Tin-manganese aqueous flow battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a tin-manganese secondary battery.
Background
Since the twenty-first century, the world's crude oil supply has been increasingly tightened by the increasing global energy demand, and people are also increasingly receiving attention from environmental problems caused by the use of fossil fuels, such as global warming and more severe haze weather. However, due to the intermittent, discontinuous and unstable characteristics of renewable energy sources (such as wind energy, solar energy, tidal energy and the like), the difficulty of large-scale integration of the renewable energy sources into the power grid is increased, and in order to improve the utilization rate of the renewable energy sources, the development of a large-scale energy storage battery system is one of effective approaches.
Battery systems expected to be applied to large-scale energy storage can be simply classified into nonaqueous electrolyte-based battery systems and aqueous electrolyte-based battery systems. For example, conventional lithium ion batteries employ an anhydrous organic solution as an electrolyte, and exhibit a high operating voltage. However, highly toxic and flammable organic electrolytes pose a risk of explosion of the battery, and this problem is more prominent in the field of large-scale energy storage. The high-temperature sodium-sulfur battery adopts liquid molten electrodes, does not contain aqueous electrolyte, and shows high working voltage and energy density, but combustible metal sodium electrodes and sulfur electrodes still have the danger of fire and explosion at high temperature, which has been proved by accidents previously. In addition, the working safety of the battery can be greatly improved by adopting the aqueous electrolyte, and the main reason is that the aqueous electrolyte is not combustible. Therefore, lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, all-vanadium redox flow batteries, zinc-bromine redox flow batteries, recently developed water-based lithium ion/sodium ion batteries and the like based on aqueous electrolyte are expected to be more widely applied to the field of large-scale energy storage. However, the large-scale use of the above-described water-based battery systems still faces these many challenges and bottleneck problems. Firstly, lead-acid batteries, nickel-cadmium vanadium flow batteries, zinc-bromine flow batteries and the like all contain environmentally unfriendly toxic elements, such as lead ions, cadmium ions and elemental bromine; secondly, the electrode reactions of aqueous lithium/sodium ion batteries and lead-acid batteries involve ion intercalation and deintercalation and conversion of crystal structures, exhibiting limited cycle life and power density; finally, the existing commercial vanadium redox flow battery and zinc-bromine redox flow battery must adopt expensive and fluorine-containing ion exchange membranes as battery diaphragms, which increases the cost and simultaneously aggravates the environmental pollution.
In view of the above problems, the present invention proposes a tin-manganese aqueous battery system. The positive pole reaction is bivalent manganese ion (Mn)2 +) Trivalent manganese ion (Mn)3+) The negative electrode reaction is tin (Sn)/tin ion (Sn)2+) In betweenAnd (3) performing a depreciation reaction, and taking an aqueous solution containing divalent tin ions and divalent manganese ions as an electrolyte. Compared with the existing battery system, the battery system has the following advantages: firstly, toxic elements such as lead (Pb), cadmium (Cd), vanadium (V) and the like are not involved in electrode reaction; secondly, toxic and combustible organic electrolyte is not adopted; thirdly, the electrode reaction is not controlled by the diffusion and phase inversion of ions in the electrode crystal structure, and the ultrahigh power characteristic is shown; fourthly, compared with the traditional flow battery which adopts an expensive ion exchange membrane, the battery system adopts a porous PBI membrane, so that the cost is reduced.
Disclosure of Invention
The invention aims to provide a tin-manganese water system flow battery which is long in service life, high in power density and high in stability.
The invention provides a tin-manganese water system flow battery, which comprises: the positive and negative current collectors, electrolyte and PBI membrane between the positive and negative electrodes; the electrolyte contains divalent tin ion (Sn)2+) And divalent manganese ion (Mn)2+) The positive electrode solution of (1); the working principle is shown in figure 1. Divalent manganese ion (Mn) in solution when charging a battery2+) Electrochemical oxidation reaction is carried out on the positive current collector, electrons are lost and oxidized into trivalent manganese ions, the lost electrons flow to the negative electrode through an external circuit, and meanwhile, bivalent tin ions in the solution obtain electrons on the negative electrode, are reduced into metallic tin and are deposited on the negative current collector. The discharging process of the battery is reversed from the charging process. The main electrode reactions of this cell are summarized as follows:
charging process (fig. 1 a):
and (3) positive electrode: mn2+→ Mn3+ + e-;
Negative electrode: sn (tin)2+ + 2e-→ Sn;
Discharge process (fig. 1 b):
and (3) positive electrode: mn3+ + e-→ Mn2+;
Negative electrode: sn → Sn2+ + 2e-。
In the invention, the positive current collector and the negative current collector can be one of a carbon felt, carbon paper, carbon cloth, a graphite felt, a graphene film, a graphene net, a carbon nanotube film, carbon nanotube paper, a conductive activated carbon film, a mesoporous carbon film, a conductive graphite plate, a conductive graphite net, a titanium net and a stainless steel net, or a composite of several of the carbon felt, the carbon paper, the carbon cloth, the graphite felt, the graphene film, the graphene net, the carbon nanotube film, the conductive activated carbon film, the mesoporous carbon film, the conductive graphite plate, the conductive graphite net, the titanium net and the stainless steel net.
