A high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water and a preparation method thereof

Abstract

The present invention provides a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water and a preparation method thereof. The preparation method mainly includes the preparation of electrode powder: preparing (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3‑δ (LSCF) powder by a liquid-phase synthesis method, and preparing M x Ce 1‑x N y O2 powder by a co-precipitation method for use in the electrode and the isolation layer; preparing a half-cell by a co-casting process; preparing the isolation layer and the oxygen electrode by a screen printing technique, and introducing high-content water vapor to achieve hydrogen production by electrolyzing water. The high-performance all-solid-state electrolytic cell prepared by the present invention has high catalytic activity for hydrogen production by electrolyzing water and a Faraday efficiency, can operate at a medium-high temperature of 650-850 °C, can effectively reduce power consumption, and improve the energy conversion efficiency.

Description

Technical Field

[0001] The present invention relates to an electrolytic cell, and particularly to a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water and a preparation method thereof. Background Art

[0002] At present, the energy crisis and environmental pollution have forced the transformation of energy. Among them, hydrogen energy has the advantages of high calorific value and no pollution, and has attracted much attention from researchers. Hydrogen energy has risen to the national energy strategic position. The current methods for hydrogen production include hydrogen production from fossil fuels, hydrogen production by methanol reforming, hydrogen production from industrial by-products, and hydrogen production by electrolyzing water. Among them, hydrogen production by electrolyzing water can couple clean electric energies such as solar energy, wind energy, and tidal energy for electrolysis, reducing the waste of excess electric energy.

[0003] Currently, there are mainly three methods for hydrogen production by electrolyzing water: alkaline water electrolyzers, proton exchange membrane electrolytic cells, and solid oxide electrolytic cells (SOECs), etc. First of all, alkaline water electrolysis technology is the most mature at present, but due to more side reactions, lower electrolysis efficiency, strong corrosiveness of the electrolyte material, there are certain safety hazards. The proton exchange membrane electrolytic cell is a new pollution-free technology, but due to its use of precious metals as electrode materials, the equipment cost is relatively high. In contrast, SOEC can operate at a high temperature of 650-850 °C, and is an energy storage device that converts electric energy and heat energy into chemical energy, which can effectively reduce the power consumption and improve the energy conversion efficiency. Therefore, hydrogen production by SOEC electrolyzing water is of great significance for the reform of new energy and for better realizing the "dual carbon goal".

[0004] The solid oxide electrolytic cell SOEC generally includes a hydrogen electrode, an electrolyte, a barrier layer, and an oxygen electrode. Among them, the performance of the barrier layer seriously affects the performance of the electrolytic cell. Too high or too low sintering temperature results in too large ohmic resistance of the cell, causing the Faraday effect of the electrolytic cell to decrease. And the performance of the oxygen electrode seriously affects the efficiency and durability of the electrolytic cell. During the long-term operation of the electrolytic cell, there are problems such as interdiffusion reaction, durability, and stability caused by high temperature in the oxygen electrode, which seriously hinders the long-term stability of the electrolytic cell. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a preparation method of a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water. The prepared high-performance all-solid-state electrolytic cell has high catalytic activity and Faraday efficiency for hydrogen production by electrolyzing water, can operate at a medium and high temperature of 650-850 °C, can effectively reduce the power consumption, and improve the energy conversion efficiency.

[0006] To solve the above technical problem, the technical solution of the present invention is as follows:

[0007] A preparation method of a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water, comprising the following steps:

[0008] S1. Mix NiO, YSZ, and an organic glue solution, ball mill for 12 - 24 h, and then use co - casting to make a support layer and a hydrogen electrode. The hydrogen electrode is set on the support layer.

[0009] S2. Mix YSZ and an organic glue evenly to obtain a YSZ slurry. Screen - print the YSZ slurry on the hydrogen electrode obtained in step S1 to form an electrolyte layer, and then sinter at high temperature for 2 - 5 h to obtain a half - cell.

[0010] S3. Weigh the inorganic salts of elements M, Ce, and N according to the stoichiometric ratio of M x Ce 1-x N y O₂, dissolve them in deionized water, add PVP, and mix evenly to obtain a mixed solution A. Here, M = Pr, La, Nd, Sm, or Gd, N = Fe, Mn, Cu, Co, Ni, or Zn, 0 ≤ x ≤ 0.3, 0 ≤ y ≤ 0.1.

