EP4559036A2 - A layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, a process for manufacturing and uses thereof - Google Patents

A layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, a process for manufacturing and uses thereof

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Publication number
EP4559036A2
EP4559036A2 EP23744741.2A EP23744741A EP4559036A2 EP 4559036 A2 EP4559036 A2 EP 4559036A2 EP 23744741 A EP23744741 A EP 23744741A EP 4559036 A2 EP4559036 A2 EP 4559036A2
Authority
EP
European Patent Office
Prior art keywords
doped
layered structure
electrolyte
single layer
thin single
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23744741.2A
Other languages
German (de)
French (fr)
Inventor
Albert TARANCÓN RUBIO
Federico BAIUTTI
Marc TORRELL FARO
Lucile BERNADET
Nerea ALAYO BUENO
Judith Driscoll
Matt Wells
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institucio Catalana de Recerca i Estudis Avancats ICREA
Fundacio Institut de Recerca en Energia de Catalunya
Cambridge Enterprise Ltd Ce
Cambridge Enterprise Ltd
Original Assignee
Institucio Catalana de Recerca i Estudis Avancats ICREA
Fundacio Institut de Recerca en Energia de Catalunya
Cambridge Enterprise Ltd Ce
Cambridge Enterprise Ltd
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Application filed by Institucio Catalana de Recerca i Estudis Avancats ICREA, Fundacio Institut de Recerca en Energia de Catalunya, Cambridge Enterprise Ltd Ce, Cambridge Enterprise Ltd filed Critical Institucio Catalana de Recerca i Estudis Avancats ICREA
Publication of EP4559036A2 publication Critical patent/EP4559036A2/en
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to electrochemical devices.
  • the present invention relates to a layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, a process for manufacturing said layered structure and uses thereof.
  • Electrodes for high-temperature energy conversion devices serve a number of purposes to allow the operation of the devices: catalysing the solid-gas reaction, allowing oxygen transport from and to the electrolyte, collecting electronic current parallel to the electrolyte, preventing cationic diffusion and consequent reaction between different layers.
  • typical electrodes for high- temperature energy conversion devices are made by different layers based on ceramic oxides: one barrier layer to prevent cationic diffusion, at least one functional layer for transporting current and catalysing solid-gas reactions.
  • US 20160156057 discloses oxygen ion conductive electrolyte membranes for use in applications such as solid oxide fuel cells.
  • Exemplary embodiments include an electrolyte membrane comprising a composite structure of first and second oxide ceramic materials, an oxygen ion conductive interface between the first and second materials extending from first to second opposing surfaces through a thickness of the membrane.
  • US2006/0234855 discloses a method for preparing an electrode for a solid oxide fuel cell, in which a conductive material, such as a metal, is electrodeposited onto a porous electrode comprising a conductive material and an electrolyte.
  • KR10-2264661 B1 discloses a solid oxide electrolyte including a thin film electrolyte layer having a multi-repeating structure.
  • the present inventors have developed a layered structure comprising a composite thin single layer deposited over a base electrolyte layer, wherein said composite thin single layer consists of an oxygen conducting and an electronic conducting material deposited at the same time by a physical or chemical deposition process, which composite thin single layer has a double functionality, as a barrier and as a functional electrode layer in SOC (solid oxide cell) devices.
  • SOC solid oxide cell
  • the present invention relates to a layered structure comprising or consisting of a composite thin single layer deposited over a base electrolyte layer in an electrochemical device.
  • the present invention relates to a process for manufacturing the layered structure according the first aspect of the invention.
  • the present invention relates to an electrochemical device comprising the layered structure according the first aspect of the invention.
  • the present invention relates to different uses of the layered structure according the first aspect of the invention.
  • Figure 1 SEM cross section of layered structure.
  • Figure 6 Sketch of full solid oxide cell comprising the layered structure.
  • the present invention relates to a layered structure comprising or consisting of a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, wherein said composite thin single layer consists of:
  • said composite thin single layer has a thickness between 10 nm and 10 .m, preferably between 10 nm and 1 .m, and wherein the total conductivity of said layer is between 1 S cnr 1 and 10000 S cnv 1 as measured in an in-plane configuration using Van der Pauw method and wherein the area-specific resistance of said layer is between 0.01 ohm cm -2 and 100 ohm cm -2 as measured by impedance spectroscopy in and out of plane configuration by applying an oscillating voltage between 10 mV and 100 mV, wherein the values for the total conductivity and the area-specific resistance are measured at a temperature range between 500 °C and 1000 °C and oxygen partial pressure >10 3 ppm.
