CN109585979B - Disposable lead-air battery - Google Patents
Disposable lead-air battery Download PDFInfo
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- CN109585979B CN109585979B CN201811250303.3A CN201811250303A CN109585979B CN 109585979 B CN109585979 B CN 109585979B CN 201811250303 A CN201811250303 A CN 201811250303A CN 109585979 B CN109585979 B CN 109585979B
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
Abstract
The invention discloses a disposable lead-air battery, and belongs to the technical field of batteries. The disposable lead-air battery comprises a battery case, an air electrode, a lead electrode and electrolyte, wherein the space between the lead electrode and the air electrode is controlled to be fixed through the battery case, the electrolyte is filled between the lead electrode and the air electrode, and the electrolyte is methanesulfonic acid aqueous solution. The disposable lead-air battery provided by the invention adopts the methanesulfonic acid aqueous solution as the electrolyte, so that the utilization rate of the active substances is obviously improved, and the specific capacity of the battery is further improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a disposable lead-air battery.
Background
The metal-air battery is a chemical power supply which takes oxygen in the air as a positive active material and metal as a negative active material to generate electric energy through chemical reaction under the catalysis of a catalyst, and comprises: zinc-air batteries, lithium-air batteries, aluminum-air batteries, etc. are constructed in a similar manner to dry batteries, except that the positive active material is oxygen in the air. For example, there is an air battery in which zinc is used as a cathode, sodium hydroxide is used as an electrolyte, and an anode is a porous carbon material, so that oxygen in the air can be used instead of a positive electrode active material (manganese dioxide) in a general dry battery.
The air battery is used as a clean energy battery, and compared with other traditional batteries, the air battery has the following advantages: 1. the battery capacity is large, which is more than 6 times of that of the traditional lead-acid battery with the same volume and more than 2 times of that of the lithium battery; 2. the energy density is high and the weight is light; the voltage is stable during discharging, the time is long and is more than 2 times that of a lithium battery, the weight is only about 50 percent of that of the lithium battery, and free discharge is less under the condition of not filling electrolyte, so that the lithium battery is convenient to store for a long time; 3. toxic and harmful substances such as lead, mercury, sulfur and the like which pollute the environment are not used, so that the problems that the traditional battery pollutes the environment and the lithium ion battery is recycled are solved; 4. safe and reliable, and can not generate the conditions of high temperature, power reduction, charging explosion and the like.
The lead-air battery is a battery for generating electricity by the action of metallic lead as a fuel and oxygen in the air, and has a negative electrode made of lead metal and a positive electrode made of a gas diffusion electrode composed of an oxygen reduction catalyst and a gas diffusion layer. For example, chinese patent application No. 201611145633.7 discloses a lead-air battery using dilute sulfuric acid as electrolyte, specifically, the lead-air battery includes an insulating housing, an electrolyte, a lead electrode, an air electrode, a nickel mesh and an insulating compact, wherein the lead electrode is mounted in the insulating housing; the air battery comprises a perfluorosulfonic acid membrane, a catalytic layer and carbon paper, wherein the perfluorosulfonic acid membrane is in contact with electrolyte; the nickel net and the air electrode are pressed on the sealing gasket by the insulating pressing block, the nickel net is located between the carbon paper and the insulating pressing block, and the insulating pressing block is fixedly connected to the insulating shell.
The lead-air battery replaces a lead dioxide electrode of the anode of the traditional lead-acid battery with an air electrode, so that the quality and the volume of the lead-acid battery are reduced, the specific capacity of the lead-acid battery is improved, the lead consumption is reduced, and the environmental influence of the lead-acid battery is reduced. However, the negative electrode reaction of the lead-air battery using dilute sulfuric acid as an electrolyte generates lead sulfate that is insoluble in the electrolyte, which limits the utilization rate of active materials of the lead-air battery, which is less than 50%, thereby limiting the specific capacity of the battery.
