CN113943942B - Carbon dioxide energy storage system driven by new energy electric energy and energy storage method - Google Patents
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Abstract
The invention provides an electrochemical catalytic carbon dioxide reduction energy storage system and an energy storage method driven by new energy electric energy.
Description
Technical Field
The invention relates to the technical field of electric energy storage, in particular to a carbon dioxide reduction energy storage method driven by new energy electric energy.
Background
From the carbon emission source, the emission of energy consumption carbon dioxide accounts for nearly nine times of the total carbon dioxide emission in China and nearly eight times of the net emission of greenhouse gases. Green color transformation in the energy field is therefore crucial for the achievement of the carbon neutralization goal. In the energy field, the carbon emission of the power department is about four times, and the occupancy rate is increased year by year. Under the great trend of electrification, the zero-carbon development of the power system is a great key for achieving the 30-60 target. Therefore, in 12 months in 2020, china makes further commitments at the climate ambition peak: the proportion of the non-fossil energy in the China to primary energy consumption in 2030 years reaches about 25%, and the total installed capacity of wind power generation and solar power generation reaches more than 12 hundred million kilowatts. As a key technology for supporting the development of renewable energy, energy storage will begin to develop in a new step-by-step manner.
Electrochemical catalytic processes are considered as a reliable solution to efficiently integrate renewable resources like wind and solar energy into current carbon and energy combinations. The scheme aims to combine an electrocatalyst with carbon dioxide, reduce the carbon dioxide through electric energy activation, convert the carbon dioxide into fuels such as methanol, ethanol and methane, and store the obtained fuels until the fuels are implemented in a high power consumption period, and convert the fuels into electric energy again, wherein the methane is a main component of Synthetic Natural Gas (SNG), and compared with methanol and ethanol, the methane is easier to transport, has higher energy storage density per unit mass and higher compatibility with the existing fuel storage equipment, so the methane is an important carrier fuel for electric energy storage and is widely applied.
There have been a large number of studies on the preparation of methane by means of electrocatalysts and carbon dioxide reduction to realize electric energy storage. Nickel-based catalysts are widely used for the reduction of carbon dioxide to produce methane due to their low cost and ready availability. However, even at low temperatures, nickel catalysts may deactivate due to sintering of nickel particles, formation of mobile nickel carbonylidene groups, or formation of carbon deposits. In addition, active metals Rh, co, fe, etc. have also been reported as effective catalysts for the reduction of carbon dioxide to methane, however, these catalysts are high in cost, limiting their industrial application.
Compared with the catalyst, the copper-based catalyst has lower cost, is the most effective catalyst for reducing carbon dioxide into hydrocarbon, has the advantage of improving the selectivity of the carbon dioxide conversion product, and is the most effective means for methanation of carbon dioxide and realization of industrial electric energy storage. By using the chemical micromolecules to modify the copper-based catalyst, the reaction rate can be improved, and the formation of methane on the surface of the copper base is further promoted by inhibiting the hydrogen evolution reaction.
However, for the copper-based catalyst, the current research has encountered a problem that the energy storage efficiency key parameter in the energy storage process of electrochemical reduction of carbon dioxide, namely, the faradaic efficiency is insufficient, and the energy input loss is large. Because conventional chemical small molecule modification of copper electrodes can increase the conversion efficiency of carbon dioxide, desorption from the copper electrodes during use and subsequent removal with the liquid flow in the cell can easily occur, resulting in a loss of input energy and faradaic efficiency.
The inventor of the application proposes that the polymer with the proton conductive side chain and the electron conductive main chain is adopted to modify the copper-based catalyst in the related application, so that the Faraday efficiency and the catalytic efficiency of the existing copper-based catalyst can be improved, the loss of input energy is reduced, and the efficient storage of electric energy is realized.
In the further research process, the copper-based catalyst modified by the polymer is used for electrochemical catalysis of carbon dioxide reduction and energy storage, and the condition in the reduction process also has great influence on the conversion efficiency of methane, so that the method for electrochemical catalysis of carbon dioxide reduction and energy storage driven by new energy is further optimized.