[0011] S4. Dissolve a precipitating agent in deionized water, mix evenly to obtain a mixed solution B. Under stirring conditions, drop the mixed solution A obtained in step S3 into the mixed solution B. After dropping, continue to stir for 2 - 4 h, and then continue to age for 12 - 24 h after stopping stirring to obtain reactant one.

[0012] S5. Centrifuge the reactant one obtained in step S4 to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water, and then centrifuge 3 times to obtain precipitate two. Dry precipitate two and then calcine at high temperature for 2 - 5 h to obtain M x Ce 1-x N y O₂ powder.

[0013] S6. Mix the M x Ce 1-x N y O₂ powder obtained in step S5 with an organic glue evenly to obtain an isolation layer slurry. Screen - print the isolation layer slurry on the surface of the hydrogen electrode of the half - cell obtained in step S2 to form an isolation layer.

[0014] S7. Weigh the inorganic salts of elements La, Sr, Co, and Fe according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. Add glycine and heat to a gel state, then transfer to a muffle furnace and sinter at high temperature for 2 - 5 h to obtain LSCF oxygen electrode powder.

[0015] S8. The M x Ce 1-x Ny Mix the O2 powder, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly to obtain an oxygen electrode paste. Screen-print the oxygen electrode paste on the surface of the isolation layer obtained in step S6 to form an oxygen electrode, and perform high-temperature sintering for 1 - 3 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0016] Furthermore, in step S1 of the present invention, the organic glue solution is composed of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, and PEG with equal weights, and the weight ratio of NiO, YSZ, and the organic glue solution is 6:4:(2 - 5); the rotation speed of ball milling is 100 - 500 r / min; the thickness of the support layer is 300 - 1000 μm, and the thickness of the hydrogen electrode is 10 - 50 μm. Among them, the support layer is the foundation of the electrolytic cell and has a certain thickness to provide sufficient structural strength to ensure that the cell does not deform or even break under various stress actions; the hydrogen electrode is the reaction site where water vapor molecules gain electrons to undergo a reduction reaction to generate oxygen ions and hydrogen molecules, and is closely connected to the electrolyte layer.

[0017] Furthermore, in step S2 of the present invention, the organic glue is composed of ethyl cellulose and terpineol with a weight ratio of (1 - 5):50, and the weight ratio of YSZ to the organic glue is 1:(1 - 5); the temperature of high-temperature calcination is 1200 - 1400 °C; the thickness of the electrolyte layer is 0.01 - 0.02 mm. The electrolyte layer is a multifunctional region that separates the hydrogen electrode and the oxygen electrode and is responsible for transporting oxygen ions and blocking electron conduction.

[0018] Furthermore, in step S3 of the present invention, M x Ce 1-x N y The ratio of M Ce N O2, deionized water, and PVP is 1 mol:(1 - 2) L:(0.1 - 0.2) g, and the inorganic salts of M, Ce, and N elements are one of the nitrates, acetates, or chlorides of M, Ce, and N elements.

[0019] Furthermore, in step S4 of the present invention, the ratio of the precipitating agent to deionized water is (0.1 - 0.75) mol:1 L, and the precipitating agent is one of ammonium carbonate, urea, ammonium oxalate, or ammonia water; the volume ratio of mixed solution A to mixed solution B is 1:(2 - 3); the dropping rate of mixed solution A is 5 - 10 mL / min; the stirring speed is 300 - 500 r / min.

[0020] Furthermore, in step S5 of the present invention, the centrifugation speed is 10000 rpm and the time is 20 min; the drying temperature is 100 - 120 °C and the time is 10 - 12 h; the temperature of high-temperature calcination is 600 - 800 °C.

[0021] Further, in step S6 of the present invention, the organic glue is composed of ethyl cellulose and terpineol with a weight ratio of (1-5):25, M x Ce 1-x N y The weight ratio of the CeO2 powder and the organic glue is 1:(1-2), and the thickness of the isolation layer is 1-5 μm. The isolation layer is an isolation belt that prevents the direct contact between the oxygen electrode and the electrolyte and inhibits the diffusion of some elements in the oxygen electrode, and has good ionic conductivity.

[0022] Further, in step S7 of the present invention, the ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ , deionized water, and glycine is 1 mol:1 L:2 mol. The inorganic salts of La, Sr, Co, and Fe elements are one of nitrates, acetates, or chlorides of La, Sr, Co, and Fe elements; the heating temperature is 80-300 °C; the high-temperature sintering temperature is 300-600 °C.

