CN114464931B - Dual-functional zinc-alkyne battery - Google Patents
Dual-functional zinc-alkyne battery Download PDFInfo
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- CN114464931B CN114464931B CN202111653787.8A CN202111653787A CN114464931B CN 114464931 B CN114464931 B CN 114464931B CN 202111653787 A CN202111653787 A CN 202111653787A CN 114464931 B CN114464931 B CN 114464931B
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention relates to a difunctional zinc-alkyne battery, which adopts metallic zinc as an anode and reacts with electrolyte to generate spontaneous oxidation reaction: zn-Zn 2+ +2e ‑ The method comprises the steps of adopting a gas diffusion electrode or a membrane electrode as a cathode, enabling an alkyne compound to contact with a catalyst through the gas diffusion electrode or the membrane electrode, obtaining electrons from an anode, obtaining hydrogen ions from electrolyte, and carrying out reduction reaction: r is R 1 ‑C≡C‑R 2 +2e ‑ +2H + (or H) 2 O)→R 1 ‑CH＝CH‑R 2 +(OH ‑ ) To form a dual-function zinc-alkyne battery. The battery can generate electric energy and simultaneously perform electrocatalytic alkyne compound reduction reaction at the cathode of the battery, so that electrocatalytic reduction of alkyne compounds to alkene compounds is realized under the condition of no external power supply. Experimental results show that the battery can achieve higher power density and energy density, not only can drive hydrogenation reaction of cathode alkyne compounds, but also can generate electric energy, and a novel functional chemical power supply integrating power generation and alkyne compound reduction is realized.
Description
Technical Field
The invention belongs to the field of novel chemical batteries, and relates to a difunctional zinc-alkyne battery.
Background
With the rapid development of human society, the problems of massive consumption of energy and environmental pollution are increasingly serious, and the appearance of novel clean energy is hopeful to solve the two important problems, namely a chemical battery. The chemical battery directly converts chemical energy into electric energy by means of the self-generated oxidation-reduction reaction inside the battery to make electrons move directionally. Metallic zinc (Zn) has a higher theoretical specific capacity (820 mAh g) due to its lower redox potential (-0.762 vs. SHE) -1 ) Low toxicity and high natural abundance are considered as an excellent anode material. Patent CN113454822a discloses a zinc-air electrochemical cell with a carbon dioxide scavenger, which avoids the effect of atmospheric carbon dioxide on cell performance by adding a carbon dioxide scavenger to the zinc-air cell. At the same time, researchers have also treated zinc anodes by various means to optimize the performance of zinc-based batteries, patentCN113488607a modifies the zinc anode with a functional nanomaterial to inhibit the formation of zinc dendrites during the charge and discharge of the zinc-based battery, thereby extending the life of the battery. It can be seen that metallic zinc and its complexes have great potential and are of great interest as chemical battery anodes.
The selective reduction of acetylenic compounds is of vital importance in industrial processes. For example, olefin feedstocks for the production of a number of important industrial applications. However, olefins produced by petrochemical processes typically contain 0.3 to 3vol.% alkyne impurities, which severely poison downstream olefin polymerization catalysts, reducing the activity and lifetime of the catalyst. Therefore, removal of alkyne impurities from the olefin feed is extremely important. In addition to the widely used thermocatalytic alkyne hydrogenation process, electrocatalytic alkyne selective hydrogenation has recently also been developed (Nature Catalysis,2021,4 (7): 557-564;Nature Catalysis,2021,4 (7): 565-574), and patents CN 112301369A and CN 113026037a also report that copper-based materials as catalysts achieve efficient electrocatalytic acetylene reduction and apply it to the preparation of olefins and removal of alkyne impurities in olefins. In addition, other acetylenic compounds can be converted into corresponding industrially valuable chemicals by electrocatalytic reduction. For example, alkenols are important pharmaceutical and chemical intermediates, and can also be prepared by electrocatalytic alkynol semi-hydrogenation. Although the electrocatalytic alkyne compound selective reduction is a clean, efficient and convenient mode, the electrocatalytic alkyne compound still needs to be driven by an external power supply, and belongs to a high energy consumption process. Taking electrocatalytic acetylene selective reduction as an example, if acetylene impurities in ethylene gas produced every year are all removed by electrocatalytic reduction, about 13.87 TW.h of electric energy is consumed, and the total energy generation amount of the ethylene gas is about 0.06 percent of the total energy generation amount of the world. The alkyne compound has higher reduction potential, for example, the standard reduction potential of converting acetylene into ethylene is 0.733V vs.
