CN114908361A - Secondary battery and electrocatalysis electrolytic cell mixing device - Google Patents

Secondary battery and electrocatalysis electrolytic cell mixing device Download PDF

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CN114908361A
CN114908361A CN202210603707.6A CN202210603707A CN114908361A CN 114908361 A CN114908361 A CN 114908361A CN 202210603707 A CN202210603707 A CN 202210603707A CN 114908361 A CN114908361 A CN 114908361A
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battery
electrode
electrocatalytic
zinc
energy storage
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夏宝玉
陈圣华
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention belongs to the field of energy storage and conversion, and discloses a secondary battery and electrocatalysis electrolytic cell mixing device, which comprises an electrolytic cell, a first electrode and a second electrode; when the secondary battery is not connected with an external power supply, the first electrode, the second electrode and the electrolyte can form the secondary battery; when the device is connected with an external power supply, the first electrode, the second electrode and the electrolyte can form an electrocatalytic reaction tank for electrocatalytic reaction; this enables the hybrid device to operate in either the energy storage battery mode or the electrocatalytic mode. The integrated secondary battery and electrocatalysis electrolytic cell mixing device obtained by the invention can run in a battery mode or an electrocatalysis mode (wherein, short-term energy storage can be realized in the battery mode, and electrochemical energy conversion can be utilized in the electrocatalysis mode to further realize long-term energy storage), so that the device is a new product category which can meet the requirements of short-term energy storage and long-term energy storage at the same time, has double functions of the battery and the electrolyzer, and can improve the overall efficiency.

Description

Secondary battery and electrocatalysis electrolytic cell mixing device
Technical Field
The invention belongs to the field of energy storage and conversion, and particularly relates to a secondary battery and electrocatalysis electrolytic cell mixing device.
Background
It is expected that the global energy demand will double in the next half of this century. The goal of paris agreement was to achieve a net zero emission economy of greenhouse gases by 2050 to limit the impact of climate change. Therefore, providing energy in a sustainable manner is one of the major challenges facing our generation. To achieve this goal, society must acquire all the energy from renewable sources and electrify the end use as much as possible. Among them, energy storage batteries are most efficient for short term storage of energy.
One of the biggest challenges facing renewable energy sources, wind and solar, is their unpredictability and intermittency. In the case of solar energy, surplus energy is generated in the daytime and summer, but the supply is reduced in the nighttime and winter. With the rapid development of the conversion of sunlight into electrical energy, the problem of storing renewable electricity becomes more prominent. Electrocatalytic carbon dioxide (CO) for production of valuable carbon-based fuels and hydrogen energy 2 ) Reduction (CO) 2 RR), electrocatalytic organic synthesis, electrolysis of water and other electrocatalytic reactions address both the need to store intermittent renewable energy sources and the urgent need to reduce the net emission of greenhouse gases. While green carbon-based fuels will play a key role in balancing renewable power supplies with longer demand.
Disclosure of Invention
In view of the above deficiencies or needs in the art, and in particular the lack of balance between renewable energy and large-scale social needs at all with the cell and electrolyzer technology available today, it is an object of the present invention to provide a secondary battery and electrocatalytic electrolysis cell hybrid device, wherein the secondary battery is made available by combining it with electrocatalytic electrolysisThe cell is functionally combined, and a battery and an electrocatalysis system are skillfully coupled, so that the integrated secondary battery and electrocatalysis electrolytic cell mixing device can operate under the configuration of a two-chamber battery electrolytic cell in a battery mode or an electrocatalysis mode (the two chambers are separated by a diaphragm), wherein short-term energy storage can be realized in the battery mode; the electrocatalysis mode can utilize electrochemical energy conversion, so that long-term energy storage is realized), the electrochemical energy storage device is a new product category which can meet the requirements of short-term energy storage and long-term energy storage at the same time, has dual-purpose energy storage of battery and electrolyzer functions, and can improve the overall efficiency. Taking the alkaline zinc ion battery and carbon dioxide reduction electrolytic cell mixing device obtained based on the invention as an example, the conversion between energy storage and electrocatalysis is very flexible and can be carried out at any time, for example, the energy storage function can be realized by charging and discharging the zinc ion battery, the external power supply can be realized, and CO is introduced into the Zn electrode end 2 The gas can realize electrocatalysis of CO 2 RR; furthermore, electrocatalysis of CO 2 The product type of RR can be regulated and controlled by the last charge-discharge state of the battery. Electrocatalysis of CO when the energy storage end is finished in a charged state 2 The product at the reducing end is CO; on the contrary, when the energy storage end is in a discharge state, the CO is electrically catalyzed 2 The product at the reducing end is formic acid.