[0023] Further, in step S8 of the present invention, the organic glue is composed of ethyl cellulose and terpineol with a weight ratio of (1-5):25, M x Ce 1-x N y The weight ratio of the CeO2 powder, the LSCF oxygen electrode powder, and the organic glue is (1-2):1:1, the high-temperature sintering temperature is 1000-1200 °C; the thickness of the oxygen electrode is 10-30 μm. The oxygen electrode is the reaction site where oxygen ions lose electrons to undergo an oxidation reaction and oxygen molecules are precipitated.

[0024] Another technical problem to be solved by the present invention is to provide a high-performance all-solid-state electrolytic cell for electrolyzing water to produce hydrogen prepared by the above preparation method.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1) The raw materials used in the present invention are economical, safe, and the material preparation process is green and environmentally friendly.

[0027] 2) In the present invention, the main materials used in the all-solid-state high-temperature electrolytic cell, such as rare earth oxides M x Ce 1-x N y O2 (M = Pr, La, Nd, Sm, Gd; N = Fe, Mn, Cu, Co, Ni, Zn; 0 ≤ x ≤ 0.3; 0 ≤ y ≤ 0.1) and (La 0.6 Sr 0.4 ) 0.95 Co 0.2Fe 0.8 O 3-δ (LSCF) and other powder materials can be synthesized by simple co-precipitation method and combustion method, with low cost and environmental friendliness, and are suitable for large-scale production.

[0028] 3) The present invention uses a co-casting process to prepare a half-cell, and screen printing technology to prepare a separator layer and an oxygen electrode. The structure of the all-solid-state electrolytic cell assembled is stable, the process is simple and the cost is low. After high-temperature sintering, it has a density of about 95%, and better electrolytic cell performance can be achieved at a wide range of operating temperatures.

[0029] 4) The all-solid-state high-temperature electrolytic cell prepared by the present invention has excellent electrochemical performance. The rare earth M x Ce 1-x N y O2 oxide exhibits high ionic conductivity at medium and high temperatures, which helps ion transport, reduces the internal resistance of the battery. As a composite electrode, it can improve the ion transport rate at the three-phase interface of the electrode, enhance the interfacial charge transfer process of the electrode, and improve the electrochemical performance of the oxygen electrode and the fuel electrode, and finally achieve high-efficiency all-solid-state electrolytic cell performance.

[0030] 5) Sealing the all-solid-state electrolytic cell prepared by the present invention on a ceramic tube, introducing water vapor with different contents and applying voltage can realize the preparation of hydrogen. The present invention can efficiently convert electrical energy and heat energy into chemical energy, that is, electrolyze water vapor into hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings described herein are used to provide a further understanding of the present invention, form a part of this application, and do not constitute an improper limitation to the present invention. In the drawings:

[0032] Figure 1 (a) is the X-ray powder diffraction pattern (XRD) of the LSCF oxygen electrode powder and M x Ce 1-x N y O2 powder prepared in Example 1 of the present invention; Figure 1 (b) is the X-ray diffraction pattern of the LSCF oxygen electrode powder and M x Ce 1-x N y O2 powder after being uniformly mixed in different proportions and calcined at 1100 °C for 2 h;

[0033] Figure 2 is the X-ray diffraction pattern of the LSCF oxygen electrode powder with different proportions and M x Ce 1-x N y(a) Nyquist plots, (b) polarization resistance values, Arrhenius curves (c) Rp, and (d) Ro of the oxygen electrode composite with O2 powder at 700 and 800 °C tests;

[0034] Figure 3 Electrolysis performance diagrams of oxygen electrodes with different ratios and components prepared by the present invention. Detailed implementation manners

[0035] The present invention will be described in detail below with reference to specific embodiments. Here, the illustrative embodiments of the present invention and the descriptions are used to explain the present invention, but not to limit the present invention.