  • Van der Pauw configuration (See for example L. J. van der Pauw, Philips Res. Rept., 13 (1958) 1 and A. Ramadan et al., Thin Solid Films 239 (1994), 272) in particular is used to determine the electrical resistance of a thin sheet of material. It utilizes a 4-probe geometry with the electrodes placed on the perimeter of the sample in the plane of the sample (in-plane configuration) and is based on applying a DC current between 2 adjacent contacts, with current flowing and measure the voltage drop between the 2 remaining contacts. The area-specific resistance is instead associated to electrochemical processes of oxygen exchange and diffusion.
  • the ionic conductor is selected from M- doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate, where M is a metal in the 3+ or 2+ oxidation state or a combination thereof, wherein M is preferably selected from La, Sm, Sc, Ca, Y and Gd.
  • the electronic conductor is selected from M-doped lanthanum manganite, ferrite, titanite and cobaltite or a combination thereof, wherein M is preferably Sr, Ba or Ca.
  • the electrolyte is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
  • the layered structure according to any of the embodiments for the first aspect further comprises an intermediate electrolyte layer between the base electrolyte layer and the composite thin single layer having a thickness between 10 nm and 10 .m and made of M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state
  • the present invention relates to a process for preparing a layered structure which comprises or consists of composite thin single layer deposited on top of an electrolyte according to any of embodiments or a combination thereof of the first aspect of the invention, comprising the steps of: a) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b) depositing via a laser ablation/evaporation/chemical reaction the composite thin single layer over the heated support obtained in step a).
  • step a) The temperature in step a) will be determined by the person skilled in the art depending on the deposition technique employed in step b).
  • the materials composing the electrode layers with the different purposes are deposited sequentially one after the other, in the present invention the materials composing the composite thin single layer are deposited at the same time.
  • the process according to the second aspect comprises the steps of: a1) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b1) depositing via a laser ablation/evaporation/chemical reaction the intermediate electrolyte layer over the heated support obtained in step a); and c1) depositing via a laser ablation/evaporation/chemical reaction the composite thin single layer over the intermediate electrolyte layer deposited in step b1).
  • step a1) The temperature in step a1) will be determined by the person skilled in the art depending on the deposition technique employed in step b1).
  • the process further comprises an annealing step over the composite thin single layer deposited on top of an electrolyte or over the intermediate electrolyte layer to be carried out after step b) or c1), respectively, at a temperature higher than 800 °C.
  • the electrolyte employed in step a) or step a1) is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
  • the ionic conductor employed in the composite thin single layer of step b) or step c1) is selected from M-doped zirconia, M- doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state, preferably wherein M is selected from La, Sm, Sc, Ca, Y and Gd.
  • the electronic conductor employed in the composite thin single layer of step b) or step c1) is selected from M 2+ -doped lanthanum manganite, ferrite and cobaltite or a combination thereof, preferably wherein M is Sr, Ba or Ca.
  • the present invention related to an electrochemical device comprising the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention.
  • said electrochemical device is a solid oxide fuel or electrolysis cell.
  • the present invention relates to the use of the composite thin single layer from the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention, for simultaneously: - protecting and isolating the cation diffusivity and reaction of the electrolyte (barrier layer) at high temperature;
  • the present invention relates to the use of the composite thin single layer from the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention, for increasing the efficiency and durability of the electrochemical device.
  • the invention determines a decrease in the current collection and increase of the electrochemical activity at the oxygen electrode, which are typically responsible for the main losses in solid oxide cell. Efficient ionic and electronic current distribution allow for increasing the durability of the device as the formation of high current and high oxygen pressure areas are prevented.
  • the full density of the layer obtained by laser ablation/evaporation/chemical reaction surprisingly efficiently blocks the migration of the ions between electrode and electrolyte.
  • Both layers are fabricated using pulsed laser deposition, by ablating ceramic pellets of the same stoichiometry as the deposited films, using a KrF excimer laser with energy fluency of around 1 J em -2 , substrate temperature 750 °C, target-substrate distance of 90 mm and chamber oxygen partial pressure of 0.7 Pa.
  • the substrate is a commercial 8 mol% Y2Os-doped ZrC>2 (YSZ) polycrystalline tape.
