CN114899466A - Ferromanganese flow battery and manufacturing method thereof - Google Patents
Ferromanganese flow battery and manufacturing method thereof Download PDFInfo
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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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention belongs to the field of batteries, and discloses a ferromanganese flow battery and a manufacturing method thereof. The ferromanganese redox flow battery comprises a battery module formed by connecting one or more than two battery units in series, an electrolyte storage tank, a circulating pump, a circulating pipe and a control system; the battery unit comprises a positive electrolyte, a negative electrolyte, an electrode and an electrode plate; the positive electrode electrolyte is an acidic solution containing manganese ions (II or III), and the negative electrode electrolyte is an acidic solution containing iron ions (II or III). The ferromanganese redox flow battery has the characteristics of low material cost, relatively high battery charging and discharging efficiency, long battery cycle charging and discharging life, stable energy storage, high safety and easy later maintenance.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a ferromanganese flow battery and a manufacturing method thereof.
Background
The energy is a necessity for human production and life. The use of fossil energy by humans results in the annual emission of significant quantities of CO to the environment 2 Gas, aggravates the global warming effect. In order to achieve the aim of "carbon neutralization", new energy power generation technologies such as solar energy and wind energy are being vigorously developed. However, the electric energy generated by these new energy power generation technologies has volatility, and direct integration into the power grid damages the power grid facilities. One of the solutions to this problem is energy storage, which is a necessary supporting facility for future wind and solar power generation. Advanced energy storage technology has become a hot spot of global science and technology competition, and is also a key technology for realizing the strategic target of new energy transformation. The existing energy storage technologies mainly comprise physical energy storage technologies such as pumped storage, compressed air energy storage, flywheel energy storage, thermal energy storage and superconducting energy storage, and lithium ion batteries, flow batteries, sodium-sulfur batteries, super capacitors, zinc ion batteries, sodium ion batteries and the likeElectrochemical energy storage technology.
Among various energy storage technologies, the secondary battery energy storage technology has the advantages of high energy efficiency, high energy density, high charging and discharging speed, no mechanical transmission, high mobility and the like, and is one of important energy storage technologies. Among various secondary batteries, the all-vanadium redox flow battery (VFB) has advantages of high safety, easy recovery of materials, and the like. VFB energy storage systems have gained increasing attention and market interest in recent years, particularly in the long term energy storage area. However, vanadium (V) is a metal resource which is not abundant in reserve resources, and the environmental pollution is relatively serious during the exploitation, use and the like, and VOSO which is one of VFB raw materials 4 This directly leads to VFB's not yet being commercially available on a large scale.
In order to avoid using elements such as V that are not high in abundance, researchers have developed flow battery systems such as zinc half-flow batteries, organic flow batteries, and iron-chromium flow batteries. However, these different flow battery systems still face the key problems of poor performance and high cost, which is the main reason why these new flow batteries are difficult to be widely used. Therefore, it is an important objective of various current research institutions and companies to develop the next generation flow battery to improve the performance of the flow battery and further reduce the material cost.
Disclosure of Invention
Aiming at the problems that the secondary battery uses the vanadium-containing raw materials and other raw materials which have less reserve resources and are easy to cause environmental pollution, the invention provides a ferromanganese flow battery and a manufacturing method thereof.
The flow battery has the advantages of extremely low cost, rich raw material resources, high safety and easiness in later maintenance, and can meet the requirements of large-scale energy storage on key indexes of the battery.
In order to achieve the purpose, the method specifically comprises the following technical scheme:
a ferromanganese redox flow battery comprises a battery module formed by connecting one or more than two battery units in series, an electrolyte storage tank, a circulating pump, a circulating pipe and a control system;
the battery unit comprises positive electrolyte and negative electrolyte;
the positive electrolyte is an acid solution containing manganese ions; the manganese ions are at least one of bivalent manganese ions and trivalent manganese ions;
the negative electrode electrolyte is an acidic solution containing iron ions; the iron ions are at least one of ferrous ions and ferric ions.
In a preferred embodiment of the present invention, the battery cell further comprises an electrode.