[0036] Example 1

[0037] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0038] S1. Mix NiO, YSZ, and organic glue solution in a weight ratio of 6:4:4. The organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate, and PEG. After ball milling at 300 r / min for 18 h, a support layer with a thickness of 1000 μm and a hydrogen electrode with a thickness of 20 μm are formed by co-casting. The hydrogen electrode is disposed on the support layer;

[0039] S2. Mix YSZ and organic glue evenly in a weight ratio of 1:1 to obtain YSZ slurry. The organic glue is composed of ethyl cellulose and terpineol in a weight ratio of 3:50. Screen-print the YSZ slurry on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.02 mm, and sinter at 1400 °C for 5 h to obtain a half cell;

[0040] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2, dissolve them in deionized water, add PVP, and mix evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:1 L:0.2 g. Among them, M = Sm, N = Mn, x = 0.15, y = 0.075. The nitrate of Sm element is Sm(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Mn element is Mn(NO3)4·4H2O;

[0041] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.75 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, dropwise add the mixed solution A obtained in step S3 into mixed solution B at a volume ratio of 1:2 and a dropping rate of 10 mL / min. After dropping, continue to stir at a speed of 400 r / min for 4 h, and then continue aging for 12 h after stopping stirring to obtain reactant one;

[0042] S5. Centrifuge the reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with anhydrous ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 115 °C for 12 h and then calcine it at 700 °C for 2 h to obtain M x Ce 1-x N y O2 powder, denoted as Mn-SDC powder;

[0043] S6. Mix the Mn-SDC powder obtained in step S5 and the organic glue evenly according to a weight ratio of 1:1 to obtain the isolation layer slurry. The organic glue consists of ethyl cellulose and terpineol with a weight ratio of 1:25. Screen-print the isolation layer slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form an isolation layer with a thickness of 3 μm;

[0044] S7. Weigh nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. After adding glycine, heat to a gel state at 200 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ to deionized water and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter at 300 °C for 2 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0045] S8. Mix the Mn-SDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly according to a weight ratio of 1:1:1 to obtain an oxygen electrode paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 1:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 20 μm, and sinter it at a high temperature of 1150 °C for 2 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0046] Seal the high-performance all-solid-state electrolytic cell prepared in Example 1 on an alumina tube, then put it into a resistance furnace and heat it up to 650 - 850 °C, and then apply a voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0047] Example 2

[0048] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0049] S1. Mix NiO, YSZ, and an organic glue solution according to a weight ratio of 6:4:3. The organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate, and PEG. After ball milling at a speed of 200 r / min for 21 h, a support layer with a thickness of 800 μm and a hydrogen electrode with a thickness of 30 μm are formed by co-casting, and the hydrogen electrode is arranged on the support layer;

[0050] S2. Mix YSZ and the organic glue evenly according to a weight ratio of 1:5 to obtain a YSZ paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 5:50. Screen-print the YSZ paste on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.01 mm, and sinter it at a high temperature of 1300 °C for 4 h to obtain a half-cell;

[0051] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2 and dissolve them in deionized water. After adding PVP, mix them evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:2 L:0.2 g. Among them, M = Sm, N = Mn, x = 0.15, y = 0.075. The nitrate of Sm element is Sm(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Mn element is Mn(NO3)4·4H2O;

[0052] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.1 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, add the mixed solution A obtained in step S3 dropwise into mixed solution B at a dropping rate of 8 mL / min according to a volume ratio of 1:2. After dropping, continue to stir at a speed of 300 r / min for 3 h, and then continue to age for 24 h after stopping stirring to obtain reactant one;

[0053] S5. Centrifuge reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 100 °C for 10 h and then calcine it at 650 °C for 4 h to obtain M x Ce 1-x N y O2 powder, denoted as Mn-SDC powder;

[0054] S6. Mix the Mn-SDC powder obtained in step S5 and the organic glue evenly according to a weight ratio of 1:2 to obtain the separator slurry. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 2:25. Screen-print the separator slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form a separator with a thickness of 4 μm;

[0055] S7. Weigh nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. After adding glycine, heat to a gel state at 200 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ , deionized water, and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter it at 400 °C for 3 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0056] S8. Mix the Mn-SDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly according to a weight ratio of 1.5:1:1 to obtain an oxygen electrode paste. The organic glue consists of ethyl cellulose and terpineol with a weight ratio of 2:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 15 μm, and sinter it at a high temperature of 1200 °C for 2 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0057] Seal the high-performance all-solid-state electrolytic cell prepared in Example 2 on an alumina tube, then place it in a resistance furnace and heat it to 650 - 850 °C, and then apply voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0058] Example 3

[0059] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0060] S1. Mix NiO, YSZ, and the organic glue solution according to a weight ratio of 6:4:2. The organic glue solution consists of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate, and PEG. After ball milling at a speed of 400 r / min for 15 h, a support layer with a thickness of 500 μm and a hydrogen electrode with a thickness of 10 μm are formed by co-casting, and the hydrogen electrode is arranged on the support layer;

