CN114464931A - Difunctional zinc-alkyne battery - Google Patents
Difunctional zinc-alkyne battery Download PDFInfo
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- CN114464931A CN114464931A CN202111653787.8A CN202111653787A CN114464931A CN 114464931 A CN114464931 A CN 114464931A CN 202111653787 A CN202111653787 A CN 202111653787A CN 114464931 A CN114464931 A CN 114464931A
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Abstract
The invention relates to a difunctional zinc-alkyne battery, which adopts metal zinc as an anode and has spontaneous oxidation reaction with the action of electrolyte: zn → Zn2++2e‑The method adopts a gas diffusion electrode or a membrane electrode as a cathode, acetylene compounds are contacted with a catalyst through the gas diffusion electrode or the membrane electrode, electrons are obtained from an anode, hydrogen ions are obtained from electrolyte, and reduction reaction is carried out: r is1‑C≡C‑R2+2e‑+2H+(or H)2O)→R1‑CH＝CH‑R2+(OH‑) And forming the dual-function zinc-alkyne battery. The battery generates electricityAt the same time, the battery cathode can generate electrocatalytic acetylene compound reduction reaction, and the electrocatalytic reduction of the acetylene compound to the alkene compound is realized under the condition of no external power supply. Experimental results show that the battery can achieve high power density and energy density, can drive the hydrogenation reaction of the cathode acetylene compounds, can also generate electric energy, and realizes a functional novel chemical power supply integrating power generation and reduction of the acetylene compounds.
Description
Technical Field
The invention belongs to the field of novel chemical batteries, and relates to a bifunctional zinc-alkyne battery.
Background
With the rapid development of human societyAt present, the problems of large energy consumption and environmental pollution are increasingly serious, and the appearance of novel clean energy is expected to solve the two serious problems, namely a chemical battery is one of the two important problems. The chemical battery makes electrons move directionally by means of the oxidation-reduction reaction which occurs spontaneously inside the battery, and chemical energy is directly converted into electric energy. Metal zinc (Zn) has lower oxidation-reduction potential (-0.762vs. SHE) and higher theoretical specific capacity (820mAh g)-1) Low toxicity and high natural abundance, and is considered to be an excellent anode material. Patent CN113454822A discloses a zinc-air electrochemical cell with a carbon dioxide scavenger, which avoids the influence of atmospheric carbon dioxide on the cell performance by adding a carbon dioxide scavenger to the zinc-air cell. Meanwhile, researchers also treat the zinc anode by various means to optimize the performance of the zinc-based battery, and the patent CN113488607A utilizes a functional nano material to modify the zinc anode to inhibit the formation of zinc dendrites in the charging and discharging processes of the zinc-based battery, thereby prolonging the service life of the battery. It can be seen that metallic zinc and its composites have great potential and gained widespread attention as anodes for chemical batteries.
The selective reduction of acetylenic compounds is of crucial importance in industrial processes. For example, olefin feedstocks for the production of a number of important industrial products. However, olefins produced by petrochemical processes often contain 0.3 to 3 vol.% of acetylenic impurities, which can severely poison downstream olefin polymerization catalysts, reducing catalyst activity and catalyst life. Therefore, removal of alkyne impurities from olefin feedstocks is extremely important. Besides the widely applied thermal Catalysis alkyne hydrogenation process, the electrocatalytic selective alkyne hydrogenation has recently made an important progress (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 are used as catalysts to realize the high-efficiency electrocatalytic acetylene reduction and are applied to the preparation of olefins and the removal of alkyne impurities in olefins. In addition, other acetylenic compounds can also be converted into corresponding industrially valuable chemicals by means of electrocatalytic reduction. For example, enol is an important medical and chemical intermediate, and can also be prepared by electrocatalytic alkynol semi-hydrogenation. Although electrocatalysis of selective reduction of acetylene compounds is a clean, efficient and convenient mode, the electrocatalysis still driven by an external power supply and belongs to a high-energy-consumption process. Taking selective reduction of acetylene to ethylene by electrocatalysis as an example, if all acetylene impurities in ethylene gas produced every year are removed by electrocatalysis reduction, about 13.87 TW.h of electric energy is consumed, which accounts for-0.06% of the total power generation. Acetylene compounds have a high reduction potential, e.g., the standard reduction potential for conversion of acetylene to ethylene is 0.733V vs. she, which is an ideal cathode reaction for chemical batteries.