In the present invention, the negative electrode solution, aqueous solution, contains tin ions (Sn)2+) In addition, it also contains hydrogen ion (H)+) (ii) a Wherein, the concentration of tin ions is between 0.01 and 10 mol/L, and the concentration of hydrogen ions is 10-6-10 mol/L.
In the present invention, the positive electrode solution is an aqueous solution containing manganese ions (Mn)2+) In addition, it also contains titanium ion (Ti)4+) And hydrogen ion (H)+) Wherein the concentration of manganese ions and titanium ions is between 0.01 and 10 mol/L, and the concentration of hydrogen ions is 10-6-10 mol/L.
In order to increase the ionic conductance of the electrolyte, the electrolyte may further include lithium ions (Li)+) Potassium ion (K)+) Sodium ion (Na)+) Magnesium ion (Mg)2+) Zinc ion (Zn)2+) Bismuth ion (Bi)3+) The concentration of one or more of the (B) is 0.01-10 mol/L.
In the electrolyte of the present invention, the anion contained is Sulfate (SO)4 2-) Nitrate radical (NO)3 -) Perchlorate (ClO)4 -) Phosphate radical (PO)4 3-) Monohydrogen phosphate (HPO)4 2-) Dihydrogen phosphate radical (H)2PO4 -) Hypophosphorous acid radical (HPO)2 -) Phosphite (HPO)3 2-) And acetate ([ CH ]3COO]−) Carbonate (CO)3 2-) Bicarbonate radical (HCO)3 -) Chloride ion (Cl)-) Bromine ion (Br)-) The corresponding ion concentration is between 0.01 mol/L and 12 mol/L. The electrolyte is circulated by an external circulation pump (figure 2) and is used for eliminating tin ions (Sn) during battery charging2+) And manganese ion (Mn)2+) Concentration polarization caused by depletion.
The diaphragm is a porous PBI (Poly-p-phenylene-imide) membrane, and can allow protons to pass through and block other ions from passing through.
To verify the electrochemical performance of the novel tin-manganese secondary battery system of the present invention, we performed relevant electrochemical tests on the assembled battery (fig. 3). Wherein the anode solution adopts 0.1mol/L MnSO4,0.1 mol/L Ti(SO4)2Aqueous solution, negative pole liquid is 0.2 mol/L SnSO4The total amount of the aqueous solution and the positive and negative electrode solutions was 10 mL. Tests show that the tin-manganese battery has good rate capability and cycling stability in a working range of 0.9-1.8V. At 50 mA/cm2Under the condition of discharge, the coulombic efficiency is about 100 percent, the operation can be stably carried out for 100 cycles, and the discharge voltage is up to 1.5V.
The invention is characterized in that the anode relates to the conversion of bivalent manganese and trivalent manganese in the solution, the cathode relates to the dissolution deposition reaction on the surface of the current collector, the electrode reaction does not relate to the diffusion control of ions in the electrode crystal structure, the ultra-high power density is shown, and the ultra-long cycle life is realized; the aqueous electrolyte has no risk of fire and explosion and has high safety. On the other hand, the porous PBI membrane is adopted, other ions are effectively blocked while protons are passed, and the coulomb efficiency is ultrahigh. In addition, compared with the existing commercial battery system, the electrode reaction of the tin-manganese battery system does not involve toxic elements such as lead (Pb), cadmium (Cd), vanadium (V) and the like, and does not contain flammable and toxic organic electrolyte, so that the tin-manganese battery system has the advantages of high safety and low toxicity. Based on the advantages of high power, ultra-long cycle life, high safety and low toxicity, the battery can be widely applied to the fields of large-scale energy storage and the like.
Drawings
Fig. 1 is a schematic diagram of charging and discharging of a tin-manganese redox flow battery.
Fig. 2 shows a manner of placing the electrolyte of the tin-manganese flow battery.
