction state of the anion of the positive electrode active material coexist in the positive electrode electrolyte, and the concentration of the oxidation state relative to the reduction state of the anion of the positive electrode active material changes at any moment along with the progress of charging and discharging, and the Nernst potential also changes at any moment.
The positive active material and the positive ions of the supporting electrolyte in the positive electrolyte relate to four types, including K+、Na+、NH4 +、Li+(ii) a When two cations are present in the positive electrode electrolyte, the molar ratio of the two cations is (1-3): (1-3); when three cations exist in the positive electrode electrolyte, the molar ratio of the three cations is (1-3): (1-3): (1-3); when four cations are present in the positive electrode electrolyte, the molar ratio of the four cations is (1-3): (1-3): (1-3): (1-3).
The positive active substance is placed in the positive electrolyte of two or more than two cations, preferably in the positive electrolyte with two cations, the positive electrolyte cations are provided by the cations of the positive active substance and the cations of the supporting electrolyte together, the positive active substance is fully mixed in the positive electrolyte, under the condition that the standard activity product of the anions of the positive active substance and each single cation is unchanged, the types of the cations existing in the positive electrolyte are increased, the activity product of the single cations and the anions of the positive active substance can be reduced, and therefore the solubility of the positive active substance in the positive electrolyte is improved.
In order to improve the volume capacity of one side of the anode, a solid energy storage material is also arranged in the anode electrolyte storage tank 2; the solid energy storage material is of a block structure and is prepared from the solid energy storage material, the solid energy storage material is composed of one or two of Prussian Blue (PB) and Prussian White (PW), the solid energy storage material cannot enter the positive half cell 1-1 from the positive electrolyte liquid storage tank 2 along with the positive electrode transmission pipeline 6 and only exists in the positive electrolyte liquid storage tank 2, and the solid energy storage material is prevented from entering the flow battery unit 1 from the positive electrolyte liquid storage tank 2 through the barrier with the three-dimensional net structure.
The solid energy storage material and the positive active material have the same oxidation-reduction potential, and in the charge-discharge process of the flow battery system, the actual potential of the positive electrolyte of the positive half battery 1-1 is as follows:
wherein c is1Is the oxidation state concentration of the anion of the positive electrode active material, c2As the reduced concentration of the anion of the positive electrode active material, E0The standard potential of the electrolyte is adopted, the Nernst potential of the anode electrolyte is increased or reduced along with the change of the concentration of the oxidation state of the anode active substance anions relative to the reduction state, the anode active substance anions can realize targeted oxidation and reduction on the solid energy storage material, in the process, the electric energy storage and discharge of the solid energy storage material are realized, the common energy storage of the anode active substance and the solid energy storage material is further realized, and the purpose of improving the volume capacity of one side of the anode is achieved.
The solid energy storage material is oxidized or reduced by the anode active substance in a targeted manner, and the solid energy storage material and the hetero-ionic effect of the anode active substance in the anode electrolyte act synergistically, so that the volume capacity of the flow battery is greatly improved, and the cycle performance is excellent.
In one embodiment of the present application, when the cathode active material is potassium ferricyanide and the solid energy storage material is prepared from Prussian Blue (PB), the specific reaction equation of the cathode active material anion to the solid energy storage material to achieve targeted oxidation and reduction is as follows:
（1）。
during the charging process, an oxidation reaction occurs on the electrode of the positive half cell 1-1, and the equation of the reaction is as follows:
formation following oxidation state [ Fe (CN)6]3-The concentration is gradually increased, the actual potential E of the positive electrolyte in the positive electrolyte storage tank 2 is gradually increased and exceeds the potential of Prussian white PW, and the reverse reaction of the formula (1) occurs, so that the oxidation state [ Fe (CN)6]3-Oxidation of reduced Prussian white PW to oxidized Prussian blue PB, solid energy storage materials store electric energy, and [ Fe (CN)6]3-Is reduced to [ Fe (CN)6]4-，[Fe(CN)6]4-Entering the positive half cell 1-1 along with the positive circulating pump 4, and continuing to perform charging reaction:
. The above process was repeated until all Prussian white PW was oxidized to Prussian blue PB, [ Fe (CN)6]4-Total oxidation to [ Fe (CN)6]3-And the charging is finished. In the process, the common energy storage of the positive active material and the solid energy storage material is completed.