[0061] S2. Mix YSZ and the organic glue evenly according to a weight ratio of 1:3 to obtain a YSZ paste. The organic glue consists of ethyl cellulose and terpineol with a weight ratio of 1:50. Screen-print the YSZ paste on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.01 mm, and sinter it at a high temperature of 1200 °C for 5 h to obtain a half-cell;

[0062] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2, dissolve them in deionized water, add PVP and mix evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:1 L:0.1 g. Among them, M = Pr, N = Mn, x = 0.3, y = 0.05. The nitrate of Pr element is Pr(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Mn element is Mn(NO3)4·4H2O;

[0063] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.2 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, add the mixed solution A obtained in step S3 dropwise to mixed solution B at a dropping rate of 5 mL / min according to a volume ratio of 1:3. After dropping, continue to stir at a speed of 500 r / min for 2 h, and then continue aging for 18 h after stopping stirring to obtain reactant one;

[0064] S5. Centrifuge the reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 120 °C for 11 h and then calcine it at 800 °C for 5 h to obtain M x Ce 1-x N y O2 powder, denoted as Mn-PDC powder;

[0065] S6. Mix the Mn-PDC powder obtained in step S5 and the organic glue evenly according to a weight ratio of 1:1 to obtain the isolation layer slurry. The organic glue consists of ethyl cellulose and terpineol with a weight ratio of 5:25. Screen-print the isolation layer slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form an isolation layer with a thickness of 2 μm;

[0066] S7. Weigh the nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. After adding glycine, heat it to a gel state at 100 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ to deionized water and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter it at 600 °C for 2 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0067] S8. Mix the Mn-PDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly according to a weight ratio of 1:1:1 to obtain an oxygen electrode paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 5:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 10 μm, and sinter it at 1100 °C for 2.5 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0068] Seal the high-performance all-solid-state electrolytic cell prepared in Example 3 on an alumina tube, then place it in a resistance furnace and heat it to 650 - 850 °C, and then apply a voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0069] Example 4

[0070] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0071] S1. Mix NiO, YSZ, and the organic glue solution according to a weight ratio of 6:4:5. The organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate, and PEG. After ball milling at a speed of 100 r / min for 24 h, a support layer with a thickness of 300 μm and a hydrogen electrode with a thickness of 10 μm are formed by co-casting, and the hydrogen electrode is disposed on the support layer;

[0072] S2. Mix YSZ and the organic glue evenly according to a weight ratio of 1:2 to obtain a YSZ paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 4:50. Screen-print the YSZ paste on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.02 mm, and sinter it at 1250 °C for 4 h to obtain a half-cell;

[0073] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2 and dissolve them in deionized water. After adding PVP, mix them evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:2 L:0.1 g. Among them, M = Pr, N = Co, x = 0.25, y = 0.025. The nitrate of Pr element is Pr(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Co element is Co(NO3)4·6H2O;

[0074] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.5 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, dropwise add the mixed solution A obtained in step S3 into mixed solution B at a volume ratio of 1:3 and a dropping rate of 10 mL / min. After dropping, continue to stir at a speed of 400 r / min for 3 h, and then continue to age for 12 h after stopping stirring to obtain reactant one;

[0075] S5. Centrifuge the reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 110 °C for 10 h and then calcine it at 650 °C for 3.5 h to obtain M x Ce 1-x N y O2 powder, denoted as Co-PDC powder;

[0076] S6. Mix the Co-PDC powder obtained in step S5 and the organic glue evenly according to a weight ratio of 1:1 to obtain the separator slurry. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 4:25. Screen-print the separator slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form a separator layer with a thickness of 1 μm;

[0077] S7. Weigh nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. After adding glycine, heat to a gel state at 80 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ to deionized water and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter at 350 °C for 4 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0078] S8. Mix the Co-PDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly according to a weight ratio of 1:1:1 to obtain an oxygen electrode paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 4:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 15 μm, and sinter it at a high temperature of 1000 °C for 3 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0079] Seal the high-performance all-solid-state electrolytic cell prepared in Example 4 on an alumina tube, then put it into a resistance furnace and heat it up to 650 - 850 °C, and then apply voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0080] Example 5