To achieve the above objects, according to one aspect of the present invention, there is provided a secondary battery and electrocatalytic electrolytic cell hybrid device, characterized by comprising an electrolytic cell, and a first electrode and a second electrode located within the electrolytic cell; the electrolytic cell is used for containing electrolyte;
when the first electrode and the second electrode are not connected with an external power supply, the first electrode, the second electrode and the electrolyte can form a secondary battery, wherein the first electrode is used as a positive electrode of the secondary battery, and the second electrode is used as a negative electrode of the secondary battery; meanwhile, when the first electrode and the second electrode are connected with an external power supply, the first electrode, the second electrode and the electrolyte can form an electrocatalytic reaction tank for electrocatalytic reaction, wherein the first electrode is used as an anode of the electrocatalytic reaction tank, and the second electrode is used as a cathode of the electrocatalytic reaction tank; this enables the hybrid device to operate in either an energy storage battery mode or an electrocatalytic mode.
As a further preferable aspect of the present invention, the secondary battery is an alkaline zinc-ion battery; preferably, the zinc ion battery is a nickel-zinc battery, a zinc-air battery, a zinc-silver battery or a zinc-mercury battery;
the electrocatalytic reaction is electrochemical reduction of carbon dioxide.
As a further preferred aspect of the present invention, the negative electrode of the zinc ion battery is zinc metal; the negative electrode of the zinc ion battery is electrochemically reduced (CO) in carbon dioxide 2 RR) and the positive electrode of the zinc ion battery serves as the anode in the electrochemical reduction of carbon dioxide.
In a further preferred embodiment of the present invention, the negative electrode of the zinc ion battery is a cathode catalyst for electrocatalytic carbon dioxide reduction, and is capable of electrocatalytic reduction of carbon dioxide in the electrolyte solution after carbon dioxide treatment; preferably, the carbon dioxide treatment is specifically carbon dioxide saturation treatment;
and when the hybrid device is switched to the electrocatalytic mode after passing through the energy storage battery mode:
when the energy storage state of the zinc ion battery is the charging condition for the last time, the corresponding electrocatalytic reaction is to react CO 2 Reducing to CO;
when the energy storage state of the zinc ion battery is the discharge condition for the last time, the corresponding electrocatalysis reaction is to react CO with CO 2 Reducing to formic acid.
As a further preferred feature of the present invention, the mixing device is further provided with CO 2 An inlet, a CO outlet, and a formic acid outlet; wherein said CO is 2 The inlet can introduce CO into the electrolyte 2 A gas; the CO outlet is arranged above the liquid level of the electrolyte; the formic acid outlet is positioned on the side wall or the bottom of the reaction cavity containing the electrolyte.
As a further preferred aspect of the present invention, the secondary battery is a copper-zinc battery, a lead-acid battery, a PbO battery 2 The electrocatalytic reaction is carbon dioxide electrochemical reduction.
As a further preferable aspect of the present invention, the secondary battery is an alkaline nickel-based battery, and the electrocatalytic reaction is electrocatalytic electrolysis of water;
or the secondary battery is a bismuth-based battery, and the electrocatalytic reaction is electrochemical nitrogen reduction;
or the secondary battery is a copper-based battery or a nickel-based battery, and the electrocatalytic reaction is electrochemical organic synthesis and conversion.
As a further preferred aspect of the present invention, the secondary battery is any one of a cobalt-based battery, a copper-based battery, a Li-ion battery, a bismuth-based battery, a molybdenum-based battery, a ruthenium-based battery, a silver-based battery, and a palladium-based battery, and the electrocatalytic reaction is electrochemical NO reduction (NORR), electrochemical nitrate reduction, or nitrogen reduction.
As a further preferred feature of the present invention, the external power source is a solar cell or a wind power generator.