During the discharge process, a reduction reaction occurs on the electrode of the positive half cell 1-1, and the equation of the reaction is as follows:
following reduction [ Fe (CN) ]6]4-The concentration is gradually increased, the actual potential E of the positive electrolyte in the positive electrolyte storage tank 2 is gradually reduced and is lower than the potential of Prussian blue PB, the forward reaction of the formula (1) occurs, and the reduction state [ Fe (CN)6]4-Reduction of Prussian blue PB to Prussian white PW, solid energy storage material releasing stored electrical energy, and [ Fe (CN)6]4-Is oxidized to [ Fe (CN) ]6]3-，[Fe(CN)6]3-And (3) entering the positive half cell 1-1 along with the positive circulating pump 4, and continuing to perform a discharge reaction:
. The above process was repeated until all Prussian blue PB was reduced to Prussian white PW, [ Fe (CN) ]6]3-Total reduction to [ Fe (CN)6]4-And the discharge is ended. The process completes the common energy release of the positive active material and the solid energy storage material.
The solid energy storage material is prepared by adopting a pouring method or an electrostatic spinning method, and the solid energy storage material prepared by the electrostatic spinning method has a high specific surface area, so that the utilization rate of the solid energy storage material is greatly improved, and the volume capacity of the flow battery is further improved.
The preparation method of the solid energy storage material specifically comprises the following steps:
s1, dissolving a high molecular polymer in an organic solvent to obtain a high molecular polymer solution;
the high molecular polymer is polyvinylidene fluoride (PVDF) with the number average molecular weight of 10-100 ten thousand;
the organic solvent comprises one or two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone;
the mass volume ratio of the high molecular polymer to the organic solvent is 1 g: 2 mL-5 mL.
S2, adding a solid energy storage substance into the high molecular polymer solution to obtain an electrostatic spinning solution; the solid energy storage material comprises one or two of Prussian Blue (PB) and Prussian White (PW);
the mass ratio of the solid energy storage substance to the high molecular polymer is (1: 9) - (9: 1);
s3, carrying out electrostatic spinning treatment on the electrostatic spinning solution, and pressing and drying the obtained disordered jet-shaped fiber material to obtain a solid energy storage material with a block structure;
the electrostatic spinning treatment specifically comprises the following steps: injecting the electrostatic spinning solution into an injector, wherein the capacity of the injector is 10-20 mL, the electrostatic spinning solution in the injector is sprayed onto a receiving plate in a high-pressure disordered manner, the distance from a needle head of the injector to the receiving plate is 10-25 cm, the spraying rate is 0.5-3 mL/h, the voltage is set to be 10-30 kV, the spinning temperature is controlled to be 20-70 ℃, the air humidity is 20-60%, the receiving plate preferably adopts aluminum foil paper or copper plate, and disordered spraying-shaped fiber materials are formed on the receiving plate. Due to the improvement of the preparation process, the specific surface area of the solid energy storage material adopted by the application is greatly improved, so that the solid utilization rate of the solid energy storage material is greatly improved, and the solid utilization rate of the solid energy storage material obtained by electrostatic spinning is improved to 80%.
In the prior art, the solid energy storage material is obtained by adopting extrusion molding and pouring molding, the specific surface area of the solid energy storage material obtained by the method is small, the contact area of the solid energy storage material and the anode electrolyte is small, and the utilization rate of the solid energy storage material is low.