[0081] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0082] S1. Mix NiO, YSZ, and the organic glue solution according to a weight ratio of 6:4:3. The organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, poly(methyl acrylate), and PEG. After ball milling at a speed of 500 r / min for 12 h, a support layer with a thickness of 400 μm and a hydrogen electrode with a thickness of 50 μm are formed by co-casting. The hydrogen electrode is arranged on the support layer;

[0083] S2. Mix YSZ and the organic glue evenly according to a weight ratio of 1:4 to obtain a YSZ paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 2:50. Screen-print the YSZ paste on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.01 mm, and sinter it at a high temperature of 1350 °C for 4 h to obtain a half-cell;

[0084] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2 and dissolve them in deionized water. After adding PVP, mix them evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:1.5 L:0.1 g, where M = Nd, N = Fe, x = 0.1, y = 0.08. The nitrate of Nd element is Nd(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Fe element is Fe(NO3)4·9H2O;

[0085] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.4 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, dropwise add the mixed solution A obtained in step S3 into mixed solution B at a volume ratio of 1:2 and a dropping rate of 5 mL / min. After dropping, continue to stir at a speed of 500 r / min for 4 h, and then continue aging for 21 h after stopping stirring to obtain reactant one;

[0086] S5. Centrifuge the reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 120 °C for 10.5 h and then calcine it at 750 °C for 3 h to obtain M x Ce 1-x N y O2 powder, denoted as Fe-NDC powder;

[0087] S6. Mix the Fe-NDC powder obtained in step S5 and the organic glue evenly at a weight ratio of 1:2 to obtain the separator slurry. The organic glue is composed of ethyl cellulose and terpineol at a weight ratio of 3:25. Screen-print the separator slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form a separator layer with a thickness of 5 μm;

[0088] S7. Weigh the nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ , dissolve them in deionized water, add glycine, and then heat to a gel state at 250 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ to deionized water and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter it at 500 °C for 2.5 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0089] S8. Mix the Fe-NDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and the organic glue evenly according to a weight ratio of 1:1:1 to obtain an oxygen electrode paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 3:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 25 μm, and sinter it at 1050 °C for 1.5 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water.

[0090] Seal the high-performance all-solid-state electrolytic cell prepared in Example 5 on an alumina tube, then place it in a resistance furnace and heat it up to 650 - 850 °C, and then apply a voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0091] Example 6

[0092] Prepare a high-performance all-solid-state electrolytic cell for hydrogen production by electrolyzing water according to the following steps:

[0093] S1. Mix NiO, YSZ, and the organic glue solution according to a weight ratio of 6:4:4. The organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate, and PEG. After ball milling at a speed of 200 r / min for 24 h, a support layer with a thickness of 600 μm and a hydrogen electrode with a thickness of 40 μm are formed by co-casting, and the hydrogen electrode is arranged on the support layer;

[0094] S2. Mix YSZ and the organic glue evenly according to a weight ratio of 1:3 to obtain a YSZ paste. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 3:50. Screen-print the YSZ paste on the hydrogen electrode obtained in step S1 to form an electrolyte layer with a thickness of 0.02 mm, and sinter it at 1400 °C for 3 h to obtain a half-cell;

[0095] S3. Weigh the nitrates of element M, element Ce, and element N according to the stoichiometric ratio of M x Ce 1-x N y O2 and dissolve them in deionized water. After adding PVP, mix them evenly to obtain a mixed solution A. The ratio of M x Ce 1-x N y O2, deionized water, and PVP is 1 mol:1.5 L:0.2 g. Among them, M = Nd, N = Mn, x = 0.15, y = 0.06. The nitrate of Nd element is Nd(NO3)3·6H2O, the nitrate of Ce element is Ce(NO3)3·6H2O, and the nitrate of Mn element is Mn(NO3)3·9H2O;

[0096] S4. Dissolve ammonium carbonate in deionized water at a ratio of 0.3 mol:1 L, mix evenly to obtain mixed solution B. Under stirring conditions, add the mixed solution A obtained in step S3 dropwise into mixed solution B at a dropping rate of 10 mL / min according to a volume ratio of 1:3. After dropping, continue to stir at a speed of 300 r / min for 3 h, and then continue to age for 15 h after stopping stirring to obtain reactant one;