According to another aspect of the invention, a method for using the hybrid device of the secondary battery and the electrocatalysis electrolytic cell is provided, which is characterized in that the hybrid device is put into an energy storage battery mode or an electrocatalysis mode to work;
preferably, the using method is that the working stage of the energy storage battery mode is firstly carried out, and then the working stage of the electrocatalysis mode is carried out, and the using method specifically comprises the following steps:
(1) Energy storage battery mode working stage: the first electrode and the second electrode are not connected with an external power supply by the regulation switch, so that the first electrode, the second electrode and the electrolyte form a secondary battery; the function of the energy storage battery is realized by charging and discharging the secondary battery;
(2) And (3) an electrocatalysis mode working stage: the first electrode and the second electrode are connected with an external power supply through the regulating switch, and the first electrode, the second electrode and the electrolyte form an electrocatalysis reaction tank, so that electrocatalysis reaction is carried out, and an electrocatalysis function is realized.
Through the technical scheme, compared with the prior art, the secondary battery and electrocatalysis electrolytic cell mixing device can work in an energy storage battery mode or an electrocatalysis mode. When the mixing device is in the battery mode by the adjusting switch, the device presents a short-term energy storage state; when the mixing device is in the electrocatalytic mode by adjusting the switch, the device can realize energy conversion and present a long-term energy storage state. The mixing device has extremely strong flexibility, can be flexibly and randomly switched between an energy storage battery mode and an electrocatalysis mode during use, and can meet social requirements to execute energy storage and electrocatalysis conversion at any time.
The mixing device of the secondary battery and the electro-catalytic electrolytic cell is a novel mixing system with switchable function and product selectivity, can meet the short-term and long-term energy storage requirements at the same time, and particularly can meet the actual requirements of a renewable energy new era. The present invention, by integrating the cell and electrolyzer hybrid system with ultra high efficiency, can operate continuously in one of a battery mode or an electrocatalytic mode so that the user can select such as: a) Executing power grid frequency modulation and peak regulation; or b) to selectively perform electrocatalytic reactions (when electricity is low and certain chemicals are expensive).
Such a hybrid system is very flexible and robust, and therefore allows to balance arbitrage, in particular between the prices of electric and electrochemically converted chemicals, stabilizing the negative effects of energy price fluctuations. For example, battery functionality may monetize daily power imbalances, while chemicals produced may monetize seasonal power imbalances and provide feedback for non-electrified industries. The novel and breakthrough integration of these technologies has significantly improved performance, reduced cost and increased uptime. The hybrid battery-electrolysis system designed by the invention is a green innovative system taking the market as a guide, and opens a new door for simultaneously realizing large-scale long-term and short-term energy storage in industry. This will drive the energy, production and consumption revolution.
By secondary electricityThe cell is an alkaline zinc ion cell, the electrocatalytic reaction cell is a carbon dioxide reduction electrolytic cell, and the mixing device has the functions of energy storage and electrocatalysis of CO 2 The reduction function can obtain the following beneficial effects when in use:
(1) Due to the complete flexibility of the system (-100%/+ 100%), continuous operation and price balancing arbitrage of electricity and carbon based fuels. Due to the high efficiency of 80-92% (HHV) and the responsible use of scarce green electrons, the cost of electricity is reduced. Due to the abundance and non-conflicting active materials (nickel and zinc), large-scale deployment is possible. Due to the synergistic effect of material usage, power electronics, factory and footprint balance, resources are effectively utilized. Due to the durable combination of alkaline electrolysis and nickel-zinc battery technology, the service life is long (more than 20 years), and the battery pack does not need to be replaced. The effective battery cost is reduced because the nickel zinc battery has a high depth of discharge without electrode degradation and is completely resistant to overcharge (electrolysis). Due to the water-based electrolyte, it is not flammable (unlike lithium ion batteries or sodium sulfur batteries). Since no hazardous materials are used (unlike PEM electrolyzers or lithium ion batteries), recycling at the end of service life is simple and low cost.
(2) The present invention provides a single platform that can simultaneously meet both short-term and long-term energy storage requirements. During continuous power supply, the system will charge and discharge according to the changes in grid demand, monetizing daily supply imbalances. In particular weather conditions, however, the power supply is intermittent and renewable, and the power is available for electrolysis and carbon monoxide or formic acid production, which are the cornerstones of hydrocarbon synthesis. This may be taken advantage of by seasonal supply imbalances. The ability to generate two revenue streams from one platform allows a balanced arbitrage between electricity and carbon dioxide prices, thereby providing an economic advantage over disposable systems. For example, the system may be used to store power and produce onsite CO at low electricity prices 2 And sell electricity when the price of electricity is high. The integration of these two technologies provides efficient utilization of resources, material usage, plant balance, and footprint.