Technical scheme
The invention aims to solve the technical problem of providing a new energy-driven electrochemical catalytic carbon dioxide reduction energy storage system and an energy storage method, wherein a polymer with a proton conductive side chain and an electronic conductive main chain is adopted to modify a copper-based catalyst to prepare an electrochemical catalytic electrode, and the current density, the temperature range and the pH value of electrolyte in the electrochemical catalytic process are optimized, so that the electrochemical catalytic carbon dioxide reduction efficiency and the methane Faraday efficiency are further improved, the loss of input energy is reduced, and the efficient storage of electric energy is realized.
Based on the electrochemical catalytic carbon dioxide reduction energy storage system driven by new energy, the electrochemical catalytic electrode serving as a cathode, electrolyte and an anode are provided, the electrochemical catalytic electrode is provided with a modified polymer, and the modified polymer is a polymer with a proton conductive side chain and an electron conductive main chain.
Wherein the anode may be an inert metal electrode or a carbon electrode.
Wherein the electrolyte may be KHCO 3 、NaHCO 3 The concentration is between 0.05M and 2M.
The invention also provides a new energy driven electrochemical catalytic carbon dioxide reduction energy storage method, which comprises the following steps:
firstly, introducing a carbon dioxide gas source into system electrolyte until the system electrolyte is saturated;
secondly, new energy is adopted to provide electric power to the carbon dioxide reduction energy storage system to carry out electrochemical catalytic reaction;
and thirdly, leading the generated methane fuel out for storage so as to be used for subsequent energy supply.
Wherein, in the second step, the pH value of the electrolyte ranges from 4.8 to 6.8.
Wherein, in the second step, the reaction temperature range is 25-65 ℃.
Wherein, in the second step, the applied catalytic potential is in the range of-0.82V to-1.02V.
Advantageous effects
The invention provides an electrochemical catalytic carbon dioxide reduction energy storage system and an energy storage method driven by new energy electric energy.
Drawings
FIG. 1 influence of different potentials on Faraday conversion efficiency and catalytic efficiency;
figure 2 influence of different electrolyte pH values on faraday conversion efficiency and catalytic efficiency;
FIG. 3 shows the percentage of maximum active current density retention for a polymer/copper catalytic electrode in 10 hours of continuous operation in an electrolyte system with different electrolyte pH values;
figure 4 effect of different reaction temperatures on faradaic conversion efficiency and catalytic efficiency.
Detailed Description
The copper-based catalyst is modified by a polymer modification group with a special structure, and the hydrophilicity and hydrophobicity of a polymer side chain influence CO 2 Protonation process of reduction reaction, and CO 2 The diffusion process at the electrode surface, both of which can further regulate the efficiency of the reaction and the product.
First, the invention provides a polymer having a side chain with a chemical property that is CO 2 Regulation of the reduction at the Cu surface, owing to the use of polymers containing proton-conducting side chains, e.g. side chains containing sulfonic acid groups orThe side chain containing phosphate group can effectively improve the concentration of CO free radicals on the surface of the Cu electrode in a reaction system and the pH value of the surface, and obviously regulates and controls the formation of products while regulating and controlling the catalytic activity, so that methane is easily formed in the whole reaction.
In addition, the polymer electron conductive main chain provided by the invention has more than one conjugated group, and the conjugated group can be alkenyl, aromatic conjugated group and the like, so that the interface impedance of the electrode can be obviously reduced, and the Faraday efficiency and the catalytic current density (catalytic efficiency) for converting into methane can be improved.
Based on the principle, the invention provides a copper-based catalyst for electrochemical catalysis carbon dioxide reduction energy storage driven by new energy, the copper-based catalyst is obtained by electroplating copper nanoparticles and a modified polymer, and the modified polymer is a polymer with a proton-conducting side chain and an electron-conducting main chain.