In a preferred embodiment of the present invention, the electrode is a carbon felt.
The carbon felt comprises at least one of graphite carbon felt and amorphous carbon felt, the thickness of the carbon felt is 0.1-10 mm, the carbon felt can be purchased commercially and can also be obtained by carbonizing polyacrylonitrile and polyurethane polymer fibers.
The connection relationship of each component of the flow battery is as follows: one end of the electrode is connected with the control system, the other end of the electrode is connected with the positive electrolyte or the negative electrolyte, and a diaphragm is arranged between the positive electrolyte and the negative electrolyte; the electrolyte storage tank stores anode electrolyte or cathode electrolyte, the circulating pipe is provided with a circulating pump, the electrolyte storage tank is connected with the battery unit through the circulating pipe, and the anode electrolyte or the cathode electrolyte flows to the battery unit from the electrolyte storage tank through the circulating pipe when the battery runs and then flows to the electrolyte storage tank from the battery unit.
In a preferred embodiment of the present invention, the battery cell further includes a sealing rubber gasket, a fixing member, and an electrode plate.
The electrode plate can be made of conventional carbon steel materials, such as stainless steel, so that the strength required for fixing each component of the flow battery is met, the corrosion resistance is realized, and each required connector or shape is formed easily. As a preferable embodiment of the invention, the side of the electrode plate facing to the positive electrolyte or the negative electrolyte is provided with a groove, the groove is used for placing a carbon felt, a gap is reserved between the carbon felt and the sealing rubber gaskets and used for filling the positive electrolyte or the negative electrolyte, the diaphragm is placed between the two sealing rubber gaskets, and the flow battery stack is fixed through the fixing component.
The fixing part is a screw.
In a preferred embodiment of the present invention, the positive electrode electrolyte is one of an acidic solution containing manganese ions or an acidic solution containing manganese ions and iron ions;
the negative electrode electrolyte is one of an acidic solution containing iron ions or an acidic solution containing manganese ions and iron ions;
the concentration of the iron ions or the manganese ions in the electrolyte is directly related to the performance of the flow battery, and the proper concentration not only saves resources, reduces unnecessary waste and improves the utilization rate of the active components, but also improves the efficiency of converting chemical energy into electric energy by the battery.
The inventor of the invention can find out through experiments that the concentration of manganese ions in the positive electrolyte is 0.1-5 mol L -1 The electrolyte can enable the performance of the battery to reach the required standard.
In a further preferred embodiment of the present invention, the concentration of the manganese ion is 0.2 to 1mol L -1 。
The inventors of the present invention have found through a large number of experiments that the electrolyte has better performance when the acid with manganese ions or iron ions is hydrochloric acid and/or sulfuric acid.
As a preferred embodiment of the present invention, the positive electrode electrolyte is an aqueous solution including a manganese salt, sulfuric acid, and hydrochloric acid.
As a preferred embodiment of the present invention, the manganese salt comprises MnSO 4 、Mn(NO 3 ) 2 、 Mn(CH 3 COO) 2 、MnCl 2 、MnCl 3 、Mn 3 (PO 4 ) 2 At least one of (1).
In a preferred embodiment of the present invention, the concentration of iron ions in the negative electrode electrolyte is 0.1 to 5mol L -1 。
In a further preferred embodiment of the present invention, the concentration of the iron ion is 0.2 to 1mol L -1 。
As a preferred embodiment of the present invention, the negative electrode electrolyte is an aqueous solution including iron salt, sulfuric acid and hydrochloric acid.
As a preferred embodiment of the present invention, the iron salt comprises FeSO 4 、FeCl 3 、FeCl 2 、 Fe(NO 3 ) 3 、Fe(NO 3 ) 2 、Fe(CH 3 COO) 2 、Fe(CH 3 COO) 2 、FeF 3 、FeI 3 At least one of (1).
