CN114959762A - Membrane electrode for solid electrolyte electrolytic cell - Google Patents
Membrane electrode for solid electrolyte electrolytic cell Download PDFInfo
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- CN114959762A CN114959762A CN202210621965.7A CN202210621965A CN114959762A CN 114959762 A CN114959762 A CN 114959762A CN 202210621965 A CN202210621965 A CN 202210621965A CN 114959762 A CN114959762 A CN 114959762A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention provides a membrane electrode of a solid electrolyte electrolytic cell, which comprises an optimized layer, wherein the optimized layer can improve the operation efficiency and safety of the electrolytic cell, and is realized by reducing the hydrogen content in an anode. The preparation process of the optimized layer structure is simple and easy to implement, and can be realized through common processes such as spraying, screen printing, blade coating and the like. The position of the assembly of the optimization layer may be between the anode catalytic layer and the membrane, or outside the anode catalytic layer, or mixed with either or both of the anode catalytic layers. The principle is that the optimized layer quenches hydrogen on the anode side through chemical reaction, and the effect of reducing the hydrogen content is achieved. Through optimization of the membrane electrode by the optimization layer, the gas purity and the hydrogen concentration of the anode side of the electrolytic cell are beyond the explosion limit on the basis of not obviously increasing the system cost and auxiliary equipment, and the effects of efficiency improvement and safe operation are achieved.
Description
Technical Field
The invention belongs to the field of water electrolysis of solid electrolyte, and particularly relates to a membrane electrode for improving the operation safety and efficiency of a solid electrolyte electrolytic cell.
Background
The water electrolysis technology by utilizing the solid electrolyte electrolytic cell is a green energy storage technology which can directly utilize renewable energy sources to generate electricity to electrolyze pure water to prepare hydrogen, and because the cathode cavity and the anode cavity of the electrolytic cell are isolated by the solid electrolyte (ion exchange membrane), high-pressure operation can be realized on two sides, high-pressure product gas is obtained on line, and the cost of later-stage gas compression is reduced. However, since hydrogen gas on the cathode side permeates to the anode side due to deviation of the sealing effect or the influence of the gas tightness of the membrane in the actual process, especially when the thickness of the membrane is reduced or the high-pressure operation is performed, the explosion limit of hydrogen gas is reached when the content of hydrogen gas in oxygen gas on the anode exceeds 4%, which poses a threat to the safe operation of the electrolytic cell, and therefore, the reduction of the content of hydrogen in the anode oxygen is an important guarantee for improving the safe operation of the electrolytic cell.
The document (CN201711372053.6) introduces an air purification structure by designing a three-dimensional electrode structure, and purifies pollutants in the air by applying a potential oxidation method, thereby solving the problems that the catalyst is easy to deactivate and SO is generated in the existing purification method 2 The purification problem, however, the technical route of purification of impurity gases by the potentiometric oxidation method requires additional consumption of electric energy, additional requirements for the cell structure and materials, and limitations on the types of impurity gases, and is not applicable to the purification of anode gases in electrolytic cells. The literature (Journal of The Electrochemical Society, 2021168114513) reports that The use of a carbon-nitrogen compound as a cathode catalyst can satisfy both hydrogen evolution and oxygen reduction activity requirementsThe carbon nitride used in the method has a remarkable effect of reducing the oxygen content in the hydrogen of the cathode, and although the carbon nitride can achieve a good gas purification effect at the cathode, the carbon nitride material is extremely easy to corrode when the anode side is heavily exposed to a strongly oxidizing environment, so that the material selection of the gas purification layer at the anode side faces a great challenge. The noble metal material adopted by the invention has quantified chemical stability, and can keep a stable structure in a strong oxidation environment of the anode of the electrolytic cell.
Disclosure of Invention
Based on the background technology, the invention aims to solve the problems of safety and Faraday efficiency improvement of the anode of the existing solid electrolyte water electrolyzer. The addition of the optimized layer can avoid adding an additional hydrogen-in-oxygen separation device, achieve the effect of purifying oxygen, improve the Faraday efficiency of gas production, and simultaneously prevent the hydrogen concentration from reaching the explosion limit, thereby having important significance for the safety improvement of high-voltage operation or thin-film electrodes.
