A tin metal battery based on an organic system

Abstract

A tin metal battery based on an organic system belongs to the field of battery technology. The tin metal battery includes an anode, a cathode and an electrolyte, wherein the anode is tin metal or a tin alloy, the cathode is a transition metal oxide or a conductive polymer, and the electrolyte is an organic electrolyte formed by dissolving a tin salt in an organic solvent. The present invention provides a tin metal battery based on an organic system, in which a tin salt is dissolved in an organic solvent as an electrolyte, and the organic solvent molecules in the electrolyte can be adsorbed on the surface of the anode, and the deposited tin grains are refined by increasing the nucleation overpotential to achieve dense deposition; at the same time, the solvent does not contain water molecules, which can avoid corrosion and gas production problems caused by water at the interface; tin ions are reversibly stored and released in the electrolyte, and the stability is good.

Description

Technical Field

[0001] The invention belongs to the technical field of batteries, and in particular relates to a tin metal battery based on an organic system, which can be applied to a large-scale energy storage system. Background Art

[0002] Due to the increasing reliance on organic electrolyte-based lithium-ion batteries, issues regarding cost and safety are becoming increasingly serious. Multivalent ion batteries have attracted widespread attention due to their high rate performance, low cost, ease of fabrication, and high safety. To date, significant progress has been made in the research of metal anodes in multivalent metal ion batteries, mainly including Zn, Mg, Cu, Al, etc. However, the low reversibility of stripping / plating, uncontrolled growth of dendrites, and side reactions such as hydrogen evolution reaction destroy the long-term stability and viable application potential of the above-mentioned metal anodes in electrolytes. Therefore, continuous research on anode materials with excellent plating / stripping ability and corrosion resistance should be encouraged to promote the further development of multivalent ion batteries.

[0003] Tin metal is one of the most attractive candidates for high-performance multivalent metal battery anodes because of its high theoretical capacity, low redox potential, and excellent environmental friendliness. More importantly, tin metal has low solubility in acidic and alkaline electrolytes, and is expected to achieve high energy density in acidic and alkaline electrolyte systems. At present, some studies have shown that tin can work reversibly in aqueous electrolytes. However, there are still many problems to be solved in aqueous tin batteries: 1. The grain size of electroplated tin in water is too large and it is not easy to deposit densely; 2. The corrosion and gas production problems caused by the aqueous solvent limit the long-term stability of the tin battery. Summary of the invention

[0004] The purpose of the present invention is to address the problems existing in the background technology and propose a tin metal battery based on an organic system. The battery uses tin salt dissolved in an organic solvent as an electrolyte. The high nucleation overpotential of the organic solvent helps to refine the tin grains. At the same time, the stable interfacial reaction can avoid the corrosion and gas production problems existing in aqueous tin metal batteries.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] A tin metal battery based on an organic system comprises an anode, a cathode and an electrolyte, wherein the anode is tin metal or a tin alloy, the cathode is a transition metal oxide or a conductive polymer, and the electrolyte is an organic electrolyte formed by dissolving a tin salt in an organic solvent.

[0007] Furthermore, the tin salt is one or more of stannous chloride, stannous sulfate, stannous fluoride, stannous bromide, stannous oxide, and stannous hydroxide.

[0008] Furthermore, the organic solvent is one or more of amide-based polar solvents such as N,N-dimethylformamide, formamide, N,N-dimethylacetamide, and acetamide.

[0009] Furthermore, in the organic electrolyte, the concentration of tin salt is 0.1-2 mol / L.

[0010] Furthermore, the anode is a single substance of tin metal, or an alloy of tin and copper, iron, magnesium, zinc, aluminum, lead or iron.

[0011] Furthermore, the transition metal oxide is V 2 O 5 , VO 2 、V 2 O 3 、MnO 2 , Mn 2 O 3 , Mn 3 O 4 , WO 3 One or more of the .

[0012] Furthermore, the conductive polymer is one or more of polyaniline, polypyrrole, polythiophene, or derivatives of polyaniline, polypyrrole, and polythiophene.

[0013] Furthermore, the separator of the tin metal battery is selected from one of non-woven fabrics, cellulose membranes, glass fiber membranes, polypropylene membranes, and polyethylene membranes.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] The present invention provides a tin metal battery based on an organic system, which uses an organic solvent to dissolve a tin salt as an electrolyte. The organic solvent molecules in the electrolyte can be adsorbed on the surface of the anode, and the deposited tin grains are refined by increasing the nucleation overpotential to achieve dense deposition. At the same time, the solvent does not contain water molecules, which can avoid corrosion and gas production problems caused by water at the interface. Tin ions are reversibly stored and released in the electrolyte, and the stability is good. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A schematic diagram of the structure of a tin metal battery based on an organic system provided by the present invention;

[0017] Figure 2 This is a schematic diagram of the reversible charge and discharge principle of the battery obtained in Example 1 of the present invention;

[0018] Figure 3 The charge and discharge curve of the battery obtained in Example 1 of the present invention;

[0019] Figure 4This is a cycle performance diagram of the battery obtained in Example 2 of the present invention;

[0020] Figure 5 The coulombic efficiency diagram of the battery obtained in Example 3 of the present invention;

[0021] Figure 6 This is the charge and discharge curve of the battery obtained in Example 4 of the present invention. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is described with the following specific embodiments, but the present invention is not limited to these examples.

