CN117577860A - Proton ceramic electrochemical cell air electrode and preparation method thereof - Google Patents
Proton ceramic electrochemical cell air electrode and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 239000002003 electrode paste Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- ODWNBAWYDSWOAF-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxybenzene Chemical compound CC(C)(C)CC(C)(C)OC1=CC=CC=C1 ODWNBAWYDSWOAF-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 238000010345 tape casting Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000005382 thermal cycling Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- -1 oxygen ions Chemical class 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011533 mixed conductor Substances 0.000 description 2
- 239000012078 proton-conducting electrolyte Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 1
- QAACABRQFOBNSR-UHFFFAOYSA-N [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[Pr+2] Chemical compound [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[Pr+2] QAACABRQFOBNSR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
- H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses an air electrode of a Proton Ceramic Electrochemical Cell (PCECs) and a preparation method thereof. The air electrode is prepared by impregnating a conventional air electrode by an impregnation method, wherein the impregnating material is Ternary Conductive Oxide (TCO) perovskite material (namely PrNi x Co 1‑x O 3‑δ ，0<x<1) The purpose of developing the high-performance PCECS air electrode is achieved. The preparation method comprises the following steps: (1) Impregnating solution preparation (PrNi according to the stoichiometric ratio x Co 1‑ x O 3‑δ ) The method comprises the steps of carrying out a first treatment on the surface of the (2) providing an air electrode paste; (3) preparing an air electrode framework; (4) impregnating the conventional air electrode with an impregnating solution; and (5) sintering to obtain the surface modified electrode. The impregnated traditional electrode developed by the invention can obviously improve the electrochemical performance of the air electrode in the medium-low temperature PCECs,such as oxygen reduction and oxygen electrolysis reactivity, durability, and thermal cycling stability.
Description
Technical Field
The invention belongs to the field of fuel electrodes, and particularly relates to an air electrode of a proton ceramic electrochemical cell and a preparation method thereof.
Background
The ever-increasing energy demands and deteriorating environmental conditions have made the development of new energy sources, hydrogen energy, urgent. Proton Ceramic Electrochemical Cells (PCECs) are high-efficiency pollution-free hydrogen energy conversion devices and have remarkable effects on development and utilization of hydrogen energy. The PCECs not only can operate in a fuel cell mode, but also can be used as an electrolytic cell for producing hydrogen by water electrolysis, and pure and dry hydrogen is produced by the electrolytic mode.
The main components of PCECs consist of dense electrolyte (proton conducting), porous fuel electrode and air electrode. The working principle of PCCs for generating electricity by hydrogen is as follows: the hydrogen of the porous fuel electrode or anode is converted into protons (2H) 2 →4H + +4e - ) And releases electrons into the electrolyte, while the electrons are sent to an external circuit. The electrolyte promotes migration of protons from the fuel electrode to the air electrode (cathode) while impeding electron flow. On the air electrode side, oxygen molecules are reduced to oxygen ions (O 2- ) And then combines with protons and electrons through an oxygen reduction reaction (O 2 +4H + +4e - →2H 2 O) water is produced. The process of generating hydrogen by PCEC electrolysis is the reverse reaction of the reaction under the action of external circuit current.
The air electrode plays a key role in determining the PCEC performance output. The advantages of constructing a novel air electrode by an immersion method are obvious: the method is characterized by reducing polarization resistance, improving power density, enhancing durability and service life under specific gas, improving flexibility of fuel and reducing cost of materials and systems. The impregnation method is to impregnate a precursor solution on a pre-existing electrode skeleton and obtain an impregnated electrode by subsequent sintering. A common electrode backbone is LSCF with mixed ion-electron conductors (MIEC), see table 1. The challenges that currently exist are: (1) As the temperature decreases, the kinetics of the Oxygen Evolution Reaction (OER) and the Oxygen Reduction Reaction (ORR) on the air electrode decrease exponentially, greatly increasing the polarization resistance (Rp) of the PCEC. The majority of air electrodes developed by impregnation are based on oxygen ion conduction (e.g., YSZ, GDC, LSGM, etc.) as the electrolyte and are not suitable for PCECs, and higher operating temperatures are typically not suitable for low temperatures. (2) The materials used for impregnation are mainly electron-conductive, oxygen ion-conductive, or mixed ion-electron-conductive, and there is a significant shortage of research on electrode materials suitable for PCECs that can conduct protons, oxygen ions, and electrons at the same time; (3) In the fuel cell mode of PCEC, the air electrode generates a large amount of water, while in the electrolysis mode, steam needs to be introduced for electrolysis, which further exacerbates polarization losses and jeopardizes the stability of the air electrode. (4) The impregnation method can solve the problem of thermal expansion compatibility of the electrolyte and the electrode, but some air electrodes developed with other non-impregnation methods in recent years have a problem in thermal expansion matching with the electrolyte.