In order to achieve the above objects, the present invention provides a membrane electrode for improving the operation safety and efficiency of a solid electrolyte electrolytic cell, the membrane electrode comprising an optimized layer, the optimized layer is located between an anode catalytic layer and a proton exchange membrane, or the optimized layer is located outside the anode catalytic layer, or the optimized layer is located in any one or two of the anode catalytic layer; the active component of the optimized layer is a hydrogen quencher with hydrogen adsorption or hydrogen oxidation activity.
Based on the above technical scheme, preferably, the specific kind of the active component is a noble metal catalyst such as Pt, Pd, PtPd alloy, and the like.
Based on the technical scheme, the optimized layer can be prepared by spraying, screen printing, blade coating and other processes.
Based on the above technical solution, preferably, the optimized layer is prepared by slurry, the composition of the slurry of the optimized layer includes active components, solvents and binders, and the types of the solvents include: volatile organic solvents such as ethanol and isopropyl alcohol; the binder is a polymer resin having proton conductivity, such as perfluorosulfonic acid resin. When the optimized layer is positioned between the anode catalyst layer and the proton exchange membrane, the mass ratio of the binder to the active component is 0.45-2: 1, preferably 0.5-1: 1, and the mass ratio of the solvent to the active component is 20-100: 1, preferably 60-80: 1; when the optimized layer is positioned outside the anode catalyst layer or doped in the anode catalyst, the mass ratio of the binder to the active component is 0.1-0.4: 1, preferably 0.2-0.4: 1, and the mass ratio of the solvent to the active component is 20-100: 1, preferably 60-80: 1.
The assembling position of the optimizing layer is positioned between the anode catalysis layer and the proton exchange membrane, or positioned outside the anode catalysis layer, or mixed in any one or two of the anode catalysis layer. The position of the optimized layer is realized by different preparation sequences of the slurry, and when the optimized layer is positioned between the anode catalyst layer and the proton exchange membrane, the optimized layer is prepared before the anode catalyst layer is assembled; when the optimization layer is positioned outside the anode catalysis layer, the slurry is carried out after the anode catalysis layer is assembled; when the optimized layer is doped in the anode catalyst, the anode slurry and the optimized layer slurry are simultaneously prepared on the membrane surface.
Based on the above technical scheme, preferably, in the membrane electrode optimization layer, the mass ratio of the active component in the optimization layer to the catalyst in the anode catalyst layer is 0.05-10: 1, preferably 0.05-2: 1, and more preferably 0.1-2: 1.
According to the position of the optimized layer and the slurry, the preparation process and the steps are as follows:
1. preparing optimized layer slurry: weighing a certain amount of active components according to the electrode area and the optimized layer loading capacity, mixing a certain amount of solvent and the active components, performing ultrasonic treatment for 10-15 min, adding a certain amount of binder based on the mass of the catalyst after the active components are uniformly dispersed in the slurry, and continuing the ultrasonic treatment for 30min to finish the preparation process of the slurry.
2. Preparing an optimized layer: the preparation of the optimized layer is carried out by adopting the processes of spraying, screen printing, blade coating and the like, an electrolyte membrane for electrode loading is placed on the surface of a negative pressure type hot table, the temperature of the hot table is controlled to be 30-120 ℃, a cathode catalyst layer, an anode catalyst layer and the optimized layer are prepared on the surface of the electrolyte membrane according to the sequence of assembly required by the position of the optimized layer, and after the completion, the electrode is placed at 60-80 ℃ for vacuum drying to completely remove the residual solvent in the electrode, so that the preparation of the membrane electrode with the optimized layer is completed.
Advantageous effects
1. The membrane electrode with the optimized layer is simple and easy to prepare, can be prepared by only adding one step of preparation of the optimized layer in the traditional membrane electrode preparation process, and is low in preparation cost; the addition of the optimization layer can avoid the addition of an additional gas purification device of the electrolytic cell, save the cost and space of the system and simplify the operation of the system.