In order to ensure high volume capacity of the flow battery full cell, the negative active material of the present application preferably adopts an active material with ultra-high volume capacity, including potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, [ DCNQI [ ]]2Any one or more of X. The concentration range of the negative electrode active substance in the negative electrode electrolyte is 0.1-12 mol/L.
The anode material of the anode half cell 1-1 is any one of carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt and carbon cloth.
The negative electrode material of the negative electrode half cell 1-3 is any one of a carbon felt, a graphite plate, a graphene modified carbon felt, a graphite alkyne modified carbon felt, carbon cloth, a nickel net and a modified nickel net.
The separator 1-2 includes any one of a Nafion film, a PE film, a PP film, a SPEEK film, a PBI film, a PEO film, a SPES film, a PIFE film, a PVDF film, and each separator modified separator. The modification method is to use LiOH, KOH, NaOH and NH4Soaking the diaphragm in any Cl aqueous solution, heating at constant temperature preferably to 40-90 ℃ for 0.5-6 h, cleaning, and drying to obtain Li+、K+、Na+Or NH4 +An ion-modified membrane.
Example 1
This implementationIn the example, the positive active material in the flow battery system adopts K of 0.65mol/L4Fe(CN)6+0.65mol/L of Na4Fe(CN)6KCl with 0.5mol/L of supporting electrolyte; k of 2mol/L of negative electrode active material2S, KCl with 1mol/L supporting electrolyte; 4g of PB solid energy storage material prepared by a casting method is loaded in the anode liquid storage tank; the diaphragm adopts modified Nafion conduction K+A diaphragm; the constant current charge-discharge cycle performance test is carried out on the flow battery system, the flow rates of the positive electrolyte and the negative electrolyte are both 20mL/min, the charge cut-off voltage is 1.4V, the discharge cut-off voltage is 0.4V, and the current density is 30mA/cm2The average coulombic efficiency of the flow battery system of this example was 99.0%, the average voltage efficiency was 78.3%, the average energy efficiency was 78.8%, and the volume capacity was 48.5 Ah/L.
Example 2
In this example, the cycle performance diagram obtained is shown in fig. 2, except that 4g of the PB solid energy storage material prepared by the electrospinning method was loaded in the positive electrode liquid storage tank, and the average coulombic efficiency of the battery of the flow battery system of this example was 99.4%, the average voltage efficiency was 79.3%, the average energy efficiency was 79.8%, and the volume capacity was 54.4Ah/L, as described in example 1. And carrying out rate performance test on the flow battery, wherein the current density is 20mA/cm2、40mA/cm2、60mA/cm2、80mA/cm2、100 mA/cm2、120mA/cm2、2mA/cm2The magnification map is obtained as shown in fig. 3.
Preparing a PB solid energy storage material with a high specific surface area through electrostatic spinning: weighing 5g of PVDF with the molecular weight of 60 ten thousand, placing the PVDF in a three-neck flask, adding 30mL of N, N-dimethylacetamide into the three-neck flask, and fully stirring and dissolving at room temperature to obtain a transparent high polymer solution; and weighing 15g of PB, adding the PB into the high polymer solution, and fully stirring to obtain the viscous electrostatic spinning solution. The method comprises the steps of extracting electrostatic spinning solution by using a 10mL injector, spraying the electrostatic spinning solution in the injector to a receiving plate in a disordered mode through high pressure, wherein the distance between a needle head of the injector and the receiving plate is 20cm, the receiving plate is a copper plate, the spinning voltage is set to be 25kV, the spraying rate is set to be 1mL/h, 8mL of electrostatic spinning solution is sprayed in total, the spinning temperature is 25 ℃, the average air humidity is 30%, a PB fiber material in a disordered spraying shape is formed on the receiving plate, and then pressing and air drying are carried out for 6 hours at the temperature of 80 ℃ to obtain the PB solid energy storage material for the flow battery.