Based on the background, a novel zinc-alkyne battery is provided, and the power generation and the selective hydrogenation of alkyne compounds are simultaneously carried out.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a difunctional zinc-alkyne battery, and based on the current demand of novel energy devices, the invention provides a functional zinc-alkyne battery which consists of a zinc anode, an alkyne reduction cathode, an ion exchange membrane and a battery shell. The metallic zinc is subjected to oxidation reaction (Zn-Zn) with electrolyte at the anode of the battery 2+ +2e - ) Electrons flow to the cathode of the battery through an external lead, the alkyne compound obtains electrons at the cathode, hydrogen is obtained from the electrolyte, and the alkyne compound undergoes selective reduction reaction (R 1 -C≡C-R 2 +2e - +2H + (H 2 O)→R 1 -CH＝CH-R 2 ). The zinc-alkyne battery generates electric energy, and simultaneously realizes selective hydrogenation reaction of alkyne compounds with important industrial significance at a cathode. In order to realize continuous and efficient reduction of alkyne compounds at the cathode, the invention adopts a flow battery, and the cathode adopts a gas diffusion electrode, a membrane electrode or a foam metal electrode, so as to realize continuous supply of cathode reactants and continuous output of reduction products. Taking a zinc plate as an anode, acetylene as a cathode raw material and 1M KOH aqueous solution as an electrolyte as an example, the structure and the discharge mechanism of the zinc-alkyne battery are shown in figure 1. The zinc-alkyne battery comprises the following technical problems:
technical proposal
A dual-functional zinc-alkyne battery is characterized by comprising anode metal zinc, a cathode, an ion exchange membrane, electrolyte, alkyne compounds, a catalyst and a cathode outer plate; an ion exchange membrane, a cathode and a cathode outer plate are sequentially arranged between the anode metal zinc and the cathode outer plate, an anolyte is arranged between the anode metal zinc and the ion exchange membrane, a catholyte is arranged between the ion exchange membrane and the cathode, and an alkyne compound is arranged between the cathode and the cathode outer plate; a catalyst is arranged on one side wall of the cathode facing the catholyte; the cathode is a gas diffusion electrode or a membrane electrode; metallic zinc is used as an anode and reacts with electrolyte to perform spontaneous oxidation reaction: zn-Zn 2+ +2e - The alkyne compound is contacted with the catalyst through a gas diffusion electrode or a membrane electrode and is obtained from the anodeElectrons, hydrogen ions are obtained from the electrolyte, and reduction reaction occurs: r is R 1 -C≡C-R 2 +2e - +2H + (or H) 2 O)→R 1 -CH＝CH-R 2 +(OH - ) To form a dual-function zinc-alkyne battery.
The metallic zinc anode includes, but is not limited to, zinc plates, zinc sheets, zinc foils, zinc foam, metallic zinc particles, zinc-based alloys, or zinc composites.
The metal zinc anode is a zinc anode obtained by loading metal zinc or alloy and compound thereof on an anode current collector by adopting spraying, dipping or electrodeposition means.
The anode current collector includes, but is not limited to, a copper current collector, a nickel current collector, a titanium current collector, carbon paper, or carbon cloth.
Such catalysts include, but are not limited to, pt, ni, cu, zn, ru, rh, pd, ag or Ir element based alloys and monoatoms thereof, metal phthalocyanines, metal nitrides, and carbon-nonmetallic compounds thereof.
The gas diffusion layer materials include, but are not limited to: carbon fiber paper, carbon fiber woven cloth, non-woven cloth or carbon black paper.