Therefore, how to improve the utilization rate of active materials by carrying out technical improvement on the lead-air battery is a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a lead-air battery to overcome the problem of low utilization rate of active substances of the conventional lead-air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the disposable lead-air battery comprises a battery case, an air electrode, a lead electrode and electrolyte, wherein the space between the lead electrode and the air electrode is controlled to be fixed through the battery case, the electrolyte is filled between the lead electrode and the air electrode, and the electrolyte is methanesulfonic acid aqueous solution.
In the above battery, the positive electrode uses oxygen in the air as an active material, the negative electrode uses lead as an active material, the positive electrode and the negative electrode are arranged in a separated manner, and an electrolyte is interposed between the positive electrode and the negative electrode, and the electrolyte is in contact with the positive electrode and the negative electrode. When the electrolyte is a methanesulfonic acid aqueous solution, the reaction of the lead electrode is that lead is converted into a soluble divalent lead form and exists in the methanesulfonic acid aqueous solution, so that the problem of low utilization rate of active substances caused by the fact that insoluble lead sulfate wraps the lead electrode in the prior art is solved. Research shows that the utilization rate of active substances of the lead electrode is close to 100% by adopting the methanesulfonic acid as the electrolyte.
Preferably, the air electrode includes a porous current collecting layer, a gas diffusion layer, and a catalytic layer, and the catalytic layer is in direct contact with the electrolyte. The air electrode does not adopt a proton exchange membrane, and the catalyst layer is directly contacted with the electrolyte, so that the mass transfer of water in the reaction process of the battery is facilitated.
The porous current collector layer may be formed by using a member known in the art, such as a porous titanium sheet.
The gas diffusion layer is selected from any one of the following materials: carbon paper, carbon cloth, carbon felt, selective oxygen permeable membrane, and combinations thereof.
The catalyst in the catalyst layer is one or a mixture of more of metals of Pt, Pd, Ag, Ir, Cu, Rh, Ni, Ru, Co, Au, Mo, W, Fe, oxides of the metals, supported catalysts of the metals and the metal oxides, carbon materials and carbon nitride.
The support of the supported catalyst may be selected from any one of the following: oxides, zeolites, clay mineral minerals, carbon, and mixtures thereof. The oxide may be: alumina, silica, zirconium oxide, titania, and the like. The carbon may be: carbon black, graphite, activated carbon, carbon fiber, and the like. The carrier of the supported catalyst is not limited to the above.
Preferably, the preparation method of the air electrode comprises the following steps: mixing a catalyst, a binder and an organic solvent, then carrying out ultrasonic oscillation to prepare slurry, and spraying the slurry on one side of a gas diffusion layer to form a catalyst layer; and then the catalyst-free side of the gas diffusion layer is bonded or mechanically pressed onto a porous current collector to produce the air electrode.
Preferably, the lead electrode is a sheet-shaped, net-shaped or foam-shaped electrode plate made of one or a mixture of more of metallic lead, lead alloy and lead-carbon composite.
Preferably, the concentration of the methanesulfonic acid aqueous solution is 2 to 4 mol/L.
Preferably, a separator is provided between the lead electrode and the air electrode, and the electrolyte is present in the separator in an impregnated form.
The separator may be made of materials known in the art, for example: a polyethylene film, a polypropylene film, or a glass fiber film, but is not necessarily limited thereto, and the separator may be absent.
The invention has the following beneficial effects:
the disposable lead-air battery provided by the invention adopts the methanesulfonic acid aqueous solution as the electrolyte, so that the utilization rate of the active substances is obviously improved, and the specific capacity of the battery is further improved.
Drawings
Fig. 1 is a schematic view of a primary lead-air battery prepared in example 1.
FIG. 2 is a linear voltammogram of a dissolution reaction of lead in different concentrations of methanesulfonic acid in water.
Fig. 3 is a graph showing the results of a constant current polarization test performed on the primary lead-air battery prepared in example 1.
FIG. 4 shows the effect of the presence or absence of a proton exchange membrane on the discharge polarization of a primary lead-air battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the primary lead-air battery comprises: a positive electrode 1 using oxygen in the air as an active material of the positive electrode; a negative electrode 3 using lead as an active material of the negative electrode, the negative electrode 3 being arranged in a spaced manner from the positive electrode 1; and the electrolyte 2 is an aqueous solution of methanesulfonic acid, the electrolyte 2 is arranged between the positive electrode 1 and the negative electrode 3, and the electrolyte 2 is in contact with the positive electrode 1 and the negative electrode 3.
