INTERLAYER FOR SOLID OXIDE CELL

Abstract

A method of forming an interlayer of a solid oxide cell unit on the surface of a substrate may include: providing a base interlayer solution comprising a solution of a soluble salt precursor of a metal oxide (crystalline) ceramic and crystalline nanoparticles, depositing the base interlayer solution onto the surface of the substrate, drying the base interlayer solution to define a nanocomposite sub-layer of the soluble salt precursor and nanoparticles, heating the sub-layer to decompose it and form a film of metal oxide comprising nanoparticles on the surface, and firing the substrate with the film on the metal surface, to form a nanocomposite crystalline layer.

Claims

1. A method for depositing a ceramic film of a solid oxide cell unit upon a ceramic or metallic surface of a substrate, the method comprising the steps of: i. providing a base suspension comprising a solution of a soluble salt precursor of a crystalline metal oxide ceramic and further comprising crystalline nanoparticles suspended in the base suspension; ii. depositing the base suspension on the surface of the substrate; iii. drying the base suspension to define a nanocomposite sub-layer of the soluble salt precursor and nanoparticles; iv. heating the sub-layer to decompose it and form a film of metal oxide comprising nanoparticles on the surface of the substrate; v. firing the substrate with the film on the surface, to form a nanocomposite crystalline layer as a deposited ceramic film.

2. The method of claim 1, wherein at step iv, the film so formed from the sub-layer has a minimum thickness of 130 nm.

3. The method of claim 1, further comprising: vi. Repeating steps ii. to iv. at least one additional time before the step v of firing, the base suspension being deposited onto the sub-layer, such that the film of metal oxide comprising nanoparticles is formed from a plurality of sub-layers.

4. The method of claim 3, wherein at step iv, the film so formed from each sub-layer has a thickness of at least 130 nm.

5. The method of claim 1, wherein the nanoparticles comprise doped zirconia nanoparticles, doped zirconium (IV) dioxide nanoparticles, 8YSZ or 10Sc1YSZ nanoparticles, or the nanoparticles are yttria stabilized.

6-8. (canceled)

9. The method of claim 1, wherein the nanoparticles exhibit ionic conductivity.

10. The method of claim 1, wherein crystalline nanoparticles are dispersions in an aqueous solvent, and step i. further comprises the sub-step of: a. solvent exchange of the nanoparticles into a non-aqueous media comprising the nanoparticles in suspension.

11. The method of claim 1, wherein crystalline nanoparticles are dispersions in non-aqueous solvent.

12. The method of claim 1, wherein the heating step involves heating the sub-layer to a temperature of between 150 and 600° C.

13. The method of claim 1, wherein the firing at step v. is at a temperature of between 500 and 1100° C.

14. The method of claim 1, wherein the surface of the substrate is an electrolyte layer, a mixed ionic electronic conducting electrolyte material, or a CGO electrolyte layer.

15-16. (canceled)

17. The method of claim 1, wherein said metal oxide crystalline ceramic is selected from the group consisting of: doped stabilized zirconia and rare earth oxide doped ceria, or wherein said metal oxide crystalline ceramic is selected from the group consisting of: scandia stabilized zirconia (ScSZ), yttria stabilized zirconia (YSZ), scandia ceria co-stabilized zirconia (ScCeSZ), scandia yttria co-stabilized zirconia (ScYSZ), ytterbia stabilized zirconia (YbSZ) samarium-doped ceria (SDC), gadolinium-doped ceria (GDC), praseodymium doped ceria (PDC), and samaria-gadolinia doped ceria (SGDC).

18. (canceled)

19. The method of claim 1, wherein said soluble salt precursor is selected from at least one of the group consisting of: zirconium acetylacetonate, scandium nitrate, [[and ]]yttrium nitrate, cerium nitrate, ytterbium nitrate, cerium acetylacetonate, and gadolinium nitrate.

20. The method of claim 1, wherein the solvent for said soluble salt precursor is selected from at least one of the group consisting of: methanol, ethanol, propanol, methoxypropanol, ethyl acetate, acetic acid, acetone, and butyl carbitol.

21. The method of claim 1, further comprising prior to step iii the step of allowing said suspension deposited onto said surface to stand for a period of at least 5 seconds.

22. The method of claim 1, being a method of forming an at least one layer of an air separation device electrolyte.

23. A surface of a substrate having deposited upon it at least one layer of metal oxide crystalline ceramic comprising nanoparticles according to the process of claim 1.