The electron-conductive main chain has one or more conjugated groups, and the conjugated group is preferably a butadienyl group.
The proton conductive side chain is a side chain of a sulfonic acid group.
The polymer is further preferably polystyrene sulfonic acid (PSS), polybutadiene sulfonic acid, polybutadiene sulfonate, polyaniline with camphor sulfonic acid as a dopant, and most preferably polybutadiene sodium sulfonate.
The copper-based catalyst can be prepared into a coating to be coated on an electrode substrate to prepare an electrochemical catalytic electrode, and the electrode substrate can be a carbon material electrode, a carbon material composite electrode, a noble metal electrode, a stainless steel electrode, a copper electrode, an iron electrode and the like.
The carbon material electrode may further be a graphite electrode, a carbon fiber electrode, a carbon paper electrode (gas diffusion electrode), a graphene electrode, a carbon nanotube electrode, a diamond electrode, or the like. Further, a carbon fiber electrode, a carbon paper electrode (gas diffusion electrode), a graphene electrode, and a carbon nanotube electrode are preferable.
The noble metal electrode may further be selected from gold, silver, platinum, and the like.
The thickness of the coating is preferably 10 μm to 20 μm, more preferably 12 μm to 16 μm, and most preferably 12 μm. By studying, we found that when the thickness of the coating is less than 10 μm or more than 20 μm, the faradaic efficiency of methane is significantly reduced, almost the conversion is less than 50%, and the maximum catalytic current density is also significantly reduced, affecting the reduction efficiency of carbon dioxide.
The electrochemical catalytic electrode is prepared by adopting an in-situ codeposition method, and the electrochemical catalytic electrode can deposit polymers on the copper electrode, so that polymer molecules can be kept on the surface of the electrode, and the problem of desorption from the copper electrode is avoided.
The invention also provides a preparation method of the electrochemical catalytic electrode, which adopts an in-situ co-deposition method and specifically comprises the following steps:
first, preparation of an electroplating bath comprising CuSO 4 Solution, the modifying polymer and Na 2 SO 4 、H 2 SO 4 Mixing the above components together in proportion;
and secondly, putting the electrode base material into the electroplating solution, and electroplating by adopting an electroplating method.
The CuSO 4 The concentration of the solution is preferably 1mM-10mM, more preferably 3mM.
The concentration of the modifying polymer is preferably 1. Mu.M to 100. Mu.M, more preferably 10. Mu.M to 100. Mu.M, and still more preferably 10. Mu.M to 20. Mu.M.
The Na is 2 SO 4 The concentration of the solution is preferably 0.05M to 0.1M, and more preferably 0.1M.
Said H 2 SO 4 The concentration of the solution is preferably 0.3M to 0.5M, and more preferably 0.5M.
The current density in the second step is preferably (-2 mA/cm) 2 )–(-6mA/cm 2 ) Further preferably (-3 mA/cm) 2 )。
The invention also provides a new energy driven electrochemical catalytic carbon dioxide reduction energy storage system, comprising: the electrochemical catalytic electrode as the cathode, the electrolyte, the anode and the electrolytic cell are composed of several parts.
The anode may be an inert metal electrode or a carbon electrode.
The electrolyte may be KHCO 3 、NaHCO 3 The concentration is, for example, 0.05M to 2M, more preferably 0.05M to 1M.
The invention also provides a new energy driven electrochemical catalytic carbon dioxide reduction energy storage method, which comprises the following steps:
firstly, introducing a carbon dioxide gas source into system electrolyte until the system electrolyte is saturated;
secondly, new energy is adopted to provide electric power to the carbon dioxide reduction energy storage system to carry out electrochemical catalytic reaction;
and thirdly, leading the generated methane fuel out for storage so as to be used for subsequent energy supply.