In a preferred embodiment of the present invention, the concentration of sulfuric acid is 0.1 to 10mol L -1 。
In a preferred embodiment of the present invention, the hydrochloric acid concentration is 0.1 to 10mol L -1 。
The inventor of the invention discovers through experimental research that a novel ferromanganese redox flow battery with standard performance and extremely low cost can be constructed by taking an acidic aqueous solution containing manganese ions or iron ions as an electrolyte solution.
In a preferred embodiment of the present invention, the separator is an ion-conducting membrane.
The ion conductive membrane is a polymer membrane with cation conductivity and can be used as a medium for ion exchange.
As a preferred embodiment of the present invention, the ion-conducting membrane comprises at least one of a perfluorosulfonic acid membrane, a sulfonated polyether ether ketone membrane, a polystyrene membrane, and a polyether sulfone membrane.
In a preferred embodiment of the present invention, the sulfonated polyether ether ketone membrane is prepared by sulfonating polyether ether ketone with concentrated sulfuric acid. The sulfonated polyether-ether-ketone membrane can be directly purchased from the market, and can be prepared in a laboratory due to the relatively simple preparation process.
A manufacturing method of a ferromanganese flow battery comprises the following steps,
s1: assembling a battery module formed by connecting one battery unit or more than two battery units in series, an electrolyte storage tank, a circulating pump, a circulating pipe and a control system to form a flow battery pile;
s2: and (4) injecting the positive electrolyte and the negative electrolyte into the flow battery pile in the step S1 to obtain the ferromanganese flow battery.
In the ferromanganese flow battery, a carbon steel material is taken as an electrode plate, and the electrode plate is provided with a groove and an interface, so that a gasket and a screw can be conveniently installed and connected with other parts; the cation conducting membrane is a diaphragm which separates the positive electrolyte from the positive electrolyte and can normally transmit cations; the carbon felt is used as an electrode, all parts are connected through rubber gaskets and screws, pipelines are well connected, positive electrolyte and positive electrolyte are respectively pumped into the positive side and the negative side through a circulating pump in the liquid storage tank, and charging and discharging are carried out through a battery control system.
Compared with the prior art, the invention has the following progress:
(1) because Mn and Fe are metal elements with abundant resources and the production cost is relatively low, the two elements are used as active substances of the battery electrolyte solution, so that the flow battery has absolute advantages in cost and resources. The ferromanganese flow battery material has low cost (about 90 yuan/degree of electricity), rich raw material resources and suitability for large-scale mass production.
(2) The ferromanganese redox flow battery has relatively high charge and discharge efficiency, long cycle charge and discharge service life and stable energy storage.
(3) The ferromanganese flow battery has high safety and easy later maintenance, and the performance index of the ferromanganese flow battery meets the requirement of large-scale energy storage on the battery, thereby having great commercial prospect.
(4) The ferromanganese redox flow battery can be connected in series without temperature control, and is abuse-resistant.
Drawings
Fig. 1 is a structural diagram of a ferro-manganese flow battery prepared in examples 1-5 and a working principle diagram thereof.
Fig. 2 is a graph of the charging performance test results of the iron-manganese flow battery prepared in example 1.
Fig. 3 is a graph of the discharge performance test results of the iron-manganese flow battery prepared in example 1.
FIG. 4 is a graph of the result of the ferro-manganese liquid flow charge-discharge cycle performance test made in example 1.
FIG. 5 is a graph of the results obtained in examples 2 and 3The charging performance test result chart of the ferro-manganese flow battery is shown, wherein the charging performance test result chart is 1.0mol/LMn 2+ /Fe 3+ Representing the charging performance test results of the iron-manganese flow battery prepared in example 2, 0.5mol/LMn 2+ /Fe 3+ The charging performance test results of the iron-manganese flow battery prepared under example 3 are represented.
FIG. 6 is a graph showing the results of testing the discharge performance of the FeMn flow batteries prepared in examples 2 and 3, 1.0mol/LMn 2+ /Fe 3+ Representing the results of the discharge performance test of the iron-manganese flow battery prepared in example 2, 0.5mol/LMn 2+ /Fe 3+ Represents the discharge performance test results of the iron-manganese flow battery prepared under the example 3.