The positive electrode 1 includes a porous current collector 1-3, a gas diffusion layer 1-2, and a catalytic layer 1-1.
Example 1
1. Preparation of primary lead-air battery
0.5mg/cm in Pt on hydrophobic carbon paper2The catalyst loading amount of the catalyst is sprayed with a carbon-supported platinum catalyst to prepare a gas diffusion layer supporting a catalyst layer, a porous titanium sheet is used as a positive electrode porous current collector, and the gas diffusion layer supporting the catalyst layer and the positive electrode porous current collector are mechanically pressed to obtain a positive electrode.
An aqueous solution of methanesulfonic acid at a concentration of 4M was used as the electrolyte.
A metal lead sheet having a thickness of 300 μm was prepared as a negative electrode.
The cathode, the electrolytic solution, and the anode prepared as described above were introduced into a battery case in such a manner that the cathode catalyst layer and the anode faced each other and the electrolytic solution was between the cathode and the anode to prepare a primary lead-air battery.
The macroscopic effective areas of the prepared positive electrode and the negative electrode of the primary lead-air battery are both 1cm2The amount of the electrolyte was 0.8 mL.
2. Performance testing of Primary lead-air batteries
2.1 FIG. 2 is a linear voltammetry curve of a dissolution reaction of lead in methanesulfonic acid aqueous solutions of different concentrations, and it can be seen that the peak overpotential of the dissolution reaction of lead in a methanesulfonic acid aqueous solution of 4mol/L is about 80mV, and the curve shows a straight line with a constant slope after the overpotential is more than 140mV, which shows that the current-voltage relationship of the reaction is mainly controlled by ohmic impedance.
2.2 in order to measure the discharge capacity of the primary lead-air battery prepared in the example, the discharge condition was controlled at a constant air pressure of 1atm and a constant temperature of 25 deg.C, and constant current discharge polarization was performed using an electrochemical workstation, in which the magnitude of the discharge current with respect to the macroscopic effective area of the electrode was 10mA/cm2。
The results of the experiments are shown in FIG. 3, where the primary lead-air battery prepared in the example was operated at 10mA/cm2The discharge time is 5h, and the volume specific capacity is calculated to be 70.3 Ah/L.
The lead content of the primary lead-air battery prepared in the example is 0.22g, the residual lead content at the end of discharge is less than 0.02g, and the utilization rate of the active material lead is more than 90%.
Example 2
A primary lead-air battery was prepared by referring to the method of example 1, except that an aqueous solution of methanesulfonic acid having a concentration of 2M was used as an electrolyte, and the conditions were the same as in example 1.
As shown in FIG. 2, the elution reaction of lead in a methanesulfonic acid aqueous solution having a concentration of 2mol/L was similar to that in example 1.
The utilization rate of the active material lead of the primary battery prepared in the example was more than 90%.
Example 3
A primary lead-air battery was prepared by referring to the method of example 1, except that an aqueous solution of methanesulfonic acid having a concentration of 3M was used as an electrolyte, and the conditions were the same as in example 1.
As shown in FIG. 2, the elution reaction of lead in a methanesulfonic acid aqueous solution having a concentration of 3mol/L was similar to that of example 1.
The utilization rate of the active material lead of the primary battery prepared in the example was more than 90%.
Comparative example 1
A primary lead-air battery was fabricated by referring to the method of example 1, except that an aqueous solution of methanesulfonic acid having a concentration of 4.5M or 5M was used as an electrolyte, and the conditions were the same as in example 1.
As shown in FIG. 2, when the concentration of the electrolyte solution is more than 4.5mol/L, an oxidation peak appears on the curve, the lead elution current rapidly decreases after crossing the oxidation peak, and the peak current and the current after crossing the oxidation peak become lower as the oxidation peak appears earlier as the concentration becomes larger. This is probably due to the limited solubility of lead in the highly concentrated aqueous solution of methanesulfonic acid, and too high a concentration results in the crystallization of lead methylsulfonate onto the surface of the lead electrode, resulting in a rapid decay of the current.