Based on the background, a novel zinc-alkyne battery is provided, which realizes simultaneous operation of power generation and selective hydrogenation of alkyne compounds.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a bifunctional zinc-alkyne battery, based on the requirement of the current stage on a novel energy device, 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 zinc metal is oxidized with the electrolyte at the anode of the battery (Zn → Zn)2+ +2e-) Electrons flow to the cathode of the battery through an external lead, the acetylene compounds obtain electrons at the cathode, hydrogen is obtained from the electrolyte, and the selective reduction reaction (R) of the acetylene compounds occurs under the action of a high-activity and high-selectivity electrocatalyst1-C≡C-R2+2e-+2H+(H2O)→R1-CH＝CH-R2). 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 the continuous and efficient reduction of the acetylene compounds at the cathode, the invention adopts a flow cell, and the cathode adopts a gas diffusion electrode, a membrane electrode or a foam metal electrode, thereby realizing the continuous supply of cathode reactants and the continuous output of reduction products. Taking the anode as a zinc plate, the cathode as acetylene and the electrolyte as 1M KOH aqueous solution as an example, the structure and the discharge mechanism of the zinc-alkyne battery are shown in figure 1. The zinc-alkyne battery includes several technical problems:
technical scheme
A difunctional 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; the metal zinc is used as an anode and reacts with the electrolyte to generate spontaneous oxidation reaction: zn → Zn2++2e-The acetylene compounds are contacted with a catalyst through a gas diffusion electrode or a membrane electrode, electrons are obtained from an anode, hydrogen ions are obtained from an electrolyte, and reduction reaction is carried out: r1-C≡C-R2+2e-+2H+(or H)2O)→R1-CH＝CH-R2+(OH-) And forming the dual-function zinc-alkyne battery.
The metallic zinc anode includes, but is not limited to, zinc plate, zinc sheet, zinc foil, zinc foam, metallic zinc particles, zinc-based alloy, or zinc composite.
The metal zinc anode is 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.
The catalyst includes but is not limited to alloys based on Pt, Ni, Cu, Zn, Ru, Rh, Pd, Ag or Ir elements and their single atoms, metal phthalocyanines, metal nitrides and carbon and its carbon-nonmetal compound catalyst.
The gas diffusion layer materials include, but are not limited to: carbon fiber paper, carbon fiber woven cloth, non-woven fabric or carbon black paper.
The acetylene compound raw material comprises but is not limited to acetylene, propyne, butyne, 1, 4-butynediol, propargyl alcohol or 2-methyl-3-butynediol, and a mixture thereof or a mixture of a carbon-carbon triple bond-containing compound and other substances.
The catholyte and the 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, and 0.01-10M KHCO3Solution or 0.01-10M KOH solution.
The discharging condition of the battery is that the flow rate of the alkyne-containing reactant 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.
Advantageous effects
The invention provides a difunctional zinc-alkyne battery, which adopts metal zinc as an anode and has spontaneous oxidation reaction with electrolyte: zn → Zn2++2e-The method adopts a gas diffusion electrode or a membrane electrode as a cathode, acetylene compounds are contacted with a catalyst through the gas diffusion electrode or the membrane electrode, electrons are obtained from an anode, hydrogen ions are obtained from electrolyte, and reduction reaction is carried out: r1-C≡C-R2+2e-+2H+(or H)2O)→R1-CH＝CH-R2+(OH-) And forming the dual-function zinc-alkyne battery. The battery can generate electric energy and simultaneously generate electrocatalytic acetylene compound reduction reaction at the cathode of the battery, so that the electrocatalytic reduction of the acetylene compound to an alkene compound is realized without an external power supply. Experimental results show that the battery can achieve high power density and energy density, can drive the hydrogenation reaction of the cathode acetylene compounds, can also generate electric energy, and realizes a functional novel chemical power supply integrating power generation and reduction of the acetylene compounds.