In the second step, the pH value of the electrolyte is 4.8-6.8, and the pH value of the electrolyte is lower than 7, so that CO can be ensured 2 After being reduced to CO radical intermediates, there is sufficient proton source in the system to supply the intermediates to protonate further to produce methane, so theoretically the lower the pH of the system, the more readily the CO radical intermediates in the system will protonate. However, too low electrolyte pH affects the stability of Cu catalyst, so an optimized pH range is required to ensure the stability of both proton donor and catalyst.
In the second step, the reaction temperature is within a given temperature range of 25-65 ℃, the influence of the temperature on the Faraday efficiency and the maximum catalytic current (catalytic efficiency) of the catalytic system is mainly reflected in the aspects of 1) thermodynamics influences the activity of the active center of the catalyst, and promotes the activity of the catalyst and CO 2 The rate of binding and dissociation and the catalytic turnover; 2) Increase of CO in the system 2 The solubility and the mass transfer speed of the catalyst are further preferably room temperature in view of green, low carbon and energy consumption.
In the second step, the applied catalytic potential range is-0.82V-1.02V, and the product distribution condition of the electro-reduction catalysis is obviously influenced by the catalytic potential applied by electrochemistry generally, so that the product proportion and the byproduct proportion of methane generated by catalytic reduction are influenced, and the Faraday efficiency and the catalytic efficiency of the methane are improved.
Embodiments of the present invention will be described in detail below with reference to examples and drawings, by which how to apply technical means to solve technical problems and achieve a technical effect can be fully understood and implemented.
Example 1 preparation of modified copper electrode
3mM of CuSO 4 Solution, 20. Mu.M sodium polybutadiene sulfonate, 0.1mM Na 2 SO 4 And 0.5mM H 2 SO 4 Pouring into an electroplating container, and stirring and mixing uniformly by adopting an in-situ co-deposition method to obtain the electroplating solution.
Placing the graphite electrode substrate in the electroplating solution, and electroplating with a deposition current density of-3 mA/cm 2 The total deposited electricity quantity is 2.5C/cm 2 The prepared catalyst layer was 12. Mu.M thick.
The Faraday efficiency is the percentage of the amount of actual product and theoretical product, i.e., the amount of reduction electrons generated by the catalytic electrode using electric energy, and the electron transfer number of the catalytic reaction is calculated, and theoretically all the electrons are used for reducing CO 2 The total amount of product that can be produced. The content of the product is obtained by gas chromatography detection.
Influence of different catalytic potentials on Faraday conversion efficiency of methane and reduction catalytic efficiency of carbon dioxide
The modified copper electrode prepared in example 1 was used as the cathode, the inert metal platinum electrode was used as the anode, and the concentration was CO 2 Saturated 0.1M sodium bicarbonate solution is used as electrolyte, the pH value of the electrolyte is adjusted to 6.8, a carbon dioxide reduction energy storage system is constructed, and CO is added 2 And introducing a gas source into the electrolyte of the system until the gas source is saturated, supplying power by adopting a solar power supply system, applying a working voltage (referring to a silver/silver chloride reference electrode) on the cathode, carrying out electrocatalytic reaction at room temperature, and inspecting different working voltages and electrochemical catalytic reaction effects, wherein the results are shown in table 1 and figure 1.
TABLE 1 influence of different potentials on Faraday conversion and catalytic efficiency
As can be seen from table 1 and fig. 1, when the applied potential is-0.42V, the main product of the catalytic system is CO, and the faradaic efficiency can reach 85%, because at this potential, the wettability of the electrode surface is insufficient, which is not favorable for proton transfer on the electrode surface, and CO radical intermediates generated by catalytic reduction of carbon dioxide are more likely to rapidly dissociate from the catalytic sites, and escape as CO to the electrolyte phase. Further reducing the catalytic potential can significantly influence the dissociation and escape of CO radical intermediates on the surface of the catalytic electrode, wherein when the catalytic potential reaches-0.82V, the Faraday efficiency of the system for generating methane is maximum, the generation of CO is significantly inhibited, and further reducing the catalytic potential can also inhibit the generation of CO, but the excessively low catalytic potential can promote the hydrogen evolution side reaction on the surface of the electrode, thereby also influencing the Faraday efficiency and the catalytic efficiency for catalyzing the generation of methane, and when the applied potential is reduced to-1.3V, the Faraday efficiency of methane is still the highest, but the Faraday efficiency of hydrogen is also significantly increased, and meanwhile, the maximum catalytic current density is significantly reduced. Through verification and analysis, when the potential is applied to-0.82V-1.02V, higher methane Faraday conversion efficiency can be ensured, and meanwhile, the maximum catalytic current density is also higher, so that higher catalytic efficiency is kept.