The concentration of the aqueous solution of methanesulfonic acid in the primary lead-air battery of the invention is therefore chosen to be 2-4 mol/L.
Comparative example 2
In addition to the lead-air battery structure shown in fig. 1, referring to chinese patent document No. 201611145633.7, a proton exchange membrane (perfluorosulfonic acid membrane) was additionally provided on the surface of the catalyst layer 1-1 of the positive electrode, and the proton exchange membrane was brought into contact with the electrolyte 2 to produce a lead-air battery.
As shown in FIG. 4, in the presence of the proton exchange membrane, 10mA/cm was reached2The polarization voltage of the current density of (a) is about 0.8V, and the polarization voltage in the case of no proton exchange membrane is about 1.0V.
The analytical reason may be that the proton transfer direction is toward the catalyst side and the water transfer direction is toward the electrolyte side during discharge, but the proton transfer in the proton exchange membrane depends on the water transfer, so that the proton exchange membrane contradicts the transfer of the reactant protons and the product water during cell discharge, resulting in increased electrode polarization.
Therefore, for the primary lead-air battery of the invention, the form without the proton exchange membrane is more beneficial to the discharge of the battery.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The disposable lead-air battery comprises a battery case, an air electrode, a lead electrode and electrolyte, wherein the battery case controls the lead electrode and the air electrode to be fixed at a certain distance, and the electrolyte is filled between the lead electrode and the air electrode;
the concentration of the methanesulfonic acid aqueous solution is 2-4 mol/L;
the lead electrode is a flaky, meshed or foamed electrode plate made of one or a mixture of more of metal lead, lead alloy and lead-carbon composite;
the preparation method of the air electrode comprises the following steps: mixing a catalyst, a binder and an organic solvent, then carrying out ultrasonic oscillation to prepare slurry, and spraying the slurry on one side of a gas diffusion layer to form a catalyst layer; and then the catalyst-free side of the gas diffusion layer is bonded or mechanically pressed onto a porous current collector to produce the air electrode.
2. The disposable lead-air battery of claim 1, wherein the air electrode comprises a porous current collection layer, a gas diffusion layer, and a catalytic layer, the catalytic layer being in direct contact with the electrolyte.
3. The disposable lead-air battery of claim 2, wherein the gas diffusion layer is a carbon paper, a carbon cloth, a carbon felt, or a selective oxygen permeable membrane.
4. The disposable lead-air battery of claim 2, wherein the catalyst in the catalytic layer is one or a mixture of metals of Pt, Pd, Ag, Ir, Cu, Rh, Ni, Ru, Co, Au, Mo, W, Fe, oxides of the metals, supported catalysts of the metals and metal oxides, and carbon nitride.
5. The disposable lead-air battery according to claim 1, wherein a separator is disposed between the lead electrode and the air electrode, and the electrolyte is present in the separator in an impregnated form.
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| CN201811250303.3A CN109585979B (en) | 2018-10-25 | 2018-10-25 | Disposable lead-air battery |
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| CN201811250303.3A CN109585979B (en) | 2018-10-25 | 2018-10-25 | Disposable lead-air battery |
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| CN101714680A (en) * | 2008-10-07 | 2010-05-26 | 中国人民解放军63971部队 | Rechargeable metal-air redox flow battery combining electrochemical preparation |
| KR101790840B1 (en) * | 2015-01-21 | 2017-10-26 | 주식회사 엘지화학 | Lithium air battery |
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Address after: 313100 Zhejiang city of Huzhou province Changxing County Meishan Industrial Park Applicant after: TIANNENG BATTERY GROUP Co.,Ltd. Applicant after: HUAZHONG University OF SCIENCE AND TECHNOLOGY Address before: 313100 Zhejiang city of Huzhou province Changxing County Meishan Industrial Park Applicant before: TIANNENG BATTERY GROUP Co.,Ltd. Applicant before: HUAZHONG University OF SCIENCE AND TECHNOLOGY |
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