24. An electrolyte material comprising an oxide material formed from a colloidal dispersion having electrolyte material, a dispersion of nanoparticles, and a liquid continuous phase; wherein the dispersion was deposited as one or more sub-layer films each sub-layer film dried to form a nanocomposite sub-layer, heated to decompose the nanocomposite sub-layer, and fired to form an electrolyte material of nanocomposite crystalline layer.

25. The method of claim 1, wherein the deposited ceramic film comprises a sub-micron thickness ceramic film.

26. The method of claim 1, wherein the deposited ceramic film comprises an interlayer of an electrolyte material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0035] FIG. 1 depicts an illustrative solid oxide cell layer structure obtained using methods of the present disclosure.

[0036] FIG. 2a is a high-magnification top-down SEM image of an interlayer obtained using methods of the present disclosure.

[0037] FIG. 2b is a high-magnification cross-sectional SEM image of an interlayer obtained using methods of the present disclosure.

DETAILED DESCRIPTION

[0038] The present disclosure provides a method for forming an interlayer of a solid oxide cell unit upon a surface of a substrate, the method including the steps of: Providing a base interlayer solution comprising a solution of a soluble salt precursor of a metal oxide (crystalline) ceramic and crystalline nanoparticles; Depositing the base interlayer solution on the surface of the substrate; Drying the base interlayer solution to define a nanocomposite sub-layer of the soluble salt precursor and nanoparticles; Heating the sub-layer to decompose it and form a film of metal oxide comprising nanoparticles on the surface; Firing the substrate with the film on the metal surface, to form a nanocomposite crystalline layer.

[0039] The solid oxide cell unit may be a cell unit of a SOFC or a SOEC. In a solid oxide cell (SOFC or SOEC), the use of a nanocomposite approach to fabricate a thin film of dense doped-zirconia on top of a CGO electrolyte by deposition of a solution of metal salts combined with a dispersion of electrochemically active or passive nanoparticles. Once dry, this forms a nanocomposite layer consisting of crystalline nanoparticles surrounded by amorphous organometallic matrix.

[0040] The film may be converted to a film of metal oxide by heat treatment to decompose the salts. The presence of nanoparticles provides reinforcement to the organometallic matrix, especially during the heat treatment to distribute the shrinkage-induced stresses that lead to cracking. Presence of the nanoparticles also reduces the amount of organic matter that needs to be removed in the heat treatment, thus reducing shrinkage-induced stresses that lead to cracking. The matrix provides a percolating network to enable ionic conductivity through the layer. Preferably, the nanoparticles will also exhibit ionic conductivity.

[0041] The surface of the substrate may be selected from the group consisting of: a metallic surface and a ceramic surface. Thus, the base interlayer solution may be deposited on the metal surface (which may be the metal support in a metal supported SOFC or SOEC) or on the ceramic surface (which may be the electrolyte of a SOFC or SOEC) by, for example, spraying, spin-coating, dip-coating, or ink-jet printing, and allowed to dry to form a thin film. The resulting nanocomposite layer may be thermally decomposed into an amorphous mixed oxide by thermal decomposition, this may be by use of an infrared heater. The process may be repeated sufficient times to build up a layer of, for example, approximately 600 nm, and then the layer may be heat treated in a furnace at 500-1100° C. to convert it to a crystalline layer of 10Sc1YSZ or 8YSZ. The whole process may be repeated to obtain a final film thickness of, for example, 1200 nm.

[0042] The base interlayer solution may comprise a solution of a soluble salt precursor of a metal oxide (crystalline) ceramic and crystalline nanoparticles at 5-30 mol %.

[0043] In an aspect, there is provided a method for forming an interlayer of a solid oxide cell unit upon a surface of a substrate. The method may include steps of: i. Providing a base interlayer solution comprising a solution of a soluble salt precursor of a metal oxide (crystalline) ceramic and crystalline nanoparticles at 5-30 mol %; ii. Depositing the base interlayer solution on the surface of the substrate, the surface optionally being selected from the group consisting of: a metallic surface and a ceramic surface; iii. Drying the base interlayer solution to define a nanocomposite sub-layer of the soluble salt precursor and nanoparticles; iv. Heating the sub-layer to a temperature of between 150 and 600° C., to decompose it and form a film of metal oxide comprising nanoparticles on the surface; v. Firing the substrate with the film on the metal surface at a temperature of 500 to 1100° C., to form a nanocomposite crystalline layer. In this way, the final nanocomposite layer may be composed of 5-30% nanoparticles by volume of the fired film.