FIG. 7 is a graph showing the results of the charging and discharging tests of the FeMn flow battery obtained in example 3, wherein the active material concentration is 0.2mol/L Mn 2+ /Fe 3+ 。
Fig. 8 is a graph showing the result of the power performance of the single iron-manganese redox flow battery prepared in example 2, wherein a straight line is the test data of the discharge voltage varying with the current density, a curve is the test data of the power density varying with the current density, and the power density is calculated by multiplying the voltage by the current density, and it can be seen that the peak output power of the single battery is 70mW cm -2 Corresponding to a current density of 160mA cm -2 。
Fig. 9 is a physical diagram of a stack obtained by connecting the iron-manganese flow batteries prepared in examples 1-5 in series.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
(1) Preparing an electrolyte
Mixing MnSO 4 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a positive electrolyte, wherein MnSO is contained in the positive electrolyte 4 Has a concentration of 1.0mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 1.0mol L, respectively -1 。
FeCl is added 3 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a negative electrode electrolyteLiquid in which FeCl 3 Has a concentration of 1.0mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 1.0mol L, respectively -1 。
(2) Preparation of the separator
3g of polyetheretherketone was sulphonated with 80mL of concentrated sulphuric acid (98%) under heating in a water bath at 70 ℃, followed by rinsing with copious amounts of ultrapure water and suction filtration, and drying in an oven at 70 ℃ to finally prepare a dry sulphonated polyetheretherketone membrane.
(3) Assembled battery
The single liquid flow battery device comprises a circulating water pump, a circulating pipe, an electrolyte liquid storage tank (10mL), a control system (Xinwei battery testing system), two stainless steel electrode plates (5x5cm), two rubber gaskets, a diaphragm and two carbon felts (2x2cm), wherein the two electrode plates are provided with grooves towards the side faces of the electrolyte and used for being respectively placed on the carbon felts, a gap is formed between the carbon felts and the sealing rubber gaskets and used for placing the electrolyte, the diaphragm is placed between the two sealing rubber gaskets, the electrode plates are fixed through screws, and a battery stack can be assembled. And (2) then injecting the positive electrolyte and the negative electrolyte prepared in the step (1) into a liquid storage tank, and respectively injecting the positive electrolyte and the negative electrolyte into the positive electrode side and the negative electrode side to form the ferromanganese redox flow battery. The circulating flow of the electrolyte is realized through the circulating high-pressure water pump and the pipeline system thereof, and the charging and discharging of the battery are realized through the control system. The membrane in this embodiment is the polyetheretherketone membrane prepared in step (2).
(4) Ferromanganese flow battery charging voltage test
The flow battery of this example was tested at a constant current of 10mA using a constant current charging method, and the battery voltage change was recorded, with the constant current discharge being converted when the voltage was charged to 1.2V. The result of the charge test is shown in FIG. 3, and the charge capacity is 4 mAh.
(5) Discharge voltage test of ferromanganese flow battery
The flow battery of this example was tested at a constant current of 10mA using a constant current discharge method, and the battery voltage change was recorded, and when the voltage dropped to 0V, it was charged at a constant current. The discharge test results are shown in fig. 2, and the discharge capacity is 3.65 mAh.
(6) Ferromanganese flow battery cycle charge-discharge life test
The flow battery of the embodiment is tested under a constant current of 10mA by adopting a constant current charging and discharging method, and the capacity retention rate of the flow battery is calculated after 180 cycles. As shown in fig. 4, the cycle test results showed that the capacity retention rate decreased and then increased, and the final capacity retention rate was 100%.
Example 2
(1) Preparing an electrolyte
Mixing MnSO 4 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a positive electrolyte, wherein MnSO is contained in the positive electrolyte 4 Has a concentration of 1.0mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 1.0mol L, respectively -1 。
FeCl 3 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a negative electrode electrolyte, wherein MnSO is contained in the negative electrode electrolyte 4 Has a concentration of 1.0mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 1.0mol L, respectively -1 。
(2) Preparation of the separator
3g of polyetheretherketone was sulphonated with 80mL of concentrated sulphuric acid (98%) under heating in a water bath at 70 ℃, followed by rinsing with copious amounts of ultrapure water and suction filtration, and drying in an oven at 70 ℃ to finally prepare a dry sulphonated polyetheretherketone membrane.