Table 1 related work reported in the dipping method to modify LSCF air electrode
The citations in table 1 are as follows:
1.Namgung,Y.,Hong,J.,Kumar,A.,Lim,D.K.&Song,S.J.One step infiltration induced multi-cation oxide nanocatalyst for load proof SOFC application.Appl.Catal.B Environ.267,118374(2020).
2.Chen,Y.et al.A Highly Efficient Multi-phase Catalyst Dramatically Enhances the Rate of Oxygen Reduction.Joule 2,938-949(2018).
3.Zeng,D.,Xu,K.,Zhu,F.&Chen,Y.Enhancing the oxygen reduction reaction activity and durability of a solid oxide fuel cell cathode by surface modification of a hybrid coating.Int.J.Hydrogen Energy(2023).doi:10.1016/j.ijhydene.2023.03.198
4.Shi,Y.et al.Surface enhanced performance of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathodes by infiltration Pr-Ni-Mn-O progress.J.Alloys Compd.902,163337(2022).
5.Wei,F.,Wang,L.,Luo,L.,Cheng,L.&Xu,X.One-pot impregnation to construct nanoparticles loaded scaffold cathode with enhanced oxygen reduction performance for LT-SOFCs.J.Alloys Compd.941,(2023).
6.Niu,Y.et al.Highly Active and Durable Air Electrodes for Reversible Protonic Ceramic Electrochemical Cells Enabled by an Efficient Bifunctional Catalyst.Adv.Energy Mater.12,1-9(2022).
7.Zhou,Y.et al.An Efficient Bifunctional Air Electrode for Reversible Protonic Ceramic Electrochemical Cells.Adv.Funct.Mater.31,1-9(2021).
disclosure of Invention
In order to overcome the problems in the background technology, the invention develops an air electrode of a proton ceramic electrochemical cell and a preparation method thereof. The air electrode material is obtained by impregnating an existing electrode framework with a ternary conductive oxide (capable of conducting protons, electrons and oxygen ions simultaneously), wherein the ternary conductive oxide has a chemical formula (PrNi x Co 1-x O 3-δ The method comprises the steps of carrying out a first treatment on the surface of the Wherein 0 is<x<1).
A method for preparing an air electrode of a proton ceramic electrochemical cell, comprising the following steps:
(1) The preparation of the impregnating solution comprises the following steps:
dissolving metal salt in solvent, and mixing the metal with PrNi according to stoichiometric ratio x Co 1-x O 3-δ Adding; subsequently adding a surfactant and a complexing agent, and stirring at room temperature until they form a uniform solution;
(2) Providing air electrode slurry which can be self-made or purchased externally;
(3) The preparation of the air electrode framework comprises the following steps:
coating the air electrode slurry in the last step on one side of a proton conducting electrolyte by using a screen printing method or a casting method, drying and sintering in a sintering furnace to obtain an air electrode framework, wherein the electrode framework material comprises LSC, LSF, LSCF, LSM, LSCF-GDC, LSCF-SDC and LSCF-BZCY;
(4) The impregnated air electrode skeleton comprises the following steps:
after obtaining the air electrode skeleton, stoichiometric PrNi is used x Co 1-x O 3-δ The impregnation is modified and subsequently dried on an oven/hotplate;
(5) Sintering to obtain the surface-modified electrode, which comprises the following steps:
impregnation of PrNi on air electrode skeleton x Co 1-x O 3-δ The cells were then sintered in a furnace at different temperatures.
Preferably, the metal in step (1) comprises praseodymium, nickel and cobalt, and the concentration of metal oxygen ions is 0.1mol L -1 ～0.2molL -1 。
Preferably, in the step (1), the solvent is deionized water or deionized water, ethanol or a mixture of deionized water and ethanol, wherein the ethanol accounts for 96-20% of the volume of the mixture of deionized water and ethanol.
Preferably, the PrNi in step (1) x Co 1-x O 3-δ The value of x: 0<x<1。
More preferably, the PrNi x Co 1-x O 3-δ The x value is between 0.45 and 0.75.
Preferably, the complexing agent in the step (1) is one or more of glycine, polyethylene glycol, citric acid, ethylenediamine tetraacetic acid and urea.