(3) When seasonal variations are considered, conventional electrocatalytic devices may result in a supply shortage and a reduction of one or more productsAnd less profit. In contrast, the hybrid system of the present invention can reduce the cost of switching between seasonal products, thereby eliminating the additional cost of disassembling/assembling the stack (not to mention disassembling the stack is not a practical option), while utilizing the full capacity of the plant for all weather. Also, the hybrid system stands out when trading off the decision to make up for long term production with upfront investment. This is important in markets where there is economic (even political) uncertainty that results in significant changes in demand, supply, and commodity prices (e.g., if an investor decides to stop production of a certain product because of an excess supply). The prediction of the technical economic analysis shows that the profit of the hybrid system can be significantly increased compared to a single-mode system (dedicated electrodes for different products), since the hybrid system can adapt to seasonal fluctuations in price and demand, generating additional energy storage functions and different CO's over long and short periods 2 RR products are used alternately to gain profit (chemical and electricity prices are floating fast).
(4) For the production of many hydrocarbons (e.g. CO and formic acid) it is also conceivable that in this case it would be more practical to simply switch the polarity of the electrolysis cell to switch the product quickly without replacing the catalyst. CO and formic acid may not be the most attractive products, but this work lays the foundation for future work, and new systems can be developed to switch between carbon rich products or gaseous and liquid products in the same system.
(5) Allowing additional solar and wind energy exploitation even if the grid is limited. Business cases for renewable energy power generation assets are improved by storing electricity and producing carbon-based fuels when low prices are reached and selling electricity when high prices are reached. And the annual renewable energy is provided for off-grid communities. Green carbon-based fuels are produced on-site for industrial customers and balance power requirements. And this effective reduction of atmospheric CO 2 Can benefit from carbon taxes based on current targets of carbon peaking, carbon neutralization.
In summary, the hybrid device of the present invention is a single platform that can satisfy both short-term and long-term energy storage requirements, is a new product category, has breakthrough flexibility, robustness, high efficiency, uses materials that are inexpensive and easy to recycle, and is expected to balance renewable energy with large-scale social needs.
Drawings
FIG. 1 is a schematic diagram of a mixing device of an alkaline zinc ion battery and a carbon dioxide reduction electrolytic cell based on the invention (CO) 2 Is selectively introduced, without introducing CO in the battery mode 2 In electrocatalysis of CO 2 CO is introduced only in RR mode 2 )。
FIG. 2 is an energy storage and electrocatalytic CO of the hybrid device shown in FIG. 1 2 Schematic diagram of RR (without CO injection in Battery mode) 2 In the electrocatalysis of CO 2 CO is introduced only in RR mode 2 )。
FIG. 3 is an electrocatalytic CO corresponding to a particular stage of the energy storage module of the hybrid device shown in FIG. 1 2 Regulating and controlling the RR product species selectivity.
Fig. 4 is a schematic view of an apparatus for a zinc-air cell.
Fig. 5 is a schematic diagram of a mixing device of an alkaline nickel-iron battery and an electrolytic water electrolysis battery based on the invention.
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. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the secondary battery and electrocatalysis electrolytic cell mixing device skillfully couples the energy storage battery and the electrocatalysis conversion, and can realize energy storage and conversion.
Taking zinc ion batteries as an example, metallic zinc is a material with high hydrogen evolution potential, and is used in waterIs electrocatalytic of CO 2 RR is very popular. Based on the invention, the alkaline zinc ion battery is electrically catalyzed by CO 2 RR is combined, a battery and an electro-catalysis system are skillfully coupled, and the obtained alkaline zinc ion battery and carbon dioxide reduction electrolytic cell mixing device can flexibly convert between energy storage and electro-catalysis so as to realize flexible adjustment of short-term energy storage and long-term energy storage. In addition, by changing the operating state (i.e., whether the last charge or discharge) of the energy storage zinc cell, electrocatalytic CO can be achieved 2 Switching regulation of RR product selectivity.