2. When the optimized layer is positioned in the anode catalyst layer, the addition of the optimized layer can realize the dispersion effect on the anode catalyst layer, improve the dispersion degree and the quality activity of the catalyst, reduce the loading capacity of the anode catalyst, and realize the purification of the gas on the anode side under the condition of ensuring that the polarization performance of the membrane electrode is not influenced.
3. When the optimized layer is positioned between the anode catalyst layer and the proton exchange membrane, the optimized layer has higher content of the binder, the binding force between the anode catalyst layer and the proton exchange membrane can be enhanced, the proton transmission is promoted, and the optimized layer has two functions of binding and purification. On one hand, the separation of the anode catalyst layer in long-term operation is avoided, and the influence of the addition of the optimized layer on the proton transmission capability is relieved; on the other hand, the gas purity and the hydrogen concentration on the anode side of the electrolytic cell are beyond the explosion limit, and the effects of improving the efficiency and safely operating are achieved;
4. when the optimization layer is positioned outside the catalytic layer, the purification of the gas on the anode side is facilitated under the condition that the polarization performance of the membrane electrode is not affected. Meanwhile, the membrane electrode can also play a role in purifying the anode deionized water, and remove insoluble impurities, metal ions and the like in the circulating water by utilizing the self-filtering and adsorbing effects of the optimized layer before the deionized water reaches the anode catalyst layer, thereby being beneficial to improving the performance and prolonging the service life of the membrane electrode; in addition, the optimized layer on the outer side can also serve as a protective layer of the anode catalyst layer, so that the loss of the catalyst in the catalyst layer and the damage of the catalyst by mechanical external force are avoided.
5. Through optimization of the membrane electrode by the optimization layer, the gas purity and the hydrogen concentration of the anode side of the electrolytic cell are beyond the explosion limit on the basis of not obviously increasing the system cost and auxiliary equipment, and the effects of efficiency improvement and safe operation are achieved.
Drawings
FIG. 1A cross-sectional profile and elemental distribution of a membrane electrode with an optimized layer prepared in example 1.
Figure 2 concentration of anodic hydrogen for membrane electrode with optimized layer (N115) cell prepared in example 1.
Figure 3 concentration of anodic hydrogen for membrane electrode with optimized layer (N1135) cell prepared in example 2.
Figure 4 concentration of anodic hydrogen for membrane electrode with optimized layer (N212) cell prepared in example 3.
Figure 5 concentration of anodic hydrogen for membrane electrode with optimized layer (N1135) cell prepared in example 4.
Figure 6 concentration of anodic hydrogen for the unoptimized layer membrane electrode (N115) cell prepared in comparative example 1.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
1. Preparing optimized layer slurry: weighing 25.6mg of platinum black catalyst, mixing 1.54g of isopropanol with the catalyst, performing ultrasonic treatment for 10min, adding 256mg of Nafion solution (with the concentration of 5 wt%) after the catalyst is uniformly dispersed in the slurry, and continuing ultrasonic treatment for 30min to finish the preparation of the slurry.
2. Preparing cathode catalyst layer slurry: 57.14mg of platinum-carbon catalyst (platinum loading is 70 wt%), 4.5g of isopropanol is added, ultrasonic treatment is carried out for 10min, 381mg of Nafion solution (concentration is 5 wt%) is added after the catalyst is uniformly dispersed in the slurry, and ultrasonic treatment is continued for 30min, so that the preparation of the slurry is completed.
3. Preparing anode catalyst layer slurry: weighing 100mg of iridium black catalyst, adding 6g of isopropanol, performing ultrasonic treatment for 10min, adding 667mg of Nafion solution (the concentration is 5 wt%) after the catalyst is uniformly dispersed in the slurry, and performing ultrasonic treatment for 30min to complete the preparation of the slurry.
4. Preparation of membrane electrode with optimized layer: the method is carried out by adopting a spraying method, a Nafion115 membrane with proper size is placed on the surface of a negative pressure type hot table, the temperature of the hot table is controlled at 80 ℃, cathode catalyst layer slurry is sprayed on one side of the membrane in sequence according to the spraying sequence required by the position of an optimized layer, then the optimized layer slurry and anode catalyst layer slurry are sprayed on the other side of the membrane in sequence, and the effective area is 50cm 2 Preparing the membrane electrode of (1). And after the spraying is finished, the electrode is placed at 80 ℃ for vacuum drying to completely remove the residual solvent in the electrode, and the preparation of the membrane electrode with the optimized layer is completed.