Example 3
In the embodiment, the positive active material in the flow battery system adopts 0.55mol/L K4Fe(CN)6+0.55mol/L of Na4Fe(CN)6Otherwise, the same procedure as in example 2 was repeated. The average coulombic efficiency of the flow battery system of the embodiment is 99.3%, the average voltage efficiency is 79.2%, the average energy efficiency is 80.6%, and the volume capacity is 49.3 Ah/L.
Example 4
In the embodiment, the positive active material in the flow battery system adopts 0.5mol/L K4Fe(CN)6+0.5mol/L of Na4Fe(CN)6+0.5mol/L of (NH)4)4Fe(CN)6Otherwise, the same procedure as in example 2 was repeated. The average coulombic efficiency of the flow battery system of the embodiment is 99.1%, the average voltage efficiency is 81.2%, the average energy efficiency is 80.5%, and the volume capacity is 59.6 Ah/L.
Example 5
In the embodiment, the positive active material in the flow battery system adopts 0.65mol/L K4Fe(CN)6+0.65mol/L of (NH)4)4Fe(CN)6Otherwise, the same procedure as in example 2 was repeated. The average coulombic efficiency of the flow battery system of the embodiment is 99.4%, the average voltage efficiency is 78.4%, the average energy efficiency is 79.7%, and the volume capacity is 54.5 Ah/L.
Example 6
In this example, 0.8mol/L K was used as the positive electrode active material4Fe(CN)6+0.8mol/L of Na4Fe(CN)6Otherwise, the same procedure as in example 2 was repeated. The average coulombic efficiency of the flow battery system of the embodiment is 99.5%, the average voltage efficiency is 68.5%, the average energy efficiency is 69.4%, and the volume capacity is 68.7 Ah/L.
Example 7
In this example, 0.65mol of the positive electrode active material was usedK of/L3Fe(CN)6+0.65mol/L of (NH)4)3Fe(CN)6Otherwise, the average coulombic efficiency of the flow battery system of this example was 99.3%, the average voltage efficiency was 80.1%, the average energy efficiency was 79.5%, and the volume capacity was 54.5Ah/L, which were the same as in example 2.
Example 8
In this example, 0.8mol/L K was used as the positive electrode active material3Fe(CN)6+0.8mol/L of (NH)4)3Fe(CN)6Otherwise, the flow battery system of this example was identical to example 2 in that the average coulombic efficiency of the battery was 98.5%, the average voltage efficiency was 78.6%, the average energy efficiency was 78.9%, and the volume capacity was 68.5 Ah/L.
Example 9
In this example, 0.1mol/L of [ DCNQI ] was used as the positive electrode active material]2NH4And 0.1mol/L of [ DCNQI]2K, Bu supporting 0.2mol/L electrolyte4NClO4The negative electrode active material was 0.1mol/L of [ DCNQI ]]2NH4Bu with 0.2mol/L supporting electrolyte4NClO4The membrane adopts modified Nafion to conduct NH4 +A diaphragm; 4g of PB solid energy storage material prepared by an electrostatic spinning method is loaded in the positive liquid storage tank; performing constant current charge and discharge test on the redox flow battery, wherein the current density is 1mA/cm2. The average coulombic efficiency of the flow battery system of the embodiment is 92.6%, the average voltage efficiency is 68.5%, the average energy efficiency is 69.3%, and the volume capacity is 22.7 Ah/L. The obtained cycle performance graph is shown in fig. 4, exhibiting excellent coulombic efficiency.
Example 10
In this example, 0.1mol/L of [ DCNQI ] was used as the positive electrode active material]2Li and 0.1mol/L of [ DCNQI]2NH4Bu with 0.2mol/L of supporting electrolyte4NClO4The negative electrode active material was 0.1mol/L of [ DCNQI ]]2NH4Bu with 0.2mol/L supporting electrolyte4NClO4The membrane adopts modified Nafion to conduct NH4 +A diaphragm; method for loading 4g electrostatic spinning in positive liquid storage tankPreparing a PB solid energy storage material; performing constant current charge and discharge test on the redox flow battery, wherein the current density is 1mA/cm2. The average coulombic efficiency of the flow battery system of the embodiment is 92.5%, the average voltage efficiency is 63.4%, the average energy efficiency is 64.2%, and the volume capacity is 24.1 Ah/L.