According to the mixing device of the alkaline zinc ion battery and the carbon dioxide reduction electrolytic cell, as shown in fig. 1, the zinc ion battery is a battery with a negative electrode made of zinc metal, and the electrolyte is alkaline electrolyte and contains saturated zinc ions.
The zinc ion battery can be an alkaline zinc ion battery which takes zinc metal as a negative electrode, such as a nickel-zinc battery, a zinc-air battery or a zinc-manganese battery.
In some embodiments, the zinc-ion battery is a nickel-zinc battery, and the battery electrocatalytic hybrid system operates in the following modes: a zinc sheet is taken as a negative electrode, a sintered nickel electrode (hydroxyl nickel oxide/nickel hydroxide) is taken as a positive electrode, the positive electrode and the negative electrode are separated by a diaphragm, and zinc oxide or zinc oxalate saturated 1-6M potassium hydroxide is taken as electrolyte. And inserting the positive electrode and the negative electrode into an electrolytic cell containing electrolyte, and carrying out charge and discharge tests on the nickel-zinc battery by using a battery test system. As shown in FIG. 2, the final state of the nickel-zinc battery is controlled to be charging, and then the nickel-zinc battery is subjected to electrocatalysis CO 2 The use of RR, the corresponding reduction product is CO. By controlling the final state of the Ni-Zn cell to discharge, followed by electrocatalysis of CO 2 The product of the conversion is formic acid.
In some embodiments, the nickel electrode is a commercial sintered nickel electrode, the zinc negative electrode is a zinc sheet with a purity of 99.9% -99.99%, the positive electrode and the negative electrode are separated by a diaphragm, and zinc oxide or zinc oxalate saturated 1-6M potassium hydroxide is used as an electrolyte. Two electrodes are directly inserted into an electrolytic cell containing electrolyte, and the area of the positive and negative electrode plates in the electrolyte is controlled to be 1 x 1cm 2 At a distance of 1-3c from each otherAnd m is selected. And carrying out charge and discharge tests on the nickel-zinc battery by using a blue battery test system.
In some embodiments, the zinc ion cell is a zinc-air cell: the zinc sheet is used as a negative electrode, oxygen in the air is used as a positive electrode, the positive electrode and the negative electrode are separated by a diaphragm, and zinc oxide or zinc oxalate saturated 1-6M potassium hydroxide is used as electrolyte. And inserting the anode and the cathode into an electrolytic cell containing electrolyte, and performing energy storage test on the zinc-air battery by using a battery test system. By controlling the final state of the zinc-air battery to be charging and then carrying out electrocatalysis on the battery to CO 2 The use of RR, the corresponding reduction product is CO. By controlling the last state of a zinc-air cell to be discharge, followed by electrocatalysis of CO 2 The product of the conversion is formic acid.
In some embodiments, the zinc-ion battery is an alkaline zinc-manganese battery, and the operation mode of the battery electrocatalytic hybrid system is as follows: using zinc sheet as cathode and MnO 2 The anode and the cathode are separated by a diaphragm, and zinc oxide or zinc chloride saturated 1-6M potassium hydroxide is used as electrolyte. And inserting the anode and the cathode into an electrolytic cell containing electrolyte, and performing energy storage test on the alkaline zinc-manganese battery by using a battery test system. By controlling the final state of the zinc-manganese battery to be charging and then carrying out electrocatalysis on the zinc-manganese battery to CO 2 The corresponding reduction product is CO. By controlling the final state of the zinc-manganese cell to discharge, followed by electrocatalysis of CO 2 The product of the conversion is formic acid.
Furthermore, based on the invention, the state of the zinc sheet cathode can be regulated and controlled by designing and optimizing the preparation process flow and regulating and controlling external factors such as charge-discharge current density, cycle number, charge-discharge time, discharge cut-off voltage, constant voltage charge-discharge and the like in the energy storage process of the battery.
For example, in a preferred embodiment, as shown in fig. 3, when the zinc ion battery (i.e., nickel zinc battery) is in full charge energy storage, the Zn electrode surface is in a Zn dendritic state, and the corresponding CO is electrocatalyzed 2 The CO product selectivity of RR is highest; when the energy storage battery is in a discharge cut-off state, the surface of the Zn electrode is in a nanosheet state, and CO is correspondingly electrocatalyzed 2 RR to formic acid product selectivity is greatestIs high. The same effect is also applicable to other zinc ion batteries, such as zinc-air batteries, zinc-manganese batteries and the like.