[0023] A tin metal battery based on an organic system, such as Figure 1 As shown, it includes an anode, a cathode and an electrolyte, wherein the anode is tin metal or a tin alloy, the cathode is a transition metal oxide or a conductive polymer, and the electrolyte is an organic electrolyte formed by dissolving a tin salt in an organic solvent. The tin ions at the cathode can be reversibly embedded in and removed from the material, and the tin ions at the anode can be reversibly plated and stripped on the surface of tin or a tin alloy, and the two electrodes are connected through an organic electrolyte containing a tin salt.

[0024] Example 1

[0025] Polyaniline powder, polytetrafluoroethylene and acetylene black were mixed and ground in a mass ratio of 6:3:1, and an appropriate amount of N-methylpyrrolidone was added to disperse evenly and then coated on a stainless steel mesh. After drying at 80°C overnight, the cathode electrode was obtained. Tin foil was used as the anode, 0.1 mol / L stannous chloride N,N-dimethylformamide solution was used as the electrolyte, and glass fiber was used as the diaphragm to encapsulate it into a CR2032 button battery for electrochemical performance testing. The upper and lower limits of the voltage are 1.6V and 0.3V, respectively. The energy storage principle of the cathode polyaniline during charging and discharging is as follows Figure 2 As shown in the figure, under high and low potential conditions, anions and cations in the organic electrolyte are respectively embedded in the polyaniline material to achieve reversible electrical energy storage. 2 The current density is used for constant current charge and discharge, and the results are as follows Figure 3 The first three discharge cycles of the battery were 14 minutes and 18 seconds, 12 minutes and 25 seconds, and 10 minutes and 57 seconds, respectively, indicating that the tin metal battery based on the organic system can achieve reversible energy storage behavior, which is due to the dense deposition of tin at the anode without gas production and corrosion in the N,N-dimethylformamide electrolyte.

[0026] Example 2

[0027] Polyaniline powder, polytetrafluoroethylene and acetylene black were mixed and ground in a mass ratio of 6:3:1, and an appropriate amount of N-methylpyrrolidone was added to disperse them evenly and then coated on a stainless steel mesh. After drying at 80°C overnight, the cathode electrode was obtained. Tin foil was used as the anode, 0.1 mol / L stannous chloride N,N-dimethylformamide solution was used as the electrolyte, and glass fiber was used as the diaphragm to encapsulate it into a CR2032 button battery for electrochemical performance testing. The upper and lower limits of the voltage were 1.6V and 0.3V, respectively. Figure 4 This is the cycle performance diagram of the battery. After ten cycles at a current density of 1 A / g, the capacity retention rate is still 55%, which indicates that there are no water-related side reactions in the organic solvent, and the tin metal battery based on the organic system has good stability.

[0028] Example 3

[0029] Will WO 3 The powder, polytetrafluoroethylene and acetylene black were mixed and ground in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added to disperse evenly and then coated on a stainless steel mesh. After drying at 80°C overnight, the cathode electrode was obtained. Tin foil was used as the anode, 0.1 mol / L stannous sulfate N,N-dimethylacetamide solution was used as the electrolyte, and glass fiber was used as the diaphragm to encapsulate it into a CR2032 button battery for electrochemical performance testing. The upper and lower limits of the voltage were 0.9V and 0V, respectively. Figure 5 This is the coulombic efficiency diagram of the battery. At a current density of 1 A / g, although the coulombic efficiency of the battery is greater than 100% at the initial stage, it gradually stabilizes after 10 cycles, indicating that organic solvents can circumvent the side reaction problems of traditional aqueous electrolytes, and the stabilized coulombic efficiency is always maintained at around 100%.

[0030] Example 4

[0031] V 2 O 5 The powder, polytetrafluoroethylene and acetylene black were mixed and ground in a mass ratio of 8:1:1, and an appropriate amount of N-methylpyrrolidone was added to disperse evenly and then coated on a stainless steel mesh. After drying at 80°C overnight, the cathode electrode was obtained. Tin foil was used as the anode, 1 mol / L stannous chloride formamide solution was used as the electrolyte, and glass fiber was used as the diaphragm to encapsulate it into a CR2032 button battery for electrochemical performance testing. The upper and lower limits of the voltage are 0.8V and 0V, respectively. The cyclic charge and discharge curve of the battery at a current density of 0.2A / g is shown in the figure. Figure 6 As shown, due to the good interface stability of the organic solvent, the charge and discharge curves of the battery tend to be stable.

Claims

1. A tin metal battery based on an organic system, characterized in that: It includes an anode, a cathode and an electrolyte, wherein the anode is tin metal or a tin alloy, the cathode is a transition metal oxide or a conductive polymer, and the electrolyte is a 0.1 mol / L stannous chloride solution in N,N-dimethylformamide or a 0.1 mol / L stannous sulfate solution in N,N-dimethylacetamide.

2. The tin metal battery based on an organic system according to claim 1, characterized in that: The anode is a single substance of tin metal, or an alloy of tin and copper, iron, magnesium, zinc, aluminum, lead or iron.

3. The tin metal battery based on an organic system according to claim 1, characterized in that: The transition metal oxide is one or more of V2O5, VO2, V2O3, MnO2, Mn2O3, Mn3O4, and WO3.

4. The tin metal battery based on an organic system according to claim 1, characterized in that: The conductive polymer is one or more of polyaniline, polypyrrole, polythiophene, or derivatives of polyaniline, polypyrrole, and polythiophene.

5. The tin metal battery based on an organic system according to claim 1, characterized in that: The separator of the tin metal battery is one of non-woven fabric, cellulose film, glass fiber film, polypropylene film and polyethylene film.

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