In this example, a 115 membrane (125 μm) was used as an electrolyte membrane to prepare a membrane electrode having an optimized layer located between an anode catalyst and a Nafion115 membrane, and as can be seen from the microscopic morphology and the elemental linearity analysis results of the membrane electrode shown in fig. 1, the optimized layer is located between the anode catalyst layer and the Nafion115 membrane in a position consistent with the expected position. The membrane electrode is subjected to an electrolytic cell performance test, the hydrogen concentration in the anode oxygen is 0.017%, and compared with the electrode without the optimized layer in the comparative example, the hydrogen concentration in the oxygen is obviously reduced.
Example 2
1. Preparing optimized layer slurry: weighing 50mg of platinum-palladium catalyst (with Pt loading capacity of 60 wt%), mixing 3g of isopropanol with the catalyst, performing ultrasonic treatment for 10min, adding Nafion solution (with the concentration of 5 wt%) with the mass of 333mg of the catalyst after the catalyst is uniformly dispersed in the slurry, and continuing ultrasonic treatment for 30min to complete preparation of the slurry.
2. Preparing cathode catalyst layer slurry: 57.14mg of platinum-carbon catalyst (platinum loading is 70 wt%), 4.5g of isopropanol is added, ultrasonic treatment is carried out for 10min, 381mg of Nafion solution (concentration is 5 wt%) is added after the catalyst is uniformly dispersed in the slurry, and ultrasonic treatment is continued for 30min, so that the preparation of the slurry is completed.
3. Preparing anode catalyst layer slurry: weighing 100mg of iridium black catalyst, adding 6g of isopropanol, performing ultrasonic treatment for 10min, adding 667mg of Nafion solution (the concentration is 5 wt%) after the catalyst is uniformly dispersed in the slurry, and performing ultrasonic treatment for 30min to complete the preparation of the slurry.
4. Preparation of membrane electrode with optimized layer: the preparation of the optimized layer is carried out by adopting a spraying method, a certain size of Nafion1135 membrane is placed on the surface of a negative pressure type hot platform, the temperature of the hot platform is controlled at 80 ℃, cathode catalysis layer slurry is sprayed on one side of the membrane in sequence according to the spraying sequence required by the position of the optimized layer, then anode catalysis layer slurry and optimized layer slurry are sprayed on the other side of the membrane in sequence, and the effective area is 50cm 2 Preparing the membrane electrode of (1). And after the spraying is finished, the electrode is placed at 80 ℃ for vacuum drying to completely remove the residual solvent in the electrode, and the preparation of the membrane electrode with the optimized layer positioned outside the anode catalyst layer is finished.
This example is a membrane electrode prepared with an N1135 membrane (75 μm) as the electrolyte membrane, with an optimized layer outside the anode catalyst, and the membrane electrode was subjected to cell performance tests with a hydrogen concentration of 0.022% in the anode oxygen, which is still significantly lower than the higher thickness N115 membrane electrode without the optimized layer in the comparative example.
Example 3
1. Preparing slurry of an optimization layer and an anode catalyst layer: weighing 10mg of platinum-palladium catalyst (with Pt loading capacity of 60 wt%) and 100mg of iridium black catalyst in the same sample bottle, carrying out ultrasonic treatment on 6.6g of isopropanol and mixed catalyst for 10min, adding a Nafion solution (with the concentration of 5 wt%) with the mass of the catalyst after the catalyst is uniformly dispersed in the slurry, and continuing the ultrasonic treatment for 30min to complete the preparation of the slurry.
2. Preparing cathode catalyst layer slurry: weighing 57.14mg of platinum-carbon catalyst (platinum loading is 70 wt%), adding 4.5g of isopropanol, performing ultrasonic treatment for 10min, adding 667mg of Nafion solution (concentration is 5 wt%) after the catalyst is uniformly dispersed in the slurry, and performing ultrasonic treatment for 30min to complete the preparation of cathode slurry.