The invention utilizes the zinc oxidation reaction of the anode and couples the hydrogenation reaction of the acetylene compounds of the cathode, thereby not only carrying out high-efficiency and high-selectivity semi-hydrogenation reduction on the acetylene compounds without consuming electric energy, but also generating additional electric energy and realizing the chemical power supply integrating power generation and reduction of the acetylene compounds under mild conditions. MiningZinc-alkyne cells (1 cm) assembled with the design of the invention2Electrode area) of 1.1V and a maximum power density of 2.2mW cm-2The energy density is 213.8Wh kgZn -1. Meanwhile, by regulating and controlling proper discharge current, the Faraday efficiency of reducing alkyne into alkene can reach 99.0 percent, so that the efficient electroreduction of alkyne compounds is realized, and the method has a wide application prospect.
Drawings
Fig. 1 shows the structure and discharge mechanism of a novel zinc-alkyne cell (taking an anode as a zinc plate, a cathode as raw material of acetylene, and an electrolyte as 1m koh aqueous solution as an example).
FIG. 2 is a graph having a length of 1cm2Electrode area discharge curve and power density curve for a zinc-acetylene cell.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
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 invention aims to solve the third technical problem of design and performance test of a zinc-alkyne battery device for continuously reducing alkyne compounds.
In order to solve one of the above technical problems, the technical solution of the present invention includes:
(1) the zinc anode is prepared by loading metal zinc or alloy and compound thereof on a current collector by means of spraying, dipping, electro-deposition and the like
(2) The zinc plate, the zinc sheet, the foam zinc or the zinc foil is directly used as the zinc anode.
To solve the second technical problem, the technical solution of the present invention includes:
(1) preparation of gas diffusion electrode: accurately weighing a certain mass (1-1000 mg) of catalyst powder, dispersing the catalyst powder in a solvent with a certain volume (0.2-200 mL), adding 3.3 muL-3.3 mL of Nafion solution (5%), and then ultrasonically dispersing for 10-120 minutes, preferably 30-60 minutes, so as to obtain catalyst slurry; placing the gas diffusion layer on a flat plate heating table, wherein the heating temperature is 50-100 ℃, and preferably 70-90 ℃; accurately measuring catalyst slurry with a certain volume (50-500 mu L), uniformly spraying the catalyst slurry on a gas diffusion layer, and fully drying to prepare the gas diffusion electrode.
(2) Preparing a membrane electrode: accurately measuring catalyst slurry with a certain volume (50-500 mu L), uniformly spraying the catalyst slurry on an ion exchange membrane, and fully drying to obtain the membrane electrode.
(3) Preparation of the foam metal electrode: preparing a copper nano structure on the surface of the foam copper or loading the copper nano material on a foam metal substrate.
To solve the third technical problem, the technical solution of the present invention includes:
(1) adopting a fluid battery, taking a gas diffusion electrode, a membrane electrode or a foam metal electrode made of a catalyst as a battery cathode, and matching with a zinc anode; the catholyte and the anolyte are separated by an ion exchange membrane; the acetylene compound raw material is supplied from the cathode chamber.
(2) In the discharging process of the battery, the flow rate of the raw material of the negative acetylene compound is 5-100 sccm, the flow rate of the negative electrolyte is 1-100 sccm, and the flow rate of the positive electrolyte is 1-100 sccm; and obtaining a corresponding acetylene compound hydrogenation product at the cathode gas 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 represented by adopting a potentiostatic method or a galvanostatic method, and the concentration of each component of a product at the cathode outlet of the battery is detected by using an online gas chromatography.