The alkyne compound raw materials include, but are not limited to, acetylene, propyne, butyne, 1, 4-butyne diol, propargyl alcohol or 2-methyl-3-butyne diol, gaseous or liquid carbon-carbon triple bond-containing compounds and mixtures thereof or mixtures of carbon-carbon triple bond-containing compounds and other substances.
The catholyte and anolyte are acidic, neutral, alkaline or solid electrolytes.
The catholyte and anolyte include, but are not limited to: 0.01-5M hydrochloric acid, 0.01-5M sulfuric acid, 0.01-5M KCl solution, 0.01-10M KHCO 3 Solution or 0.01-10M KOH solution.
The discharge condition of the battery comprises that the flow rate of alkyne-containing reactant is 5-100 sccm, the flow rate of catholyte is 1-100 sccm, and the flow rate of anolyte is 1-100 sccm.
Advantageous effects
The invention provides a double-functionZinc-alkyne battery, adopt metallic zinc as positive pole, react with electrolyte and take place spontaneous oxidation reaction: zn-Zn 2+ +2e - The method comprises the steps of adopting a gas diffusion electrode or a membrane electrode as a cathode, enabling an alkyne compound to contact with a catalyst through the gas diffusion electrode or the membrane electrode, obtaining electrons from an anode, obtaining hydrogen ions from electrolyte, and carrying out reduction reaction: r is R 1 -C≡C-R 2 +2e - +2H + (or H) 2 O)→R 1 -CH＝CH-R 2 +(OH - ) To form a dual-function zinc-alkyne battery. The battery can generate electric energy and simultaneously perform electrocatalytic alkyne compound reduction reaction at the cathode of the battery, so that electrocatalytic reduction of alkyne compounds to alkene compounds is realized under the condition of no external power supply. Experimental results show that the battery can achieve higher power density and energy density, not only can drive hydrogenation reaction of cathode alkyne compounds, but also can generate electric energy, and a novel functional chemical power supply integrating power generation and alkyne compound reduction is realized.
The invention utilizes zinc oxidation reaction of anode and hydrogenation reaction of alkyne compound of coupling cathode, can carry out semi-hydrogenation reduction of alkyne compound with high efficiency and high selectivity without consuming electric energy, can generate additional electric energy, and realizes chemical power supply integrating power generation and alkyne compound reduction under mild condition. Zinc-alkyne cells assembled using the design of the invention (1 cm 2 Electrode area) is 1.1V, the maximum power density is 2.2mW cm -2 Energy density is 213.8Wh kg Zn -1 . Meanwhile, the Faraday efficiency of reducing alkyne into alkene can reach 99.0% by regulating and controlling proper discharge current, so that the high-efficiency electric reduction of alkyne compounds is realized, and the method has a wide application prospect.
Drawings
Fig. 1 shows the structure and discharge mechanism of the novel zinc-alkyne cell (taking the anode as a zinc plate, the cathode as acetylene and the electrolyte as 1m koh aqueous solution as an example).
FIG. 2 is a graph having a length of 1cm 2 Electrode area discharge curve and power density curve of zinc-acetylene cell.
Detailed Description
The invention will now be further described with reference to examples, figures:
one of the technical problems to be solved by the invention is the preparation of a zinc anode;
the second technical problem to be solved by the invention is the preparation of a gas diffusion electrode, a membrane electrode or a foam metal electrode;
the third technical problem to be solved by the invention is to design and test performance of a zinc-alkyne battery device for continuously reducing alkyne compounds.
In order to solve one of the above technical problems, the technical scheme of the present invention includes:
(1) The zinc anode is prepared by loading metallic zinc or alloy and compound thereof on a current collector through means of spraying, dipping, electrodeposition and the like
(2) Directly using zinc plate, zinc sheet, foam zinc or zinc foil as zinc anode.