The following are specific examples:
example 1
(1) Assembling the nickel-zinc battery: the nickel electrode is a commercial sintered nickel electrode, the zinc cathode is a zinc sheet with the purity of 99.9-99.99%, and zinc oxide or zinc oxalate saturated 6M potassium hydroxide is used as electrolyte. And carrying out charge and discharge tests on the nickel-zinc battery by using a blue battery test system. CO 2 2 RR performance evaluation: in CO 2 Saturated 0.1M KHCO 3 In the method, an electrochemical workstation connected with a Gas Chromatograph (GC) is adopted, carbon dioxide is reduced by constant potential electrolysis, and the potential range is-0.9V-1.5V vs Reversible Hydrogen Electrode (RHE). CO 2 2 And the gas product of RR is subjected to calibration detection by gas chromatography, and the liquid product is subjected to calibration detection by nuclear magnetic resonance.
(2) By regulating and controlling the charging and discharging conditions: charging and discharging current density (10, 20, 30mA cm) -2 ) Electrocatalytic CO charging/discharging to zinc sheet cathode, charging time (10, 20, 30, 40, 50 min), discharge cut-off voltage (1.0, 1.2,1.4, 1.6V) and constant voltage charging/discharging, etc 2 The performance of RR is regulated. By controlling the above experimental parameters, the last state is regulated and controlled by charging and electrocatalysis of CO 2 The major product of RR is CO; controlling the final charge-discharge state of the battery to be discharge, and electrocatalysis of CO 2 The major product of RR is formic acid.
Example 2
(1) A mixing device of a zinc-air battery and a carbon dioxide reduction electrolytic cell. Assembling a zinc-air battery: the air electrode is commercial activated carbon (sprayed on the foamed nickel), the zinc cathode is a zinc sheet with the purity of 99.9-99.99%, and zinc oxide or zinc oxalate saturated 6M potassium hydroxide is used as an electrolyte. And finally, assembling the battery (figure 4), wherein the battery shell is made of PMMA material, and a blue battery testing system is utilized to perform charging and discharging tests on the zinc-air battery. CO of the system 2 RR performance evaluation was consistent with example 1.
(2) Zinc-air battery and electrocatalytic CO 2 Performance testing of the recovery System same as the example1 are identical.
By regulating and controlling the charging and discharging conditions: charging and discharging current density (10, 20, 30mA cm) -2 ) Electrocatalytic CO charging/discharging to zinc sheet cathode, charging time (10, 20, 30, 40, 50 min), discharge cut-off voltage (1.0, 1.2,1.4, 1.6V) and constant voltage charging/discharging, etc 2 The performance of RR is regulated. By controlling the above experimental parameters, the last state of regulation is charging, electrocatalysis of CO 2 The major product of RR is CO; controlling the final charge-discharge state of the battery to be discharge and electrocatalysis of CO 2 The major product of RR is formic acid.
Example 3
(1) A lead-acid battery and carbon dioxide reduction electrolytic cell mixing device. Assembling the lead-acid battery: in the discharge state of the lead-acid battery, the main component of the positive electrode is lead dioxide, and the main component of the negative electrode is lead; in a charging state, the main components of the positive electrode and the negative electrode are lead sulfate. And taking sulfuric acid as electrolyte, and carrying out charge and discharge tests on the alkaline zinc-manganese battery by using a blue battery test system. CO of the system 2 RR performance evaluation was consistent with example 1.
(2) Lead acid battery and electrocatalytic CO 2 The performance test of the RR system is identical to example 1.
And corroding and regenerating the positive and negative electrodes of the lead-acid battery by selecting charge and discharge parameters. Electrocatalytic CO on lead sulphate 2 The performance of RR is regulated. By controlling the above experimental parameters, CO is electrocatalyzed 2 The major product of RR is formic acid.
Example 4
A mixing device of a nickel-iron battery and electrolytic water. Nickel-iron batteries have undesirable nodules that produce hydrogen gas. When the nickel-iron battery is in an overcharged state, the nickel-iron battery starts to electrolyze water. Wherein, the nickel electrode terminal generates electrochemical oxygen evolution reaction, and the iron electrode terminal generates electrochemical hydrogen evolution reaction.