Influence of different pH value ranges on Faraday conversion efficiency of methane and reduction and catalysis efficiency of carbon dioxide
The modified copper electrode and energy storage system prepared in example 1 were used, the same carbon dioxide reduction conversion energy storage method as described above was used, the operating voltage applied to the cathode was-0.82V, electrocatalytic reactions were performed at room temperature, and different electrolyte pH ranges were selected for comparison, and the results are shown in table 2 and fig. 2.
TABLE 2 influence of different electrolyte pH values on Faraday conversion and catalytic efficiency
The previous research shows that the alkali propertyThe use of electrolytes is believed to be through reduction of CO 2 Activated energy barrier, promotion of c-c coupling and inhibition of H 2 Is favorable for the production of ethylene (Dinh, C. -T.et al. CO) 2 electroreduction to ethylene via hydroxide-mediated
chip catalyst at an abrupt interface science 360,783-787 (2018). While the acid electrolyte will be guaranteed to be in CO 2 After being reduced to CO radical intermediates, there is sufficient proton source in the system to supply the intermediates to protonate further to produce methane, so theoretically the lower the pH of the system, the more readily the CO radical intermediates in the system will protonate. However, too low electrolyte pH affects the stability of Cu catalyst, so an optimized pH range is required to ensure the stability of both proton donor and catalyst. Therefore, in the catalytic system of this patent directed to methanogenesis, to investigate the beneficial effect of pH, CO was performed using a range of electrolytes with pH ranging from 2.8 to 7.8 2 And (4) performing catalytic reduction test. The performance of the catalysis in different pH electrolyte systems is plotted in table 2 and fig. 2. As can be seen from the data in the table and the figure, when the pH of the system is in a weak alkaline environment of 7.8, the Faraday efficiency of the system for catalyzing methane production is obviously reduced, the yield of the byproduct CO is obviously increased, and the overall catalytic efficiency is also obviously reduced. In the range of pH 2.8-6.8, the hydrogen evolution side reaction of the catalytic system is inhibited with the increase of pH, and the Faraday efficiency of CO byproduct production is inhibited with the decrease of pH, and due to the balance of the two factors, the Faraday efficiency of methane production reaches the highest at pH 6.8. Although the catalytic efficiency, i.e. the maximum catalytic current density, of the catalytic system increases significantly with decreasing pH, the more acidic pH has a significant effect on the stability of the copper-based catalyst. Comprehensively considering, the Faraday efficiency of methane and the catalytic reduction efficiency of carbon dioxide are both higher within the range of pH value of 4.8-6.8, thereby not only meeting the higher catalytic reduction efficiency, but also meeting the requirement of single product.
Fig. 3 shows the percentage of activity of the polymer/copper catalytic electrode in the electrolyte system with different pH values, i.e. the ratio of the maximum catalytic current density after 10 hours of continuous operation to the initial maximum catalytic current density, indicating the stability of the catalyst at different pH values, as shown in the figure, the stability of the copper-based catalyst in the strongly acidic environment with pH 2.8 only maintains 48% of the initial catalytic activity after 10 hours of continuous operation, while the activity of the copper-based catalyst in the pH 6.8 electrolyte environment maintains more than 77%.