(3) Assembled battery
The single liquid flow battery device comprises a circulating water pump, a circulating pipe, an electrolyte liquid storage tank (10mL), a control system (Xinwei battery testing system), two stainless steel electrode plates (5x5cm), two rubber gaskets, a diaphragm and two carbon felts (2x2cm), wherein the two electrode plates are provided with grooves towards the side faces of the electrolyte and used for being respectively placed on the carbon felts, a gap is formed between the carbon felts and the sealing rubber gaskets and used for placing the electrolyte, the diaphragm is placed between the two sealing rubber gaskets, the electrode plates are fixed through screws, and a battery stack can be assembled. And (2) then injecting the positive electrolyte and the negative electrolyte prepared in the step (1) into a liquid storage tank, and respectively injecting the positive electrolyte and the negative electrolyte into the positive electrode side and the negative electrode side to form the ferromanganese redox flow battery. The circulating flow of the electrolyte is realized through the circulating high-pressure water pump and the pipeline system thereof, and the charging and discharging of the battery are realized through the control system. The membrane in this embodiment is the polyetheretherketone membrane prepared in step (2).
(4) Charging performance test of ferromanganese flow battery
The charging curve of the flow battery of the embodiment is tested under the condition of 300mA constant current charging by adopting a constant current charging method. The result of the charge test is shown in fig. 5, and the charge capacity is 161.5 mAh.
(5) Discharge performance test of ferromanganese flow battery
The discharge curve of the flow battery of this example was tested under a constant current discharge condition of 300mA using a constant current discharge method, and the test result is shown in fig. 5, where the discharge capacity is 108.6 mAh.
Example 3
(1) Preparing an electrolyte
Mixing MnSO 4 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a positive electrolyte, wherein MnSO is contained in the positive electrolyte 4 Has a concentration of 0.2mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.2mol L, respectively -1 。
FeCl 3 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a negative electrode electrolyte, wherein MnSO is contained in the negative electrode electrolyte 4 Has a concentration of 0.2mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.2mol L, respectively -1 。
(2) Preparation of the separator
Sulfonated with 80mL of concentrated sulfuric acid (98%) in a water bath at 70 ℃ for 3g of polyetheretherketone, followed by rinsing with copious amounts of ultrapure water and suction filtration, and dried in an oven at 70 ℃ to prepare a dry sulfonated polyetheretherketone membrane.
(3) Assembled battery
The single liquid flow battery device comprises a circulating water pump, a circulating pipe, an electrolyte liquid storage tank (10mL), a control system (Xinwei battery testing system), two stainless steel electrode plates (5x5cm), two rubber gaskets, a diaphragm and two carbon felts (2x2cm), wherein the two electrode plates are provided with grooves towards the side faces of the electrolyte and used for being respectively placed on the carbon felts, a gap is formed between the carbon felts and the sealing rubber gaskets and used for placing the electrolyte, the diaphragm is placed between the two sealing rubber gaskets, the electrode plates are fixed through screws, and a battery stack can be assembled. And (2) then injecting the positive electrolyte and the negative electrolyte prepared in the step (1) into a liquid storage tank, and respectively injecting the positive electrolyte and the negative electrolyte into the positive electrode side and the negative electrode side to form the ferromanganese redox flow battery. The circulating flow of the electrolyte is realized through the circulating high-pressure water pump and the pipeline system thereof, and the charging and discharging of the battery are realized through the control system. The membrane in this embodiment is the polyetheretherketone membrane prepared in step (2).
(4) Charging performance test of ferromanganese flow battery
The charging curve of the flow battery of the embodiment is tested under the condition of 300mA constant current charging by adopting a constant current charging method. The charging test results are shown in fig. 7.