Nickel-iron batteries are nickel-iron electrodes that have been available since the edison age, and the hybrid devices obtained based on the present invention incorporate the alkaline electrolysis technology that is commercially available today. Such a battery system can capture and store hydrogen gas at high pressure, which makes it very energy efficient and competitive with battery technology. Conventional batteries, such as lithium-based batteries, can store energy for a short period of time, but when they are fully charged, they must release excess energy, otherwise they can overheat and degrade. On the other hand, the nickel-iron battery remains stable when fully charged, at which time it can be converted to produce hydrogen.
The above embodiments are merely examples, and other secondary batteries (e.g., copper zinc batteries, lead-acid batteries, pbO) may also be used based on the present invention 2 A Cu cell, a nickel-cadmium cell, a bismuth-based cell) and a carbon dioxide reduction electrolytic cell mixing device; other secondary batteries and electrocatalytic hybrid devices, such as alkaline nickel-based batteries with electrolyzed water, copper-based batteries or nickel-based batteries with electrochemical organic synthesis and conversion; other secondary batteries (e.g., cobalt-based batteries, copper-based batteries, li-ion batteries, bismuth-based batteries, molybdenum-based batteries, ruthenium-based batteries, silver-based batteries, and palladium-based batteries) are reacted with electrochemical NO reduction (NORR), electrochemical nitrate reduction, or nitrogen reduction. In addition, the detail components of the system can be flexibly adjusted according to the existing technology or the known improvement direction of the water electrolysis industry, for example, the development of a dual-function catalyst (HER/OER with high efficiency) can be further researched to reduce the complexity of a supply chain; of course, existing renewable energy systems may also be connected (e.g., renewable energy provided by photovoltaic solar roofs connected to hybrid systems), balancing arbitrage between local electric vehicle charging, heavy transport hydrogenation, and grid balancing, and mitigating the negative effects of energy price fluctuations.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.

Claims (10)

1. A secondary battery and electrocatalysis electrolytic cell mixing device is characterized by comprising an electrolytic cell, a first electrode and a second electrode, wherein the first electrode and the second electrode are positioned in the electrolytic cell; the electrolytic cell is used for containing electrolyte;
when the first electrode and the second electrode are not connected with an external power supply, the first electrode, the second electrode and the electrolyte can form a secondary battery, wherein the first electrode is used as a positive electrode of the secondary battery, and the second electrode is used as a negative electrode of the secondary battery; meanwhile, when the first electrode and the second electrode are connected with an external power supply, the first electrode, the second electrode and the electrolyte can form an electrocatalytic reaction tank for electrocatalytic reaction, wherein the first electrode is used as an anode of the electrocatalytic reaction tank, and the second electrode is used as a cathode of the electrocatalytic reaction tank; this enables the hybrid device to operate in either an energy storage battery mode or an electrocatalytic mode.
2. The hybrid device according to claim 1, wherein the secondary battery is an alkaline zinc-ion battery; preferably, the zinc ion battery is a nickel-zinc battery, a zinc-air battery, a zinc-silver battery or a zinc-mercury battery;
the electrocatalytic reaction is electrochemical reduction of carbon dioxide.
3. The hybrid device of claim 2, wherein the negative electrode of the zinc ion battery is zinc metal; the negative electrode of the zinc ion battery is electrochemically reduced in carbon dioxide (CO) 2 RR) and the positive electrode of the zinc ion battery acts as an anode in the electrochemical reduction of carbon dioxide.
4. The mixing device of claim 2, wherein the negative electrode of the zinc ion battery is a cathode catalyst for electrocatalytic carbon dioxide reduction, capable of electrocatalytic reduction of carbon dioxide in the carbon dioxide treated electrolyte; preferably, the carbon dioxide treatment is specifically carbon dioxide saturation treatment;
and when the hybrid device is switched to the electrocatalytic mode after passing through the energy storage battery mode:
when the zinc ion battery is in an energy storage stateThe last time under charging conditions, the corresponding electrocatalytic reaction is to convert CO 2 Reducing to CO;
when the energy storage state of the zinc ion battery is the last time under the discharge condition, the corresponding electrocatalytic reaction is to react CO 2 Reduced to formic acid.