Fig. 3 is a discharge curve and cycle life of a tin-manganese flow battery of the present invention. Wherein, (a) 50 mA/cm2Current density discharge curve (b) cycling performance.
Detailed Description
The invention is further illustrated by the following examples.
Example 1: a tin-manganese liquid flow secondary battery, the negative current collector is carbon paper, and the positive current collector is carbon paper.
In this example, carbon paper (3 cm x 3 cm) was used as the negative electrode current collector, carbon paper (3 cm x 3 cm) was used as the positive electrode current collector, and the positive electrode solution contained 2 mol/L sulfuric acid, 0.1mol/L manganese sulfate, and 0.1mol/L titanium sulfate. The negative pole solution is 2 mol/L sulfuric acid and 0.2 mol/L stannous sulfate. The membrane is a PBI membrane. Flow rate 30mL s-1Within the working interval of 1-1.85V, 10 mA/cm2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
Example 2: a tin-manganese liquid flow secondary battery is characterized in that a negative current collector is a carbon felt, and a positive current collector is a carbon felt.
In this example, a carbon felt (3 cm x 3 cm) was used as the negative electrode current collector, a carbon felt (3 cm x 3 cm) was used as the positive electrode current collector, and the positive electrode solution contained 3 mol/L sulfuric acid, 0.5 mol/L manganese sulfate, and 0.5 mol/L titanium sulfate. The negative pole solution is 3 mol/L sulfuric acid and 0.5 mol/L stannous sulfate. The membrane is a PBI membrane. Flow rate 80mL s-180 mA/cm in the working range of 0.6-2V2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
Example 3: a tin-manganese liquid flow secondary battery is characterized in that a negative current collector is carbon cloth, and a positive current collector is carbon cloth.
In this example, carbon cloth (3 cm x 3 cm) was used as the negative electrode current collector, carbon cloth (3 cm x 3 cm) was used as the positive electrode current collector, and the positive electrode solution contained 2 mol/L sulfuric acid, 1mol/L manganese sulfate, and 1mol/L titanium sulfate. The negative pole solution is 2 mol/L sulfuric acid and 1mol/L stannous sulfate. The membrane is a PBI membrane. Flow rate 80mL s-1Within the working range of 0.8-1.9V, 100 mA/cm2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
Example 4: a tin-manganese liquid flow secondary battery is characterized in that a negative current collector is a graphite felt, and a positive current collector is a graphite felt.
In this example, graphite felt (3 cm x 3 cm) was used as the negative electrode current collector, graphite felt (3 cm x 3 cm) was used as the positive electrode current collector, and positive electrode liquid was used as the positive electrode liquidContains 3 mol/L sulfuric acid, 0.5 mol/L manganese sulfate and 0.5 mol/L titanium sulfate. The negative pole solution is 3 mol/L hydrochloric acid and 0.5 mol/L stannous chloride. The membrane is a PBI membrane. Flow rate 50mL s-180 mA/cm in the working range of 0.6-2V2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
Example 5: a tin-manganese liquid flow secondary battery, the negative current collector is carbon felt, and the positive current collector is carbon cloth.
In this example, carbon paper (3 cm x 3 cm) was used as the negative electrode current collector, carbon paper (3 cm x 3 cm) was used as the positive electrode current collector, and the positive electrode solution contained 2 mol/L sulfuric acid, 0.1mol/L manganese acetate, and 0.1mol/L titanium sulfate. The negative electrode solution is 2 mol/L nitric acid and 0.2 mol/L stannic acetate. The membrane is a PBI membrane. Flow rate 30mL s-1Within the working interval of 0 to 1.9V, 30 mA/cm2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
Example 6: a tin-manganese liquid flow secondary battery, the negative current collector is graphite felt, and the positive current collector is carbon paper.
In this example, graphite felt (3 cm x 3 cm) was used as a negative electrode current collector, carbon paper (3 cm x 3 cm) was used as a positive electrode current collector, and the positive electrode solution contained 2 mol/L sulfuric acid, 0.1mol/L manganese acetate, 0.1mol/L titanium sulfate, and 0.1mol/L sodium sulfate. The negative pole solution is 2 mol/L nitric acid, 0.2 mol/L stannic acetate and 0.2 mol/L sodium acetate. The membrane is a PBI membrane. Flow rate 30mL s-1Within the working interval of 0 to 1.9V, 30 mA/cm2The coulombic efficiency after 100 cycles under the current density is close to 100 percent.
TABLE 1 performances of Sn-Mn redox flow batteries using different anodes, cathodes and electrolytes