(5) Discharge performance test of ferromanganese flow battery
The discharge curve of the flow battery of this example was tested under a constant current discharge condition of 300mA using a constant current discharge method, and the test results are shown in fig. 7.
Example 4
(1) Preparing an electrolyte
Mixing MnSO 4 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a positive electrolyte, wherein MnSO is contained in the positive electrolyte 4 Has a concentration of 0.5mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.5mol L, respectively -1 。
FeCl is added 3 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a negative electrode electrolyte, wherein MnSO is contained in the negative electrode electrolyte 4 Has a concentration of 0.5mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.5mol L, respectively -1 。
(2) Preparation of the separator
3g of polyetheretherketone was sulphonated with 80mL of concentrated sulphuric acid (98%) under heating in a water bath at 70 ℃, followed by rinsing with copious amounts of ultrapure water and suction filtration, and drying in an oven at 70 ℃ to finally prepare a dry sulphonated polyetheretherketone membrane.
(3) Assembled battery
The single liquid flow battery device comprises a circulating water pump, a circulating pipe, an electrolyte liquid storage tank (10mL), a control system (Xinwei battery testing system), two stainless steel electrode plates (5x5cm), two rubber gaskets, a diaphragm and two carbon felts (2x2cm), wherein the two electrode plates are provided with grooves towards the side faces of the electrolyte and used for being respectively placed on the carbon felts, a gap is formed between the carbon felts and the sealing rubber gaskets and used for placing the electrolyte, the diaphragm is placed between the two sealing rubber gaskets, the electrode plates are fixed through screws, and a battery stack can be assembled. And (2) then injecting the positive electrolyte and the negative electrolyte prepared in the step (1) into a liquid storage tank, and respectively injecting the positive electrolyte and the negative electrolyte into the positive electrode side and the negative electrode side to form the ferromanganese redox flow battery. The circulating flow of the electrolyte is realized through a circulating high-pressure water pump and a pipeline system thereof, and the charging and discharging of the battery are realized through a control system. The membrane in this embodiment is the polyetheretherketone membrane prepared in step (2).
(4) Charging performance test of ferromanganese flow battery
The charging curve of the flow battery of the embodiment is tested under the condition of 300mA constant current charging by adopting a constant current charging method. The result of the charge test is shown in fig. 6, and the charge capacity is 76.4 mAh.
(5) Discharge performance test of ferromanganese flow battery
The discharge curve of the flow battery of this example was tested under a constant current discharge condition of 300mA using a constant current discharge method, and the test result is shown in fig. 6, where the discharge capacity is 65.9 mAh.
Example 5
(1) Preparing an electrolyte
Mixing MnSO 4 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a positive electrolyte, wherein MnSO is contained in the positive electrolyte 4 Has a concentration of 0.5mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.5mol L, respectively -1 。
FeCl is added 2 Dissolving the powder in a mixed solution of sulfuric acid and hydrochloric acid to obtain a negative electrode electrolyte, wherein MnSO is contained in the negative electrode electrolyte 4 Has a concentration of 0.5mol L -1 The concentrations of sulfuric acid and hydrochloric acid were 0.5mol L, respectively -1 。
(2) Preparation of the separator
3g of polyetheretherketone was sulphonated with 80mL of concentrated sulphuric acid (98%) under heating in a water bath at 70 ℃, followed by rinsing with copious amounts of ultrapure water and suction filtration, and drying in an oven at 70 ℃ to finally prepare a dry sulphonated polyetheretherketone membrane.
(3) Assembled battery
The single liquid flow battery device comprises a circulating water pump, a circulating pipe, an electrolyte liquid storage tank (10mL), a control system (Xinwei battery testing system), two stainless steel electrode plates (5x5cm), two rubber gaskets, a diaphragm and two carbon felts (2x2cm), wherein the two electrode plates are provided with grooves towards the side faces of the electrolyte and used for being respectively placed on the carbon felts, a gap is formed between the carbon felts and the sealing rubber gaskets and used for placing the electrolyte, the diaphragm is placed between the two sealing rubber gaskets, the electrode plates are fixed through screws, and a battery stack can be assembled. And (2) then injecting the positive electrolyte and the negative electrolyte prepared in the step (1) into a liquid storage tank, and respectively injecting the positive electrolyte and the negative electrolyte into the positive electrode side and the negative electrode side to form the ferromanganese redox flow battery. The circulating flow of the electrolyte is realized through the circulating high-pressure water pump and the pipeline system thereof, and the charging and discharging of the battery are realized through the control system. The membrane in this embodiment is the polyetheretherketone membrane prepared in step (2).