In order to solve the second technical problem, the technical scheme of the invention comprises the following steps:
(1) Preparation of a gas diffusion electrode: accurately weighing catalyst powder with a certain mass (1-1000 mg), dispersing in a certain volume (0.2-200 mL) of solvent, adding 3.3 mu L-3.3 mL of Nafion solution (5%), and then performing ultrasonic dispersion for 10-120 minutes, preferably 30-60 minutes to obtain catalyst slurry; placing the gas diffusion layer on a flat heating table, wherein the heating temperature is 50-100 ℃, preferably 70-90 ℃; accurately measuring a certain volume (50-500 mu L) of catalyst slurry, uniformly spraying the catalyst slurry on the gas diffusion layer, and fully drying to obtain the gas diffusion electrode.
(2) Preparation of a membrane electrode: accurately measuring a certain volume (50-500 mu L) of catalyst slurry, uniformly spraying the catalyst slurry on an ion exchange membrane, and fully drying to prepare the membrane electrode.
(3) Preparation of foam metal electrode: copper nano-structures are prepared on the surface of the foam copper or copper nano-materials are loaded on a foam metal substrate.
In order to solve the third technical problem, the technical scheme of the invention comprises the following steps:
(1) A fluid battery is adopted, and a gas diffusion electrode, a membrane electrode or a foam metal electrode which is made of a catalyst is used as a battery cathode and is matched with a zinc anode; the catholyte and the anolyte are isolated by an ion exchange membrane; the alkyne compound raw material is supplied from the cathode chamber.
(2) In the discharging process of the battery, the flow rate of the cathode alkyne compound raw material is 5-100 sccm, the flow rate of the catholyte is 1-100 sccm, and the flow rate of the anolyte is 1-100 sccm; and obtaining a corresponding alkyne compound hydrogenation product at a cathode outlet of the battery.
(3) The discharge performance of the zinc-alkyne battery is tested by adopting an electrochemical workstation or a battery test system, the selective electrocatalytic hydrogenation performance of different alkyne compounds on the cathode of the zinc-alkyne battery is characterized by adopting a potentiostatic method or a galvanostatic method, and the concentration of each component of the product at the outlet of the cathode of the battery is detected by using an online gas chromatograph.
In making a battery anode, the metallic zinc anode includes, but is not limited to: zinc plates, zinc sheets, zinc foils, zinc foam, zinc metal particles, zinc-based alloys, zinc composites, and the like.
The anode current collector includes, but is not limited to: copper current collector, nickel current collector, titanium current collector, carbon paper, carbon cloth, etc.
The thickness of the zinc plate, zinc sheet, zinc foil and foam zinc comprises but is not limited to 0.05-1.0 mm, and the area of the zinc plate comprises but is not limited to 1-40 cm 2 。
In making the cathode of the cell, the catalyst powder includes, but is not limited to, pd-based alloys, metal nitrides, metal phthalocyanine complex-based catalysts.
Such catalytic materials include, but are not limited to, pt, ni, cu, zn, ru, rh, pd, ag, ir and like elemental based alloys and monoatoms thereof, metal phthalocyanines, metal nitrides, carbon and carbon-nonmetallic compounds thereof, and the like.
The gas diffusion layer materials include, but are not limited to: carbon paper, carbon cloth, nonwoven fabric, carbon black paper, or the like.
The catholyte and anolyte are acidic, neutral, alkaline or solid electrolytes, etc., but are not limited to: 0.01-5M hydrochloric acid, 0.01-5M sulfuric acid, 0.01-5M KCl solutionKHCO of 0.01-10M 3 Solution or 0.01-10M KOH solution.
The alkyne compound raw materials include, but are not limited to, acetylene, propyne, butyne, 1, 4-butyne diol, propargyl alcohol, 2-methyl-3-butyne diol and other gaseous or liquid carbon-carbon triple bond-containing compounds and mixtures thereof or mixtures of carbon-carbon triple bond-containing compounds and other substances.
The zinc-alkyne battery is assembled by combining specific alkyne compounds and catalysts, and the performance of the assembled battery and the content of product components at a cathode outlet are tested.
The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments of the application. When the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or groups thereof. The technical scheme of the invention is described below with reference to examples.