3. Preparing a membrane electrode with an optimized layer: adopting a knife coating method, placing a certain size of Nafion212 film on the surface of a negative pressure type hot table, controlling the temperature of the hot table at 80 ℃, sequentially knife-coating a cathode catalyst layer on one side of the film, knife-coating mixed slurry of an optimized layer and an anode catalyst layer on the other side of the film, and finishing an effective surfaceThe product is 50cm 2 Preparing the membrane electrode of (1). And after the scraping coating is finished, the electrode is placed at 80 ℃ for vacuum drying to completely remove residual solvent in the electrode, and the preparation of the membrane electrode with an optimized layer positioned outside the anode catalyst layer is finished.
In this example, a 212 membrane (50 μm) was used as an electrolyte membrane to prepare a membrane electrode with an optimized layer, the optimized layer was dispersed in an anode catalyst layer, and an electrolytic cell performance test was performed on the membrane electrode, where the hydrogen concentration in the anode oxygen was 0.044%, and compared with an N115 membrane electrode with a higher thickness without the optimized layer in the comparative example, the hydrogen concentration was still significantly reduced.
Example 4
1. Preparing optimized layer slurry: weighing 50mg of platinum-palladium catalyst (with Pt loading capacity of 60 wt%), mixing 3g of isopropanol with the catalyst, performing ultrasonic treatment for 10min, adding Nafion solution (with the concentration of 5 wt%) with the mass of the catalyst after the catalyst is uniformly dispersed in the slurry, and continuing ultrasonic treatment for 30min to complete preparation of optimized layer slurry.
2. Preparing cathode catalyst layer slurry: 57.14mg of platinum-carbon catalyst (platinum loading is 70 wt%), 4.5g of isopropanol is added, ultrasonic treatment is carried out for 10min, 381mg of Nafion solution (concentration is 5 wt%) is added after the catalyst is uniformly dispersed in the slurry, and ultrasonic treatment is continued for 30min, so that the preparation of the slurry is completed.
3. Preparing anode catalyst layer slurry: weighing 100mg of iridium black catalyst, adding 6g of isopropanol, performing ultrasonic treatment for 10min, adding 667mg of Nafion solution (the concentration is 5 wt%) after the catalyst is uniformly dispersed in the slurry, and performing ultrasonic treatment for 30min to complete the preparation of the slurry.
4. Preparation of membrane electrode with optimized layer: the optimized layer is prepared by adopting a spraying method, a certain size of Nafion1135 membrane is placed on the surface of a negative pressure type heating table, the temperature of the heating table is controlled to be 80 ℃, cathode catalysis layer slurry is sprayed on one side of the membrane in sequence according to the spraying sequence required by the position of the optimized layer, then anode catalysis layer slurry and optimized layer slurry are sprayed on the other side of the membrane in sequence, and the effective area is 50cm 2 Preparing the membrane electrode of (1). After the spraying is finished, the electrode is placed at 80 ℃ for vacuum drying to completely remove the residual solvent in the electrode, and the anode catalyst layer with an optimized layer positioned outside the anode catalyst layer is completedPreparing the membrane electrode of (1).
In this example, a membrane electrode having an optimized layer prepared by using an N1135 membrane (75 μm) as an electrolyte membrane, wherein the optimized layer is located outside an anode catalyst, and the mass ratio of a binder to an active component is 0.5:1, and when an electrolytic cell performance test is performed on the membrane electrode, the hydrogen concentration in anode oxygen is 0.109%, compared with example 2, the hydrogen content is significantly increased; and compared with the N115 membrane electrode with higher thickness without the optimized layer in the comparative example, the hydrogen concentration is still obviously reduced, which indicates that the function of the optimized layer still exists.
Comparative example 1
1. Preparing cathode catalyst layer slurry: 57.14mg of platinum-carbon catalyst (platinum loading is 70 wt%), 4.5g of isopropanol is added, ultrasonic treatment is carried out for 10min, 381mg of Nafion solution (concentration is 5 wt%) is added after the catalyst is uniformly dispersed in the slurry, and ultrasonic treatment is continued for 30min, so that the preparation of the slurry is completed.