Influence of different electrocatalytic reaction temperature ranges on Faraday conversion efficiency of methane and reduction catalytic efficiency of carbon dioxide
The modified copper electrode and the energy storage system prepared in example 1 were used, the same carbon dioxide reduction conversion energy storage method as described above was used, the working voltage applied to the cathode was-0.82V, the pH of the electrolyte was selected to be 6.8, and different electrocatalytic reaction temperatures were selected for comparison, and the results are shown in table 3 and fig. 4.
TABLE 3 influence of different reaction temperatures on Faraday conversion and catalytic efficiency
As can be seen from Table 3 and FIG. 4, the maximum catalytic current density (catalytic efficiency) of the catalytic system increases with increasing temperature in the range of 5-85 deg.C, and the influence of temperature on the Faraday efficiency and the maximum catalytic current (catalytic efficiency) of the catalytic system is mainly expressed in two aspects, 1) the activity of the active center of the catalyst is thermodynamically influenced, and the catalyst and CO are promoted 2 The rate of binding and dissociation and the catalytic turnover; 2) Increase of CO in the system 2 Solubility and mass transfer rate. It can be seen from the figure that the methane-generating faradaic efficiency of the catalytic system is obviously reduced at 5 ℃ and is kept above 90% at other temperatures, but the hydrogen evolution side reaction of the catalytic system is enhanced with the temperature higher than 45 ℃, so that the methane-generating faradaic efficiency is slightly reduced. Finally, it is also from practiceFrom the standpoint of simultaneous consideration of carbon-neutralized CO 2 In the two aspects of conversion and energy storage, the balance of catalytic efficiency, electricity utilization efficiency and system energy consumption is sought by combining with an actual scene, the reaction range of 25-65 ℃ is optimized, the room temperature is most optimized, the energy consumption can be reduced to the maximum extent, and the Faraday efficiency and the catalytic efficiency are ensured.
All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are to the reserved rights based on the new products of the present invention.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. The utility model provides a carbon dioxide energy storage system of new forms of energy electric drive which characterized in that includes: the electrochemical catalytic electrode is provided with a modified polymer, wherein the modified polymer is a polymer with a proton-conducting side chain and an electron-conducting main chain;
the modified polymer is polystyrene sulfonic acid, polybutadiene sulfonate and polyaniline with camphorsulfonic acid as a dopant, and the electrochemical catalytic electrode is a copper-based catalyst electrode.
2. The new energy electric energy driven carbon dioxide energy storage system of claim 1, wherein: the anode is an inert metal electrode or a carbon electrode.
3. As claimed inAsk 1 or 2 carbon dioxide energy storage system of new forms of energy electric drive, its characterized in that: the electrolyte is KOH and NaHCO 3 The concentration is between 0.05M and 2M.
4. An electrochemical catalytic carbon dioxide reduction energy storage method driven by new energy electric energy is characterized by comprising the following steps:
firstly, introducing a carbon dioxide gas source into system electrolyte until the system electrolyte is saturated;
a second step of providing electric power to the carbon dioxide energy storage system according to any one of claims 1 to 3 by using a new energy source to perform electrochemical catalytic reaction;
and thirdly, leading the generated methane fuel out for storage so as to be used for subsequent energy supply.
5. The method for storing energy by electrochemical catalytic carbon dioxide reduction driven by new energy electric energy according to claim 4, characterized by comprising the following steps: in the second step, the pH value of the electrolyte ranges from 4.8 to 6.8.
6. The method for storing energy by electrochemical catalytic carbon dioxide reduction driven by new energy electric energy according to claim 4 or 5, characterized by comprising the following steps: in the second step, the reaction temperature is in the range of 25-65 ℃.
7. The method for storing energy by electrochemical catalytic carbon dioxide reduction driven by new energy electric energy according to claim 4 or 5, characterized by comprising the following steps: in the second step, the applied catalytic potential is in the range of-0.82V to-1.02V.
8. The method for storing energy by electrochemical catalytic carbon dioxide reduction driven by new energy electric energy according to claim 4 or 5, characterized by comprising the following steps: the new energy is photovoltaic and wind energy.
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