[0097] S5. Centrifuge the reactant one obtained in step S4 at a speed of 10000 rpm for 20 min to obtain precipitate one. Wash precipitate one with absolute ethanol and deionized water and then centrifuge 3 times to obtain precipitate two. Dry precipitate two at 110 °C for 11.5 h and then calcine it at 700 °C for 2.5 h to obtain M x Ce 1-x N y O2 powder, denoted as Mn-NDC powder;

[0098] S6. Mix the Mn-NDC powder obtained in step S5 and the organic glue evenly according to a weight ratio of 1:2 to obtain the separator slurry. The organic glue is composed of ethyl cellulose and terpineol with a weight ratio of 2:25. Screen-print the separator slurry on the hydrogen electrode surface of the half-cell obtained in step S2 to form a separator with a thickness of 3 μm;

[0099] S7. Weigh nitrates of La element, Sr element, Co element, and Fe element according to the stoichiometric ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ and dissolve them in deionized water. After adding glycine, heat it to a gel state at 150 °C. The ratio of (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ to deionized water and glycine is 1 mol:1 L:2 mol. Transfer it to a muffle furnace and sinter it at 450 °C for 5 h to obtain LSCF oxygen electrode powder. Among them, the nitrate of La element is La(NO3)3·9H2O, the nitrate of Sr element is Sr(NO3)2, the nitrate of Co element is Co(NO3)2·6H2O, and the nitrate of Fe element is Fe(NO3)3·9H2O;

[0100] S8. Mix the Mn-NDC powder obtained in step S5, the LSCF oxygen electrode powder obtained in step S7, and an organic binder uniformly according to a weight ratio of 2:1:1 to obtain an oxygen electrode paste. The organic binder consists of ethyl cellulose and terpineol with a weight ratio of 4:25. Screen-print the oxygen electrode paste on the surface of the separator layer obtained in step S6 to form an oxygen electrode with a thickness of 30 μm, and then sinter it at 1150 °C for 2 h to obtain a high-performance all-solid-state electrolytic cell for hydrogen production by water electrolysis.

[0101] Seal the high-performance all-solid-state electrolytic cell prepared in Example 6 on an alumina tube, then place it in a resistance furnace and heat it to 650 - 850 °C, and then apply a voltage while passing water at different temperatures, and hydrogen gas can be precipitated on the surface of the hydrogen electrode.

[0102] Comparative Example 1:

[0103] The difference from Example 1 is that Mn(NO3)4·4H2O was not used in step S3, and the SDC powder was prepared in step S5. Comparative Example 2:

[0104] The difference from Example 1 is that Mn(NO3)4·4H2O was not used in step S3, the SDC powder was prepared in step S5, and in step S8, the weight ratio of the SDC powder to the LSCF oxygen electrode powder is 1.5:1.

[0105] Comparative Example 3:

[0106] The difference from Example 1 is that the Mn-SDC powder was not used in step S8.

[0107] Experimental Example

[0108] Measure the polarization resistance and hydrogen production performance of the electrolytic cells prepared in Examples 1 - 6 and Comparative Examples 1 - 3 respectively according to GB / T 34582-2017, and the test results are shown in Table 1.

[0109]

[0110] Table 1

[0111] It can be seen from Table 1 that the polarization resistance and hydrogen production performance of Examples 1 - 6 of the present invention are both better than those of Comparative Example 3. Some of the raw materials and preparation steps used in Comparative Examples 1 - 2 are different from those in Example 1. Compared with Example 1, the hydrogen production performance of the electrolyzed water in Comparative Examples 1 - 2 is significantly reduced, indicating that the separator layer and oxygen electrode used in the present invention can effectively improve the hydrogen production performance of the all-solid-state electrolytic cell at medium and high temperatures.