In making the battery anode, the metallic zinc anode includes, but is not limited to: zinc sheet, zinc foil, zinc foam, metallic zinc 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, the zinc sheet, the zinc foil and the foamed zinc comprises but is not limited to 0.05-1.0 mm, and the area of the zinc plate comprises but is not limited toLimited to 1-40 cm2。
When the cathode of the battery is manufactured, the catalyst powder comprises but is not limited to Pd, Pd-based alloy, metal nitride and metal phthalocyanine complex catalyst.
The catalytic material includes but is not limited to alloys based on elements such as Pt, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Ir, etc., and single atoms thereof, metal phthalocyanines, metal nitrides, carbon and carbon-nonmetal compound catalysts thereof, etc.
The gas diffusion layer materials include, but are not limited to: carbon paper, carbon cloth, non-woven fabric, carbon black paper, or the like.
The catholyte and the anolyte are acidic, neutral, alkaline electrolyte or solid electrolyte, but not limited to: 0.01-5M hydrochloric acid, 0.01-5M sulfuric acid, 0.01-5M KCl solution, and 0.01-10M KHCO3Solution or 0.01-10M KOH solution.
The acetylene compound raw material comprises, but is not limited to acetylene, propyne, butyne, 1, 4-butynediol, propargyl alcohol, 2-methyl-3-butynediol and other gaseous or liquid compounds containing carbon-carbon triple bonds and mixtures thereof or mixtures of carbon-carbon triple bond compounds and other substances.
The zinc-alkyne cells were assembled in combination with specific acetylenic compounds and catalysts and the performance of the assembled cells and the product component content at the cathode outlet were tested.
The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments of the present 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 combinations thereof. The technical solution of the present invention is described below with reference to examples.
[ example 1 ]
(1) Taking a gas diffusion electrode made of Cu dendrites as a battery cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; both the catholyte and anolyte were 0.5M H2SO4The solutions are separated by proton exchange membrane, and assembled into 1cm as shown in figure 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of Cu dendrite by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatograph, and calculating Faraday efficiency.
[ example 2 ]
(1) Taking a gas diffusion electrode made of Cu dendrites as an electrolytic cell cathode; taking polished Zn foil with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne cell.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of Cu dendrite by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatograph, and calculating Faraday efficiency.
[ example 3 ]
(1) Taking a gas diffusion electrode made of Cu dendrites as an electrolytic cell cathode; foamed zinc with the thickness of 1mm is used as a battery anode; the catholyte and the anolyte are 0.5M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of Cu dendrite by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatograph, and calculating Faraday efficiency.
[ example 4 ] A method for producing a polycarbonate
(1) Taking a gas diffusion electrode made of Cu dendrites as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: 1% acetylene, 99% ethylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting a discharge curve of the Cu dendritic crystal by using an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu dendritic crystal by using a constant current method, determining the content of each component in outlet gas by using an online gas chromatography, and calculating Faraday efficiency.
[ example 5 ]
(1) Preparing a gas diffusion electrode made of Cu dendrites as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: 1% of propine and 99% of propylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu dendrite catalyst by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatograph, and calculating Faraday efficiency.
[ example 6 ]
(1) Taking a gas diffusion electrode made of Cu dendrites as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: 1% butyne, 9% 1, 3-butadiene, and the balance argon.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu dendrite catalyst by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatograph, and calculating Faraday efficiency.
[ example 7 ]
(1) Taking a gas diffusion electrode made of Cu nano particles as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1.0M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: 1% acetylene, 99% ethylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu nanoparticles by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatography, and calculating Faraday efficiency.
[ example 8 ]
(1) Gas diffusion electrode made of Cu nanoparticles asA cathode of the electrolytic cell; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 0.5M KOH solution, separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu nanoparticles by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatography, and calculating Faraday efficiency.
[ example 9 ]
(1) Taking a membrane electrode made of Ag nanowires as the cathode of the electrolytic cell; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the anolyte was 0.5M H2SO4The solutions are separated by proton exchange membrane, and assembled into 1cm as shown in figure 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) And collecting a discharge curve by using an electrochemical workstation, calculating power density, representing the catalytic activity of the Ag nanowire by using a constant current method, determining the content of each component in outlet gas by using an online gas chromatography, and calculating Faraday efficiency.