Example 11
In this example, 0.1mol/L of [ DCNQI ] was used as the positive electrode active material]2Li, 0.1mol/L [ DCNQI ]]2NH40.1mol/L of [ DCNQI]2Na, 0.1mol/L of [ DCNQI]2K, Bu supporting 0.2mol/L electrolyte4NClO4The negative active material is 0.1mol/L of [ DCNQI]2NH4Bu with 0.2mol/L supporting electrolyte4NClO4The membrane adopts modified Nafion to conduct NH4 +A diaphragm; 4g of PB solid energy storage material prepared by an electrostatic spinning method is loaded in the positive liquid storage tank; performing constant current charge and discharge test on the redox flow battery, wherein the current density is 1mA/cm2. The average coulombic efficiency of the flow battery system in the embodiment is 91.1%, the average voltage efficiency is 66.4%, the average energy efficiency is 67.1%, and the volume capacity is 29.1 Ah/L.
Example 12
The same as example 2 except that the negative electrode active material was 1mol/L potassium sulfide +1mol/L calcium sulfide; the average coulombic efficiency of the flow battery system of the embodiment is 97.8%, the average voltage efficiency is 69.5%, the average energy efficiency is 70.5%, and the volume capacity is 54.1 Ah/L.
Example 13
The same as example 2 except that the concentration of the negative electrode active material was 12 mol/L; the average coulombic efficiency of the flow battery system of the embodiment is 96.4%, the average voltage efficiency is 68.5%, the average energy efficiency is 69.3%, and the volume capacity is 54.5 Ah/L.
Comparative example 1
In the comparative example, 0.8mol/L K is used as the positive electrode active material in the flow removal battery system3Fe(CN)6The positive liquid storage tank is not loaded with PB solid energy storage material, the rest is the same as the embodiment 2, and the average coulombic efficiency of the comparative example battery is 962%, an average voltage efficiency of 70.0%, an average energy efficiency of 72.8%, and a volume capacity of 22.2Ah/L, a cycle performance graph is obtained as shown in fig. 5, and a cell capacity voltage graph of the flow battery systems obtained in this comparative example and example 2 is obtained as shown in fig. 6.
Comparative example 2
In the comparative example, 0.8mol/L K is used as the positive electrode active material in the flow removal battery system3Fe(CN)6Otherwise, the same as example 2, the average coulombic efficiency of the cell of this comparative example was 97.2%, the average voltage efficiency was 72.3%, the average energy efficiency was 70.6%, and the volume capacity was 11.9 Ah/L.
Comparative example 3
In the comparative example, the operation is the same as that in example 2 except that no PB solid energy storage material is loaded in the positive liquid storage tank in the flow battery system, the average coulombic efficiency of the flow battery system of the comparative example is 99.7%, the average voltage efficiency is 69.3%, the average energy efficiency is 69.5%, and the volume capacity is 34.4Ah/L, and the obtained cycle performance graph is shown in fig. 7. The volume capacity voltage comparison graph of example 2, comparative example 1, and comparative example 3 is shown in fig. 8.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A high-volume-capacity flow battery system is characterized in that two ferricyanides, two to three ferrocyanides or two to four [ DCNQI ] active substances with different cations are used as the positive active substances]2X; the iron cyanidationThe substance comprises potassium ferricyanide or ammonium ferricyanide; the ferrocyanide comprises potassium ferrocyanide, sodium ferrocyanide or ammonium ferrocyanide; the [ DCNQI ]]2X comprises [ DCNQI]2Na、[DCNQI]2K、[DCNQI]2Li or [ DCNQI ]]2NH4(ii) a When the positive active substance is two ferricyanides and two to three ferrocyanides with different cations, the anion concentration range of the positive active substance is 1.1mol/L to 1.6 mol/L; the positive active substance is two to four kinds of [ DCNQI ] with different cations]2When X is higher, the anion concentration range of the positive active material is 0.2-0.4 mol/L; the negative active material is selected from potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, [ DCNQI ]]2Any one or more of X, wherein the concentration range of the negative active material is 0.1-12 mol/L; the supporting electrolyte in the positive electrolyte or the negative electrolyte comprises LiCl and Li2SO4、LiNO3、LiOH、KCl、K2SO4、KNO3、KOH、NaCl、Na2SO4、NaNO3、NaOH、NH4Cl、(NH4)2SO4、Bu4NClO4Any one or more of; and a solid energy storage material is arranged in the anode electrolyte liquid storage tank, and the solid energy storage material is composed of one or two of Prussian blue and Prussian white.