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A ferromanganese flow battery is characterized by comprising a battery module formed by connecting one or more than two battery units in series, an electrolyte storage tank, a circulating pump, a circulating pipe and a control system;
the battery unit comprises a positive electrolyte and a negative electrolyte;
the positive electrolyte is an acid solution containing manganese ions; the manganese ions are at least one of bivalent manganese ions and trivalent manganese ions;
the negative electrode electrolyte is an acidic solution containing iron ions; the iron ions are at least one of ferrous ions and ferric ions.
2. The ferromanganese flow battery of claim 1, wherein the cell further comprises an electrode; one end of the electrode is connected with the control system, the other end of the electrode is connected with the positive electrolyte or the negative electrolyte, and a diaphragm is arranged between the positive electrolyte and the negative electrolyte; the electrolyte storage tank stores anode electrolyte or cathode electrolyte, the circulating pipe is provided with a circulating pump, the electrolyte storage tank is connected with the battery unit through the circulating pipe, and the anode electrolyte or the cathode electrolyte flows to the battery unit from the electrolyte storage tank through the circulating pipe when the battery runs and then flows to the electrolyte storage tank from the battery unit.
3. The ferromanganese flow battery of claim 1, wherein the concentration of manganese ions is 0.1-5 mol L -1 The concentration of the iron ions is 0.1-5 mol L -1 。
4. The ferromanganese flow battery of claim 3, wherein the concentration of manganese ions is 0.2-1 mol L -1 The concentration of the iron ions is 0.2-1 mol L -1 。
5. The ferromanganese flow battery of any of claims 1-4, wherein the negative electrolyte is an aqueous solution comprising iron salts, sulfuric acid, and hydrochloric acid; the anode electrolyte is an aqueous solution containing manganese salt, sulfuric acid and hydrochloric acid.
6. The ferromanganese flow battery of claim 5, wherein said manganese salt comprises MnSO 4 、Mn(NO 3 ) 2 、Mn(CH 3 COO) 2 、MnCl 2 、MnCl 3 、Mn 3 (PO 4 ) 2 At least one of; said iron salt comprises FeSO 4 、FeCl 3 、FeCl 2 、Fe(NO 3 ) 3 、Fe(NO 3 ) 2 、Fe(CH 3 COO) 2 、Fe(CH 3 COO) 2 、FeF 3 、FeI 3 At least one of; the concentration of the sulfuric acid is 0.1-10 mol L -1 (ii) a The concentration of the hydrochloric acid is 0.1-10 mol L -1 。
7. The ferromanganese flow battery of claim 2, wherein said separator is an ion conducting membrane; the electrode is a carbon felt.
8. The ferromanganese flow battery of claim 7, wherein the ion conducting membrane comprises at least one of a perfluorosulfonic acid membrane, a sulfonated polyetheretherketone membrane, a polystyrene membrane, a polyethersulfone membrane; the carbon felt comprises at least one of graphite carbon felt and amorphous carbon felt.
9. The ferromanganese flow battery of any of claims 1-4, wherein the cell further comprises a sealing rubber gasket, a securing feature, and an electrode plate.
10. The method of making a ferromanganese flow battery as in any one of claims 1-9, comprising the steps of,
s1: assembling a battery module formed by connecting one battery unit or more than two battery units in series, an electrolyte storage tank, a circulating pump, a circulating pipe and a control system to form a flow battery pile;
s2: and (4) injecting the positive electrolyte and the negative electrolyte into the flow battery pile in the step S1 to obtain the ferromanganese flow battery.
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