[ example 1 ]
(1) Taking a gas diffusion electrode made of Cu dendrite as a cathode of the battery; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; both catholyte and anolyte were 0.5. 0.5M H 2 SO 4 The solutions are separated by proton exchange membrane, and assembled into 1cm as shown in the schematic diagram of the device in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu dendrite by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 2 ]
(1) Taking a gas diffusion electrode made of Cu dendrite as a cathode of the electrolytic cell; taking the polished Zn foil with the thickness of 0.1mm as a battery anode; both the catholyte and the anolyte are 1.0M KOH solutionIs isolated by an anion exchange membrane and assembled into 1cm by the schematic diagram of the device shown in figure 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu dendrite by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 3 ]
(1) Taking a gas diffusion electrode made of Cu dendrite as a cathode of the electrolytic cell; 1mm thick zinc foam was used as the cell anode; the catholyte and the anolyte are 0.5M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu dendrite by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 4 ]
(1) Taking a gas diffusion electrode made of Cu dendrite as a cathode of the electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: 1% acetylene, 99% ethylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu dendrite by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 5 ]
(1) The gas diffusion electrode made of Cu dendrite is used as the cathode of the electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: 1% of propyne and 99% of propylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) The discharge curve is collected by an electrochemical workstation, the power density is calculated, the catalytic activity of the Cu dendrite catalyst is characterized by a constant current method, the content of each component in the outlet gas is determined by adopting online gas chromatography, and the Faraday efficiency is calculated.
[ example 6 ]
(1) Taking a gas diffusion electrode made of Cu dendrite as a cathode of the electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: 1% butyne, 9%1, 3-butadiene, the balance being argon.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) The discharge curve is collected by an electrochemical workstation, the power density is calculated, the catalytic activity of the Cu dendrite catalyst is characterized by a constant current method, the content of each component in the outlet gas is determined by adopting online gas chromatography, and the Faraday efficiency is calculated.
[ example 7 ]
(1) Taking a gas diffusion electrode made of Cu nano particles as a cathode of an electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: 1% acetylene, 99% ethylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu nano particles by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 8 ]
(1) Taking a gas diffusion electrode made of Cu nano particles as a cathode of an electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 0.5M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu nano particles by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 9 ]
(1) Taking a membrane electrode made of Ag nano wires as a cathode of an electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; anolyte solutions of 0.5 and 0.5M H 2 SO 4 The solutions are separated by proton exchange membrane, and assembled into 1cm as shown in the schematic diagram of the device in FIG. 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of the Ag nanowire by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
[ example 10 ]
(1) Taking a metal electrode prepared from foam copper as a cathode of an electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution and assembled into 1cm 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: 2-methyl-3-butynediol.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) Collecting a discharge curve by using an electrochemical workstation, calculating power density, characterizing catalytic activity of Cu nano particles by using a constant current method, determining content of each component in the outlet gas by using online gas chromatography, and calculating Faraday efficiency.
Comparative example 1
(1) Taking a gas diffusion electrode made of supported 5% Pd/C as a cathode of an electrolytic cell; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1M KOH solution, and are isolated by an anion exchange membrane, and are shown in figure 1The schematic diagram of the device is assembled into 1cm 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) The discharge curves were collected with an electrochemical workstation and the power density was calculated, the catalytic activity of 5% Pd/C was characterized by a constant current method, the content of each component in the outlet gas was determined by on-line gas chromatography and the Faraday efficiency was calculated.
Comparative example 2
(1) Taking a gas diffusion electrode made of 10% Pd/C as an electrolytic cell cathode; taking the polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1M KOH solution, are isolated by an anion exchange membrane, and are assembled into 1cm by a schematic diagram of the device shown in figure 1 2 Zinc-alkyne cells.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flowmeter, and the raw materials of the alkyne compound used in the experiment comprise the following components: high purity acetylene.
(3) The flow rates of the catholyte and anolyte were controlled to 50sccm using peristaltic pumps.