2. The high volumetric capacity flow battery system of claim 1, wherein the solid energy storage material is prepared from a solid energy storage substance by a casting method or an electrospinning method.
3. The high volume capacity flow battery system of claim 1, wherein the sum of the concentrations of supporting electrolyte in the anolyte or catholyte is 0.2-4 mol/L.
4. The high volume capacity flow battery system of claim 3, wherein the cation species of the supporting electrolyte in the positive electrolyte solution is 1-4 species, and the cation species of the supporting electrolyte in the negative electrolyte solution is one species.
5. The high volume capacity flow battery system of claim 1 or 4, wherein when two cations are present in the positive electrolyte, the molar ratio of the two cations is (1-3): (1-3); when three cations exist in the positive electrode electrolyte, the molar ratio of the three cations is (1-3): (1-3): (1-3); when four cations are present in the positive electrode electrolyte, the molar ratio of the four cations is (1-3): (1-3): (1-3): (1-3).
6. The high volumetric capacity flow battery system of claim 2, wherein the solid energy storage material is prepared by an electrospinning process comprising the steps of:
s1, dissolving a high molecular polymer in an organic solvent to obtain a high molecular polymer solution;
the high molecular polymer is polyvinylidene fluoride with the number average molecular weight of 10-100 ten thousand; the organic solvent comprises any one or two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone; the mass volume ratio of the high molecular polymer to the organic solvent is 1 g: 2 mL-5 mL;
s2, adding a solid energy storage substance into the high molecular polymer solution to obtain an electrostatic spinning solution; the mass ratio of the solid energy storage substance to the high molecular polymer S1 is (1: 9) - (9: 1);
and S3, carrying out electrostatic spinning treatment on the electrostatic spinning solution, and pressing and drying the obtained disordered jet-shaped fiber material to obtain the solid energy storage material.
7. The high volume capacity flow battery system of claim 6, wherein in S3, the electrospinning process is specifically: injecting the electrostatic spinning solution into an injector, wherein the capacity of the injector is 10-20 mL, the electrostatic spinning solution in the injector is sprayed onto a receiving plate in a high-pressure disordered manner, the distance from a needle head of the injector to the receiving plate is 10-25 cm, the spraying rate is 0.5-3 mL/h, the voltage is set to be 10-30 kV, the spinning temperature is controlled to be 20-70 ℃, the air humidity is 20-60%, the receiving plate is aluminum foil paper or copper plate, and a disordered spraying-shaped fiber material is formed on the receiving plate.
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Effective date of registration: 20221130 Address after: Room 915-23, 9/F, Building B2, Lugu Science and Technology Innovation and Entrepreneurship Park, No. 1698, Yuelu West Avenue, Changsha Hi tech Development Zone, Hunan 410205 Patentee after: Hunan Chuangda Energy Storage Technology Co.,Ltd. Address before: 410114 No. 960, Section 2, Wanjiali South Road, Tianxin District, Changsha City, Hunan Province Patentee before: CHANGSHA University OF SCIENCE AND TECHNOLOGY |