5. The mixing device of claim 2, wherein the mixing device is further provided with CO 2 An inlet, a CO outlet, and a formic acid outlet; wherein said CO is 2 The inlet can introduce CO into the electrolyte 2 A gas; the CO outlet is arranged above the liquid level of the electrolyte; the formic acid outlet is positioned on the side wall or the bottom of the reaction cavity containing the electrolyte.
6. The hybrid device according to claim 1, wherein the secondary battery is a copper-zinc battery, a lead-acid battery, a PbO battery 2 The electrochemical reaction is carbon dioxide electrochemical reduction.
7. The hybrid device according to claim 1, wherein the secondary battery is an alkaline nickel-based battery, and the electrocatalytic reaction is electrocatalytic electrolysis of water;
or the secondary battery is a bismuth-based battery, and the electrocatalytic reaction is electrochemical nitrogen reduction;
or the secondary battery is a copper-based battery or a nickel-based battery, and the electrocatalytic reaction is electrochemical organic synthesis and conversion.
8. The hybrid device according to claim 1, wherein the secondary battery is any one of a cobalt-based battery, a copper-based battery, a Li-ion battery, a bismuth-based battery, a molybdenum-based battery, a ruthenium-based battery, a silver-based battery, and a palladium-based battery, and the electrocatalytic reaction is an electrochemical NO reduction (NORR), an electrochemical nitrate reduction, or a nitrogen reduction reaction.
9. The hybrid device of claim 1, wherein the external power source is a solar cell or a wind generator.
10. The method of using a hybrid device of a secondary battery and an electrocatalytic electrolytic cell as recited in any one of claims 1-9, wherein said method of using is to place the hybrid device in an energy storage battery mode or an electrocatalytic mode of operation;
preferably, the using method is that the working stage of the energy storage battery mode is firstly carried out, and then the working stage of the electrocatalysis mode is carried out, and the using method specifically comprises the following steps:
(1) Energy storage battery mode working stage: the first electrode and the second electrode are not connected with an external power supply by adjusting and controlling the switch, so that the first electrode, the second electrode and the electrolyte form a secondary battery; the function of the energy storage battery is realized by charging and discharging the secondary battery;
(2) Electrocatalysis mode working stage: the first electrode and the second electrode are connected with an external power supply through the regulating switch, and the first electrode, the second electrode and the electrolyte form an electrocatalysis reaction tank, so that electrocatalysis reaction is carried out, and an electrocatalysis function is realized.
CN202210603707.6A 2022-05-30 2022-05-30 Secondary battery and electrocatalysis electrolytic cell mixing device Pending CN114908361A (en)

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Publication number Priority date Publication date Assignee Title
WO2020138668A1 (en) * 2018-12-27 2020-07-02 울산과학기술원 Secondary battery generating hydrogen by using carbon dioxide and complex power generation system having same
CN112962108A (en) * 2019-11-27 2021-06-15 华中科技大学 Application of regeneration electrode of zinc ion battery in electrochemical reduction of carbon dioxide
CN112981430A (en) * 2019-12-13 2021-06-18 华中科技大学 Application of regeneration electrode of alkaline nickel-based battery in electrocatalytic hydrogen evolution reaction
US20210238756A1 (en) * 2018-06-28 2021-08-05 Monash University An electrolytic composition and cathode for the nitrogen reduction reaction
CN113564624A (en) * 2021-07-16 2021-10-29 华中科技大学 Method for preparing formate by recovering lead material through carbon dioxide reduction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210238756A1 (en) * 2018-06-28 2021-08-05 Monash University An electrolytic composition and cathode for the nitrogen reduction reaction
WO2020138668A1 (en) * 2018-12-27 2020-07-02 울산과학기술원 Secondary battery generating hydrogen by using carbon dioxide and complex power generation system having same
CN112962108A (en) * 2019-11-27 2021-06-15 华中科技大学 Application of regeneration electrode of zinc ion battery in electrochemical reduction of carbon dioxide
CN112981430A (en) * 2019-12-13 2021-06-18 华中科技大学 Application of regeneration electrode of alkaline nickel-based battery in electrocatalytic hydrogen evolution reaction
CN113564624A (en) * 2021-07-16 2021-10-29 华中科技大学 Method for preparing formate by recovering lead material through carbon dioxide reduction

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