(4) The discharge curves were collected with an electrochemical workstation and the power density was calculated, the catalytic activity of 10% Pd/C was characterized by a constant current method, the content of each component in the outlet gas was determined by on-line gas chromatography and the Faraday efficiency was calculated.
The specific evaluation results are shown in Table 1.
TABLE 1
The scope of the claims of the present invention is not limited to the above-described embodiments, and all other embodiments obtained by a person having ordinary skill in the art without making any inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Claims (10)
1. A dual-functional zinc-alkyne battery is characterized by comprising anode metal zinc, a cathode, an ion exchange membrane, electrolyte, alkyne compounds, a catalyst and a cathode outer plate; an ion exchange membrane and a cathode are sequentially arranged between the anode metal zinc and the cathode outer plate, an anolyte is arranged between the anode metal zinc and the ion exchange membrane, a catholyte is arranged between the ion exchange membrane and the cathode, and an alkyne compound is arranged between the cathode and the cathode outer plate; a catalyst is arranged on one side wall of the cathode facing the catholyte; the cathode is a gas diffusion electrode or a membrane electrode; metallic zinc is used as an anode and reacts with electrolyte to perform spontaneous oxidation reaction: zn-Zn 2+ +2e - The alkyne compound contacts with the catalyst through a gas diffusion electrode or a membrane electrode, electrons are obtained from the anode, hydrogen ions are obtained from the electrolyte, and reduction reaction occurs: r is R 1 -C≡C-R 2 +2e - +2H + →R 1 -CH＝CH-R 2 +(OH - ) To form a dual-function zinc-alkyne battery.
2. The dual function zinc-alkyne cell of claim 1, wherein: the metal zinc anode comprises a zinc plate, a zinc sheet, a zinc foil, foam zinc, metal zinc particles or zinc-based alloy.
3. The dual function zinc-alkyne cell of claim 1, wherein: the metal zinc anode is a zinc anode obtained by loading metal zinc or alloy thereof on an anode current collector by adopting spraying, dipping or electrodeposition means.
4. A dual function zinc-alkyne cell according to claim 3, wherein: the anode current collector comprises a copper current collector, a nickel current collector, a titanium current collector, carbon paper or carbon cloth.
5. The dual function zinc-alkyne cell of claim 1, wherein: the catalyst comprises an alloy based on Pt, ni, cu, zn, ru, rh, pd, ag or Ir elements and a single atom thereof, metal phthalocyanines, metal nitrides and carbon-nonmetal compounds thereof.
6. The dual function zinc-alkyne cell of claim 1, wherein: the gas diffusion layer material comprises: carbon fiber paper, carbon fiber woven cloth, non-woven cloth or carbon black paper.
7. The dual function zinc-alkyne cell of claim 1, wherein: the alkyne compound raw material comprises one or more of gaseous or liquid acetylene, propyne, butyne, 1, 4-butyne diol, propargyl alcohol and 2-methyl-3-butyne diol.
8. The dual function zinc-alkyne cell of claim 1, wherein: the catholyte and anolyte are acidic, neutral, alkaline or solid electrolytes.
9. The dual function zinc-alkyne cell of claim 1, wherein: the catholyte and anolyte comprise: 0.01-5M hydrochloric acid, 0.01-5M sulfuric acid, 0.01-5M KCl solution, 0.01-10M KHCO 3 Solution or 0.01-10M KOH solution.
10. The dual function zinc-alkyne cell of claim 1, wherein: the discharge condition of the battery comprises that the flow rate of alkyne-containing reactant is 5-100 sccm, the flow rate of catholyte is 1-100 sccm, and the flow rate of anolyte is 1-100 sccm.
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| EP3266061A4 (en) * | 2015-03-04 | 2018-12-05 | Zhongwei Chen | Tri-electrode zinc-air battery with flowing electrolyte |
| KR101793711B1 (en) * | 2016-11-04 | 2017-11-07 | 한국에너지기술연구원 | Device and Method for preparing carbonate and/or formate from carbon dioxide |
| US11296373B2 (en) * | 2017-10-26 | 2022-04-05 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Rechargeable zinc/air batteries |
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