[ example 10 ]
(1) A metal electrode prepared from foam copper is used as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and anolyte were 1.0M KOH solution and assembled to 1cm2A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: 2-methyl-3-butynediol.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of the Cu nanoparticles by a constant current method, determining the content of each component in outlet gas by adopting an online gas chromatography, and calculating Faraday efficiency.
Comparative example 1
(1) Taking a gas diffusion electrode made of supported 5% Pd/C as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1M KOH solution, and are separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of 5% Pd/C by a constant current method, determining the content of each component in outlet gas by adopting on-line gas chromatography, and calculating Faraday efficiency.
Comparative example 2
(1) Taking a gas diffusion electrode made of load type 10% Pd/C as an electrolytic cell cathode; taking a polished Zn plate with the thickness of 0.1mm as a battery anode; the catholyte and the anolyte are 1M KOH solution, and are separated by anion exchange membrane, and assembled into 1cm by the schematic diagram of the device shown in FIG. 12A zinc-alkyne battery.
(2) The flow rate of the mixed reaction gas is controlled to be 50sccm by using a gas mass flow meter, and the acetylene compound raw material used in the experiment comprises the following components: high purity acetylene.
(3) The catholyte and anolyte flow rates were controlled at 50sccm with a peristaltic pump.
(4) Collecting the discharge curve by an electrochemical workstation, calculating power density, representing the catalytic activity of 10% Pd/C by a constant current method, determining the content of each component in outlet gas by adopting on-line gas chromatography, and calculating Faraday efficiency.
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-mentioned embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention are within the scope of the present invention without any creative effort.
Claims (10)
1. A difunctional 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; the metal zinc is used as an anode and reacts with the electrolyte to generate spontaneous oxidation reaction: zn → Zn2++2e-The acetylene compounds are contacted with a catalyst through a gas diffusion electrode or a membrane electrode, electrons are obtained from an anode, hydrogen ions are obtained from an electrolyte, and reduction reaction is carried out: r1-C≡C-R2+2e-+2H+(or H)2O)→R1-CH＝CH-R2+(OH-) And forming the dual-function zinc-alkyne battery.
2. The bifunctional zinc-alkyne battery of claim 1, wherein: the metallic zinc anode includes, but is not limited to, zinc plate, zinc sheet, zinc foil, zinc foam, metallic zinc particles, zinc-based alloy, or zinc composite.
3. The bifunctional zinc-alkyne battery of claim 1, wherein: the metal zinc anode is obtained by loading metal zinc or alloy and compound thereof on an anode current collector by adopting spraying, dipping or electrodeposition means.
4. The bifunctional zinc-alkyne battery of claim 3, wherein: 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.
5. The bifunctional zinc-alkyne battery of claim 1, wherein: the catalyst includes but is not limited to alloys based on Pt, Ni, Cu, Zn, Ru, Rh, Pd, Ag or Ir elements and their single atoms, metal phthalocyanines, metal nitrides and carbon and its carbon-nonmetal compound catalyst.
6. The bifunctional zinc-alkyne battery of claim 1, wherein: the gas diffusion layer materials include, but are not limited to: carbon fiber paper, carbon fiber woven cloth, non-woven fabric or carbon black paper.
7. The bifunctional zinc-alkyne battery of claim 1, wherein: the acetylene compound raw material comprises but is not limited to acetylene, propyne, butyne, 1, 4-butynediol, propargyl alcohol or 2-methyl-3-butynediol, and a mixture thereof or a mixture of a carbon-carbon triple bond-containing compound and other substances.
8. The bifunctional zinc-alkyne battery of claim 1, wherein: the catholyte and the anolyte are acidic, neutral, alkaline or solid electrolytes.
9. Bifunctional zinc as in claim 1-an alkyne battery, characterized in that: 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, and 0.01-10M KHCO3Solution or 0.01-10M KOH solution.
10. The bifunctional zinc-alkyne battery of claim 1, wherein: the discharging condition of the battery is that the flow rate of the alkyne-containing reactant 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.
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