Preferably, the surfactant in step (1) is one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, and polyethylene oxide tert-octylphenyl ether.
Preferably, the sintering conditions in the sintering furnace in step (3): sintering in a sintering furnace at 900-1100 ℃ for 60-120 minutes.
Preferably, the PrNi in step (4) x Co 1-x O 3-δ Accounting for 1 to 10 percent of the framework mass, and drying the framework on an oven/hot plate for 2 to 15 minutes.
More preferably, the PrNi x Co 1-x O 3-δ Accounting for 2 to 5.5 percent of the mass of the framework.
Preferably, step (5) co-fires the cells in a furnace at different temperatures from 600 to 800 ℃ for 60 to 120 minutes.
Compared with the prior art, the invention has the following technical advantages:
(1) The novel air electrode material has ternary conductive PrNi x Co 1-x O 3-δ The impregnated air electrode material exhibits excellent ORR and OER catalytic activity at low temperatures (e.g., 400-700 ℃);
(2) The impregnating component may conduct protons, oxygen ions, and electrons simultaneously;
(3) The modified air electrode shows higher activity and durability under water vapor;
(4)PrNi x Co 1-x O 3-δ when used alone as an air electrode, the electrolyte is liable to be detached from the electrolyte when the battery is produced due to thermal expansion mismatch with the proton-conducting electrolyte. By impregnating PrNi x Co 1-x O 3-δ On the electrode framework, the method is simple and efficient, and can solve the problem of thermal expansion matching.
Drawings
FIG. 1 is PrNi 0.7 Co 0.3 O 3-δ Scanning Electron Microscopy (SEM) and elemental profile of air electrodes impregnated with LSCF.
FIG. 2 is a surface modified PrNi x Co 1-x O 3-δ The EIS spectra of the LSCF electrode at different temperatures (air atmosphere).
FIG. 3 is a surface modified PrNi x Co 1-x O 3-δ Is provided with a LSCF electrode containing 3%H at different temperatures 2 The EIS spectrum of O air uses BZTYYb as electrolyte material.
FIG. 4 untreated and PrNi 0.7 Co 0.3 O 3-δ Polarization resistance of the modified LSCF air electrode as a function of temperature and atmosphere (air, air containing 3% water vapor).
Detailed Description
In order to clarify the objects, technical solutions and advantages of the present invention, a detailed description of the present invention is provided below in connection with the following description. However, the described embodiments are only some embodiments, but not all embodiments, of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of an air electrode framework: lanthanum Strontium Cobalt Ferrite (LSCF) slurry is provided and coated on one side of proton conductor electrolyte (BZTYYb), after being dried for 180 minutes in an oven at 80 ℃, the slurry is moved into a high temperature furnace for sintering for 120 minutes at 1100 ℃, and the heating and cooling speed is 3 ℃/min.
Preparing an impregnating solution: according to stoichiometric ratio PrNi x Co 1-x O 3-δ (wherein x is 0.1,0.3,0.5,0.7,0.9 respectively) the following nitrates are weighed: nitrate praseodymium nitrate (Pr (NO) 3 ) 3 )、(Ni(NO 3 ) 2 .6H 2 O), cobalt nitrate (Co (NO) 3 ) 2 .6H 2 O) and adding water ethanol for dissolution (mass ratio water: ethanol=4:1), followed by glycine (complexing agent) and polyvinylpyrrolidone (PVP, surfactant). The concentration of metal salt ions in the impregnating solution was 0.1mol L -1 。
Preparation of surface-modified air electrode: the impregnation liquid prepared in the above way is adopted to be impregnated on the LSCF skeleton in a fractional manner, and the loading of the impregnated metal oxide is 3 percent (namely, the impregnated metal oxide accounts for the mass percent of the LSCF skeleton). After impregnation, it was co-fired in a box oven at 700 ℃ for 120 minutes.
The chemical names, structural formulas and using instructions of the materials are shown in the following table.
FIG. 1 shows PrNi 0.7 Co 0.3 O 3-δ Scanning Electron Microscopy (SEM) and elemental profile of air electrode of solution impregnated LSCF. PrNi was observed 0.7 Co 0.3 O 3-δ The LSCF air electrode was modified by dipping.