  • YSZ YSZ
  • a cathode layer of (Lao.6Sro.4)o.97Coo.2Feo.803 (LSCF) was deposited by a 3-axis automated airbrush using an ethanol-based dispersion ink.
  • the full structure was heat treated for co-sintering at 1000 °C. Sketch of the full cell is represented in Figure 2.
  • the area-specific resistance of the nanocomposite thin single layer (prepared with the method mentioned above) is reported.
  • the cell was composed by a YSZ electrolyte, the nanocompsite thin layer, a gold current collector and a low impedance counter-electrode made by porous Ag.
  • the real and imaginary part of the impedance are shown in axis X and Y, respectively.
  • the measurement was carried out by AC impedance spectroscopy, measuring the sample impedance across the cell and using voltage oscillations of 50 mV with varying frequency, from 1 MHz to 100 mHz.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device. The present invention further relates to a process for manufacturing said layered structure and uses thereof.

Description

A LAYERED STRUCTURE COMPRISING A COMPOSITE THIN SINGLE LAYER DEPOSITED OVER A BASE ELECTROLYTE LAYER FOR AN ELECTROCHEMICAL DEVICE, A PROCESS FOR MANUFACTURING AND USES THEREOF
Disclosure of agreement
This project has received funding from the European Union’s H2020 research and innovation programme under grant agreement number 101017709.
Field of the invention
The present invention relates to electrochemical devices. In particular, the present invention relates to a layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, a process for manufacturing said layered structure and uses thereof.
Background
Electrodes for high-temperature energy conversion devices (e.g. solid oxide cells) serve a number of purposes to allow the operation of the devices: catalysing the solid-gas reaction, allowing oxygen transport from and to the electrolyte, collecting electronic current parallel to the electrolyte, preventing cationic diffusion and consequent reaction between different layers. In order to fulfil these requirements, typical electrodes for high- temperature energy conversion devices are made by different layers based on ceramic oxides: one barrier layer to prevent cationic diffusion, at least one functional layer for transporting current and catalysing solid-gas reactions.
For example, US 20160156057 discloses oxygen ion conductive electrolyte membranes for use in applications such as solid oxide fuel cells. Exemplary embodiments include an electrolyte membrane comprising a composite structure of first and second oxide ceramic materials, an oxygen ion conductive interface between the first and second materials extending from first to second opposing surfaces through a thickness of the membrane. US2006/0234855 discloses a method for preparing an electrode for a solid oxide fuel cell, in which a conductive material, such as a metal, is electrodeposited onto a porous electrode comprising a conductive material and an electrolyte.
KR10-2264661 B1 discloses a solid oxide electrolyte including a thin film electrolyte layer having a multi-repeating structure.
In view of the above prior art, there is the need to develop one single layer capable of having both functionalities (barrier and functional layer) which indeed would make its manufacturing process simpler and the performance thereof would be improved. In this sense, the structure developed by the present inventors have the following technical advantages:
- the formation of local oxygen high pressure areas are prevented;
- the in-plane electronic conductivity for current collection is maximized;
- the lack of a well-defined current pathway leading to degradation due to high current density areas is overcome.
Accordingly, the present inventors have developed a layered structure comprising a composite thin single layer deposited over a base electrolyte layer, wherein said composite thin single layer consists of an oxygen conducting and an electronic conducting material deposited at the same time by a physical or chemical deposition process, which composite thin single layer has a double functionality, as a barrier and as a functional electrode layer in SOC (solid oxide cell) devices.
Summary of the invention
In a first aspect, the present invention relates to a layered structure comprising or consisting of a composite thin single layer deposited over a base electrolyte layer in an electrochemical device.
In a second aspect, the present invention relates to a process for manufacturing the layered structure according the first aspect of the invention.
In a third aspect, the present invention relates to an electrochemical device comprising the layered structure according the first aspect of the invention. In a fourth aspect, the present invention relates to different uses of the layered structure according the first aspect of the invention.
Brief description of the drawings
Figure 1 . SEM cross section of layered structure.
Figure 2. In-plane DC conductivity of the composite thin single layer.
Figure 3. Electrochemical impedance Nyquist plot indicating the area-specific resistance of the layered structure at 750 °C in air atmosphere.
Figure 4. Electrochemical impedance Nyquist plot indicating the area-specific resistance of the composite thin single layer at 750 °C in air atmosphere.