[0112] The above embodiments are only illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water, characterized in that: The following steps are involved: S1. NiO, YSZ and organic glue solution are mixed, ball-milled for 12-24 hours, and then co-cast to form a support layer and a hydrogen electrode, and the hydrogen electrode is disposed on the support layer; S2. YSZ and organic glue are mixed evenly to obtain YSZ slurry, the YSZ slurry is screen-printed on the hydrogen electrode obtained in step S1 to form an electrolyte layer, and sintered at high temperature for 2-5h to obtain a half-cell; S3. According to M x Ce 1-x N y The inorganic salts of M, Ce, and N elements are weighed and dissolved in deionized water, and PVP is added and mixed evenly to obtain a mixed solution A, wherein M = Pr, La, Nd, Sm or Gd, N = Fe, Mn, Cu, Co, Ni or Zn, 0≤x≤0.3, 0≤y≤0.1, M x Ce 1-x N y The ratio of O2, deionized water and PVP is 1 mol: (1-2) L: (0.1-0.2) g, and the inorganic salt of M, Ce and N elements is one of the nitrates, acetates or chlorides of M, Ce and N elements; S4. The precipitant was dissolved in deionized water, mixed to obtain a mixed solution B, and the mixed solution A obtained in step S3 was added dropwise to the mixed solution B under stirring, and stirring was continued for 2-4h after the addition was completed. After stopping stirring, aging was continued for 12-24h to obtain a reactant; S5. The reaction product obtained in step S4 is centrifuged to obtain a precipitate, the precipitate is washed with anhydrous ethanol and deionized water and centrifuged three times to obtain a precipitate, the precipitate is dried and calcined at high temperature for 2-5h to obtain M x Ce 1-x N y O2 powder; S6. The M obtained in step S5 is x Ce 1-x N y O2 powder and organic glue are uniformly mixed to obtain an isolation layer slurry, and the isolation layer slurry is screen-printed on the surface of the hydrogen electrode of the half-cell obtained in step S2 to form an isolation layer; S7. According to (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ Inorganic salts of La, Sr, Co, and Fe are weighed and dissolved in deionized water in a stoichiometric ratio, glycine is added and heated to a gel state, and then sintered in a muffle furnace at high temperature for 2-5 hours to obtain LSCF oxygen electrode powder; S8. The M obtained in step S5 is x Ce 1-x N y O2 powder, LSCF oxygen electrode powder obtained in step S7, and organic glue are evenly mixed to obtain oxygen electrode slurry, and the oxygen electrode slurry is screen-printed on the surface of the isolation layer obtained in step S6 to form an oxygen electrode, and sintered at high temperature for 1-3 hours to obtain a high-performance all-solid-state electrolytic cell for electrolyzing water to produce hydrogen.

2. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In the step S1, the organic glue solution is composed of equal weights of ethanol, xylene, triethanolamine, castor oil, polyvinyl butyral, polymethyl acrylate and PEG, and the weight ratio of NiO, YSZ and organic glue solution is 6:4:(2-5); the rotation speed of the ball mill is 100-500r / min; the thickness of the support layer is 300-1000μm, and the thickness of the hydrogen electrode is 20-50μm.

3. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In the step S2, the organic glue is composed of ethyl cellulose and pinene alcohol in a weight ratio of (1-5):50, and the weight ratio of YSZ to organic glue is 1:(1-5); the temperature of high-temperature calcination is 1200-1400°C; and the thickness of the electrolyte layer is 0.01-0.02mm.

4. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In the step S4, the ratio of the precipitant to the deionized water is (0.1-0.75) mol:1L, the precipitant is one of ammonium carbonate, urea, ammonium oxalate or ammonia water; the volume ratio of the mixed solution A to the mixed solution B is 1:(2-3); the dropping speed of the mixed solution A is 5-10 mL / min; and the stirring speed is 300-500 r / min.

5. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In step S5, the centrifugal speed is 10000 rpm, the time is 20 min; the drying temperature is 100-120° C., the time is 10-12 h; the high temperature calcination temperature is 600-800° C.

6. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In step S6, the organic glue is composed of ethyl cellulose and pinene alcohol in a weight ratio of (1-5):25, M x Ce 1- x N y The weight ratio of O2 powder and organic glue is 1: (1-2), and the thickness of the isolation layer is 1-5μm.

7. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In step S7, (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ , deionized water, and glycine in a ratio of 1 mol:1L:2 mol; the inorganic salt of La, Sr, Co, and Fe elements is one of the nitrates, acetates, or chlorides of La, Sr, Co, and Fe elements; the heating temperature is 80-300°C; and the high-temperature sintering temperature is 300-600°C.

8. The method for preparing a high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water according to claim 1, characterized in that: In step S8, the organic glue is composed of ethyl cellulose and pinene alcohol in a weight ratio of (1-5):25, M x Ce 1- x N y The weight ratio of O2 powder, LSCF oxygen electrode powder and organic glue is (1-2):1:1, the high temperature sintering temperature is 1000-1200°C; the thickness of the oxygen electrode is 10-30μm.

9. A high-performance all-solid-state electrolytic cell for producing hydrogen by electrolysis of water, prepared according to the preparation method according to any one of claims 1 to 8.

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