Electrochemical Impedance Spectroscopy (EIS) can obtain the polarization resistance of an air electrode. FIG. 2 shows impregnation of LSCF with PrNi by solution impregnation at different temperatures (in an air atmosphere of 25 ml/min) x Co 1-x O 3-δ (wherein PrNi 0.1 Co 0.9 O 3-δ ＝PNC-19，PrNi 0.3 Co 0.7 O 3-δ ＝PNC-37，PrNi 0.5 Co 0.5 O 3-δ ＝PNC-55，PrNi 0.7 Co 0.3 O 3-δ =pnc-73, prNi 0.9 Co 0.1 O 3-δ =pnc-91). PrNi of different compositions can be obtained by EIS test x Co 1-x O 3-δ To select R p The lowest best combination. As can be seen from EIS analysis, relative to other PrNi x Co 1-x O 3-δ Composition, prNi 0.7 Co 0.3 O 3-δ PNC-73 shows the lowest R p Values.
FIG. 3 shows surface modified PrNi x Co 1-x O 3-δ At different temperatures, contains 3% H 2 The EIS spectrum of O air uses BZTYYb as electrolyte material.
FIG. 4 shows untreated and PrNi 0.7 Co 0.3 O 3-δ Polarization resistance of the modified LSCF air electrode as a function of temperature and atmosphere (air, air containing 3% water vapor). PNC impregnated significantly improved the electrochemical performance of the electrode compared to untreated LSCF air electrode, while significantly improving its electrochemical performance in 3% water vapor air.
Claims (10)
1. An air electrode of a proton ceramic electrochemical cell and a preparation method thereof are characterized by comprising the following steps:
(1) The preparation of the impregnating solution comprises the following steps:
dissolving metal salt in solvent, and mixing the metal with PrNi according to stoichiometric ratio x Co 1-x O 3-δ Adding; subsequently adding a surfactant and a complexing agent, and stirring at room temperature until they form a uniform solution;
(2) Providing an air electrode paste;
(3) The preparation of the air electrode framework comprises the following steps:
coating the air electrode slurry in the previous step on one side of the proton conductive electrolyte by using a screen printing method or a tape casting method, drying and sintering in a sintering furnace to obtain an air electrode framework;
(4) The impregnated air electrode skeleton comprises the following steps:
after obtaining the air electrode skeleton, stoichiometric PrNi is used x Co 1-x O 3-δ The impregnation is modified and subsequently dried on an oven/hotplate;
(5) Sintering to obtain the surface-modified electrode, which comprises the following steps:
impregnation of PrNi on air electrode skeleton x Co 1-x O 3-δ The cells were then sintered in a furnace at different temperatures.
2. The method for preparing an air electrode for a proton ceramic electrochemical cell according to claim 1, wherein the metal in step (1) comprises praseodymium, nickel and cobalt, and the concentration of metal cations is 0.1mol -1 ～0.2molL -1 。
3. The method for preparing an air electrode of a proton ceramic electrochemical cell according to claim 1, wherein the solvent in the step (1) is deionized water, ethanol or a mixture of deionized water and ethanol, and the volume ratio of ethanol in the mixture of deionized water and ethanol is 96% -20%.
4. The method for preparing an air electrode for a proton ceramic electrochemical cell according to claim 1, wherein in step (1)The PrNi x Co 1-x O 3-δ The value of x: 0<x<1。
5. The method for preparing an air electrode of a proton ceramic electrochemical cell according to claim 1, wherein the complexing agent in the step (1) is one or more of glycine, polyethylene glycol, citric acid, ethylenediamine tetraacetic acid and urea.
6. The method for preparing an air electrode of a proton ceramic electrochemical cell according to claim 1, wherein the surfactant in the step (1) is one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide and polyethylene oxide tert-octylphenyl ether.
7. The method for preparing an air electrode for a proton ceramic electrochemical cell according to claim 1, wherein the conditions for sintering in a sintering furnace in step (3): sintering in a sintering furnace at 900-1100 ℃ for 60-120 minutes.
8. The method of preparing an air electrode for a proton ceramic electrochemical cell according to claim 1, wherein the PrNi in step (4) x Co 1-x O 3-δ Accounting for 1 to 10 percent of the framework mass, and drying the framework on an oven/hot plate for 2 to 15 minutes.
9. The method for preparing an air electrode for a proton ceramic electrochemical cell according to claim 1, wherein the step (5) is to co-fire the cell in a furnace at 600 to 800 ℃ for 60 to 120 minutes at different temperatures.
10. A proton ceramic electrochemical cell air electrode prepared according to the method of any one of claims 1 to 9.
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| CN202311504482.XA CN117577860A (en) | 2023-11-13 | 2023-11-13 | Proton ceramic electrochemical cell air electrode and preparation method thereof |
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