Figure 5. Current-voltage and current-power curves for a full cell with layered structure.
Figure 6. Sketch of full solid oxide cell comprising the layered structure.
Detailed description
In a first aspect, the present invention relates to a layered structure comprising or consisting of a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, wherein said composite thin single layer consists of:
- an ionic conductor; and
- an electronic conductor, and wherein said composite thin single layer has a thickness between 10 nm and 10 .m, preferably between 10 nm and 1 .m, and wherein the total conductivity of said layer is between 1 S cnr1 and 10000 S cnv1 as measured in an in-plane configuration using Van der Pauw method and wherein the area-specific resistance of said layer is between 0.01 ohm cm-2 and 100 ohm cm-2 as measured by impedance spectroscopy in and out of plane configuration by applying an oscillating voltage between 10 mV and 100 mV, wherein the values for the total conductivity and the area-specific resistance are measured at a temperature range between 500 °C and 1000 °C and oxygen partial pressure >103 ppm. Van der Pauw configuration (See for example L. J. van der Pauw, Philips Res. Rept., 13 (1958) 1 and A. Ramadan et al., Thin Solid Films 239 (1994), 272) in particular is used to determine the electrical resistance of a thin sheet of material. It utilizes a 4-probe geometry with the electrodes placed on the perimeter of the sample in the plane of the sample (in-plane configuration) and is based on applying a DC current between 2 adjacent contacts, with current flowing and measure the voltage drop between the 2 remaining contacts. The area-specific resistance is instead associated to electrochemical processes of oxygen exchange and diffusion. It is typically measured by AC impedance spectroscopy using an electrochemical cell comprising the measured layer (working electrode) and a counter electrode, separated by an oxygen ion electrolyte. The impedance response of the cell is measured by applying an oscillating voltage, in the range 10 mV-100 mV, between the working electrode and the counter electrode (out of plane configuration). By carrying out a frequency sweep (typically between 1 MHz to 0.1 Hz), the different electrode processes can be separated and the area-specific resistance of each electrode can be identified. The maximization of the inplane conductivity and minimization of the area-specific resistance are directly linked to low device power losses.
In a preferred embodiment of the first aspect, the ionic conductor is selected from M- doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate, where M is a metal in the 3+ or 2+ oxidation state or a combination thereof, wherein M is preferably selected from La, Sm, Sc, Ca, Y and Gd.
In a preferred embodiment of the first aspect, the electronic conductor is selected from M-doped lanthanum manganite, ferrite, titanite and cobaltite or a combination thereof, wherein M is preferably Sr, Ba or Ca.
In a preferred embodiment of the first aspect, the electrolyte is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
In another preferred embodiment, the layered structure according to any of the embodiments for the first aspect, further comprises an intermediate electrolyte layer between the base electrolyte layer and the composite thin single layer having a thickness between 10 nm and 10 .m and made of M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state In a second aspect, the present invention relates to a process for preparing a layered structure which comprises or consists of composite thin single layer deposited on top of an electrolyte according to any of embodiments or a combination thereof of the first aspect of the invention, comprising the steps of: a) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b) depositing via a laser ablation/evaporation/chemical reaction the composite thin single layer over the heated support obtained in step a).
The temperature in step a) will be determined by the person skilled in the art depending on the deposition technique employed in step b).
In contrast with prior art processes in which the materials composing the electrode layers with the different purposes are deposited sequentially one after the other, in the present invention the materials composing the composite thin single layer are deposited at the same time.
In the case the layered structure according to any of the embodiments for the first aspect, further comprises an intermediate electrolyte layer between the base electrolyte layer and the composite thin single layer, the process according to the second aspect comprises the steps of: a1) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b1) depositing via a laser ablation/evaporation/chemical reaction the intermediate electrolyte layer over the heated support obtained in step a); and c1) depositing via a laser ablation/evaporation/chemical reaction the composite thin single layer over the intermediate electrolyte layer deposited in step b1).
The temperature in step a1) will be determined by the person skilled in the art depending on the deposition technique employed in step b1).
In a preferred embodiment of the second aspect, the process further comprises an annealing step over the composite thin single layer deposited on top of an electrolyte or over the intermediate electrolyte layer to be carried out after step b) or c1), respectively, at a temperature higher than 800 °C. In a preferred embodiment of the second aspect, the electrolyte employed in step a) or step a1) is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
In a preferred embodiment of the second aspect, the ionic conductor employed in the composite thin single layer of step b) or step c1) is selected from M-doped zirconia, M- doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state, preferably wherein M is selected from La, Sm, Sc, Ca, Y and Gd.