2. Preparing anode catalyst layer slurry: weighing 100mg of iridium black catalyst, adding 6g of isopropanol, performing ultrasonic treatment for 10min, adding 667mg of Nafion solution (the concentration is 5 wt%) after the catalyst is uniformly dispersed in the slurry, and performing ultrasonic treatment for 30min to complete the preparation of the slurry.
3. Preparation of membrane electrode without optimization layer: the method is carried out by adopting a spraying method, a certain size of Nafion115 membrane is placed on the surface of a negative pressure type hot table, the temperature of the hot table is controlled at 80 ℃, cathode catalyst layer and anode catalyst layer slurry are sprayed on two sides of the membrane in sequence, and the effective area is 50cm 2 Preparing the membrane electrode of (1). And after the spraying is finished, the electrode is placed at 80 ℃ for vacuum drying to completely remove the residual solvent in the electrode, and the preparation of the membrane electrode is finished.
Comparative example 1 is a membrane electrode without an optimized layer prepared with a 115 membrane as an electrolyte membrane, and the membrane electrode was subjected to an electrolytic cell performance test, and the hydrogen concentration in oxygen was 0.209%, which was significantly higher than that of the membrane electrode with an optimized layer of the present application.
Claims (7)
1. A membrane electrode for a solid electrolyte electrolytic cell, characterized in that the membrane electrode comprises an optimized layer; the optimized layer is positioned between the anode catalyst layer and the proton exchange membrane, or the optimized layer is positioned outside the anode catalyst layer, or the optimized layer is positioned in one or two of the anode catalyst layers; the active component of the optimization layer is a catalyst with hydrogen adsorption or hydrogen oxidation function.
2. The membrane electrode of claim 1, wherein the active component is at least one of Pt, Pd, PtPd alloy.
3. A membrane electrode assembly according to any one of claims 1 to 2, wherein the optimised layer is prepared by spraying, screen printing or knife coating the active ingredient onto the membrane electrode.
4. A membrane electrode according to claim 3, wherein: the optimized layer is prepared into a membrane electrode in the form of slurry, and the slurry comprises an active component, a binder and a solvent; the binder is high molecular resin with proton conduction function; the solvent is a volatile organic solvent.
5. The membrane electrode of claim 4, wherein the binder is a perfluorosulfonic acid resin; the solvent is ethanol or isopropanol.
6. A membrane electrode according to claim 3, characterized in that the order of assembly of the optimized layers on the membrane electrode is performed according to a positional structure; when the optimized layer is positioned between the anode catalyst layer and the proton exchange membrane, the optimized layer is prepared on the surface of the proton exchange membrane before the anode catalyst layer is assembled, the mass ratio of the binder to the active components in slurry of the optimized layer is 0.45-2: 1, and the mass ratio of the solvent to the active components is 20-100: 1;
when the optimized layer is positioned at the outer side of the anode catalyst layer, the preparation of the optimized layer is carried out after the assembly of the anode catalyst layer; when the optimized layer is doped in the anode catalyst, the anode catalyst layer slurry and the optimized layer slurry are simultaneously dispersed on the surface of the proton exchange membrane; in the slurry of the optimized layer, the mass ratio of the binder to the active component is 0.1-0.4: 1, and the mass ratio of the solvent to the active component is 20-100: 1.
7. The membrane electrode assembly according to any one of claims 1 to 6, wherein the mass ratio of the active component in the optimized layer to the catalyst in the anode catalytic layer is 0.05 to 10: 1.
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| US20070009783A1 (en) * | 2003-08-05 | 2007-01-11 | Lg Chem, Ltd. | Hybrid membrane-electrode assembly with minimal interfacial resistance and preparation method thereof |
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| US20070009783A1 (en) * | 2003-08-05 | 2007-01-11 | Lg Chem, Ltd. | Hybrid membrane-electrode assembly with minimal interfacial resistance and preparation method thereof |
| CN101388463A (en) * | 2008-10-23 | 2009-03-18 | 上海交通大学 | Membrane electrode for proton exchange membrane water electrolysis battery and preparation thereof |
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| CN113235120A (en) * | 2021-03-30 | 2021-08-10 | 清华大学 | Membrane electrode assembly and water electrolysis device |
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