In a preferred embodiment of the second aspect, the electronic conductor employed in the composite thin single layer of step b) or step c1) is selected from M2+-doped lanthanum manganite, ferrite and cobaltite or a combination thereof, preferably wherein M is Sr, Ba or Ca.
In a third aspect, the present invention related to an electrochemical device comprising the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention. In a preferred embodiment, said electrochemical device is a solid oxide fuel or electrolysis cell.
In a fourth aspect, the present invention relates to the use of the composite thin single layer from the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention, for simultaneously: - protecting and isolating the cation diffusivity and reaction of the electrolyte (barrier layer) at high temperature;
- for enhancing the catalytic activity for the oxygen reduction reaction or oxygen evolution reaction;
- collecting current.
In another embodiment, the present invention relates to the use of the composite thin single layer from the layered structure according to any of the embodiments or a combination thereof of the first aspect of the invention, for increasing the efficiency and durability of the electrochemical device. The invention determines a decrease in the current collection and increase of the electrochemical activity at the oxygen electrode, which are typically responsible for the main losses in solid oxide cell. Efficient ionic and electronic current distribution allow for increasing the durability of the device as the formation of high current and high oxygen pressure areas are prevented. Moreover, the full density of the layer obtained by laser ablation/evaporation/chemical reaction surprisingly efficiently blocks the migration of the ions between electrode and electrolyte.
The invention will be now illustrated by way of one or more examples which do not intend to limit the scope of the invention.
EXAMPLE
A layered structure is composed by the sequential deposition of an electrolyte layer thin film with composition Ceo.8Smo.2O2 (SDC in Figure 1), thickness =200 nm, and of a composite thin single layer of composition Ceo.8Smo.202+(Lao.8Sro.2)Mn03, 50:50 ratio, thickness =200 nm (LSM+SDC in Figure 1). Both layers are fabricated using pulsed laser deposition, by ablating ceramic pellets of the same stoichiometry as the deposited films, using a KrF excimer laser with energy fluency of around 1 J em-2, substrate temperature 750 °C, target-substrate distance of 90 mm and chamber oxygen partial pressure of 0.7 Pa. The substrate is a commercial 8 mol% Y2Os-doped ZrC>2 (YSZ) polycrystalline tape. On top of the layered structure, a cathode layer of (Lao.6Sro.4)o.97Coo.2Feo.803 (LSCF) was deposited by a 3-axis automated airbrush using an ethanol-based dispersion ink. The full structure was heat treated for co-sintering at 1000 °C. Sketch of the full cell is represented in Figure 2.
In Figure 2, the in-plane conductivity of the nanocomposite thin single layer is reported. The measurement was carried out by Van Der Pauw method. The measured conductivity is between 0.5 S*cnv1 and 2.5 S*cnr1 in the temperature range 100-320 °C and it increases with temperature.
In figure 3, the area-specific resistance of a symmetric cell with YSZ electrolyte and comprising the nanocomposite thin single layer+LSCF cathode (fabricated as in the methods) is reported. The real and imaginary part of the impedance are shown in axis X and Y, respectively. The measurement was carried out by AC impedance spectroscopy, measuring the sample impedance across the cell and using voltage oscillations of 50 mV with varying frequency, from 1 MHz to 100 mHz. The intercept of the plot with the X-axis (Z’=0.48 ohm*cm2, Z”=0 ohm*cm2) indicates the value of the area-specific resistance. Measurement conditions were T=750 °C, synthetic air atmosphere.
In figure 4, the area-specific resistance of the nanocomposite thin single layer (prepared with the method mentioned above) is reported. The cell was composed by a YSZ electrolyte, the nanocompsite thin layer, a gold current collector and a low impedance counter-electrode made by porous Ag. The real and imaginary part of the impedance are shown in axis X and Y, respectively. The measurement was carried out by AC impedance spectroscopy, measuring the sample impedance across the cell and using voltage oscillations of 50 mV with varying frequency, from 1 MHz to 100 mHz. The intercept of the plot with the X-axis (Z -7.1 ohm*cm2, Z”=0 ohm*cm2) indicates the value of the areaspecific resistance. Measurement conditions were T=750 °C, synthetic air atmosphere.
In Figure 5, the performance of a full cell comprising of the layered structure (as in the sketch in Figure 6) is reported. The measurement was carried out under dry H2 fuel in the anodic compartment and synthetic air and oxygen in the cathode with a flow density of 22.22 Nml min'1 cnr2. The curves are obtained by imposing the flow of DC current across the device (current sweep from 0 A*crrr2 to 1 A*crrr2) and measuring the potential drop. The device power density is then obtained as the product of potential and current. The obtained potential values are:
-current=0->potential 1.02 V
-current=1 A*cm-2->potential 0.61 V, power density 0.61 W*cnr2.

Claims

1. A layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, wherein said composite thin single layer consists of:
- an ionic conductor; and
- an electronic conductor, and wherein said composite thin single layer has a thickness between 10 nm and 1 .m, and wherein the total conductivity of said layer is between 1 S cnr1 and 10000 S cnv1 as measured in an in-plane configuration using Van der Pauw method and wherein the area-specific resistance of said layer is between 0.01 ohm cnr2 and 100 ohm cnr2 as measured by impedance spectroscopy in and out of plane configuration by applying an oscillating voltage between 10 mV and 100 mV, wherein the values for the total conductivity and the area-specific resistance are measured at a temperature range between 500 °C and 1000 °C and oxygen partial pressure >103 ppm.
2. The layered structure according to claim 1 , wherein the ionic conductor is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
3. The layered structure according to claim 2, wherein M is selected from La, Sm, Sc, Ca, Y and Gd.
4. The layered structure according to any of claims 1 to 3, wherein the electronic conductor is selected from M-doped lanthanum manganite, ferrite, titanite and cobaltite or a combination thereof, preferably wherein M is Sr, Ba or Ca.
5. The layered structure according to any of claims 1 to 4, wherein the electrolyte is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate, where M is a metal in the 3+ or 2+ oxidation state.
6. The layered structure according to any of claims 1 to 5 further comprising an intermediate electrolyte layer between the base electrolyte layer and the composite thin single layer having a thickness between 10 nm and 10 and made of M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
7. A process for preparing a layered structure which comprises a composite thin single layer deposited on top of an electrolyte according to any of claims 1 to 6, comprising the steps of: a) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b) depositing via a laser ablation/evaporation/chemical reaction the composite thin single layer over the heated support obtained in step a).
8. The process for preparing a layered structure which comprises a composite thin single layer deposited on top of an electrolyte further comprising an intermediate electrolyte layer between the base electrolyte layer and the composite thin single layer comprising the steps of: a1) heating an electrolyte as a support at a temperature between room temperature and 950 °C; b1) depositing via a laser ablation/evaporation chemical reaction the intermediate electrolyte layer over the heated support obtained in step a); and c1) depositing via a laser ablation/evaporation the composite thin single layer over the intermediate electrolyte layer deposited in step b1).
9. The process according to claim 7 or 8, wherein an annealing step over the composite thin single layer deposited on top of an electrolyte or over the intermediate electrolyte layer is carried out after step b) or c1), respectively, at a temperature higher than 800 °C.
10. The process according to any of claims 7 to 9, wherein the ionic conductor is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state, wherein M is preferably selected from La, Sm, Sc, Ca, Y and Gd.
11 . The process according to any of claims 7 to 10, wherein the electronic conductor is selected from M2+-doped lanthanum manganite, ferrite and cobaltite or a combination thereof, preferably wherein M is Sr, Ba or Ca.
12. The process according to any of claims 7 to 11 , wherein the electrolyte is selected from M-doped zirconia, M-doped ceria, M-doped barium zirconate, M-doped barium cerate or a combination thereof, where M is a metal in the 3+ or 2+ oxidation state.
13. An electrochemical device comprising the layered structure according to any of claims 1 to 6.
14. The electrochemical device according to claim 13, which is a solid oxide fuel or electrolysis cell.
15. Use of the composite thin single layer from the layered structure according to any of claims 1 to 6, for simultaneously: - protecting and isolating the cation diffusivity and reaction of the electrolyte (barrier layer) at high temperature;
- for enhancing the catalytic activity for the oxygen reduction reaction or oxygen evolution reaction;
- collecting current.
EP23744741.2A 2022-07-19 2023-07-19 A layered structure comprising a composite thin single layer deposited over a base electrolyte layer for an electrochemical device, a process for manufacturing and uses thereof Pending EP4559036A2 (en)

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