[0044] The film so formed at step iv from the sub-layer may have a minimum thickness of 130 nm. Due to the inherent nature of the nanocomposite, it is capable of yielding a thicker sub-layer in a single pass, so that the resulting final nanocomposite crystalline layer can be produced with a smaller number of passes.

[0045] Steps of depositing, drying, and heating. may be repeated at least one additional time before the step of firing, the base interlayer solution being deposited onto the sub-layer, such that the film of metal oxide comprising nanoparticles is formed from a plurality of sub-layers

[0046] At the step of heating, the film so formed from each sub-layer may have a thickness of at least 130 nm, preferably within the range of 150 to 500 nm, more preferably 150 to 200 nm, even more preferably 175 to 200 nm. In an example, the thickness of each sub-layer in the film has a thickness of 200-300 nm.

[0047] The nanoparticles may comprise doped zirconia nanoparticles. In an example, the nanoparticles doped zirconium (IV) dioxide nanoparticles. In an example, the nanoparticles are yttria stabilized. In an example, the nanoparticles are 8YSZ or 10Sc1YSZ nanoparticles.

[0048] In the case that the nanoparticles are YSZ/yttria stabilized zirconia ((ZrO.sub.2).sub.1-x(Y.sub.2O.sub.3).sub.x), Stabilization of zirconium dioxide nanoparticles with yttria improves the microstructure of the sintered layer by encouraging cation mobility and enhancing sintering. YSZ, can offer the benefits of enabling thicker layers to be deposited while simultaneously offering ionic conductivity.

[0049] The nanoparticles may be spherical with an average diameter of between 1 and 100 nm. In an example, they may have an average diameter of between 1 and 10 nm, preferably between 3 and 6 nm, more preferably between 3 and 5 nm. In another example the nanoparticles may have average diameter of between 1 and 50 nm, between 50 and 150 nm or between 100 and 150 nm.

[0050] In an example, the nanoparticles exhibit ionic conductivity. In an example the crystalline nanoparticles are dispersions in an aqueous solvent, and step of providing further comprises the sub-step of: solvent exchange of the nanoparticles into a non-aqueous media comprising the nanoparticles in suspension.

[0051] Solvent exchange describes process of changing the environment of the nanoparticle. This may involve the steps of, starting with nanoparticle in isopropanol or water, step 1: addition of ethylene glycol to the nanoparticle solution, a condensation reaction occurs to form water and a gel, an alternative to ethylene glycol is dipropylene glycol. During the condensation reaction, heat may be applied. The gel traps the nanoparticle in a structure which limits agglomeration and maintains particle size. Step 2: addition of acetic acid to reduce viscosity of the gel. Step 3: form a dispersion using EtOH (80%) and 1-methoxy-2-propanol, MEP (20%) and a binder, such that the nanoparticles are 5% by weight of resulting solution. This dispersion is stirred on hotplate. The binder may be polyvinyl butyral, for example Butvar® B-76. Polyvinyl butyral is a thermoplastic, resin that offers a combination of properties for coating or adhesive applications. The use or addition of polyvinyl butyral to a system imparts adhesion, toughness, and flexibility. Other suitable potential binders include polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG). In general any polymer system which is soluble in the solvents used and burns out cleanly without residue during heat treatment may be used.

[0052] In an example, the crystalline nanoparticles are dispersions in a non-aqueous solvent. In an example, the heating step involves heating the sub-layer to a temperature of between 150 and 600° C.

[0053] In an example, the firing at step v. is at a temperature of between 500 and 1100° C. In an example, the firing at step v. may be between 750 and 850° C., in another example the firing at step v. may be at around 800° C.

[0054] In an example, the nanocomposite crystalline layer may be at least 90% dense. The nanocomposite crystalline layer may be at least 95% dense. The nanocomposite crystalline layer may be at least 97% dense.

[0055] In an example, the surface of the substrate is an electrolyte layer. In an example, the surface is a mixed ionic electronic conducting electrolyte material. In an example, the surface is a CGO electrolyte layer.

[0056] In an example, the metal oxide crystalline ceramic is selected from the group consisting of: doped stabilized zirconia, and rare earth oxide doped ceria.

[0057] In an example, the metal oxide crystalline ceramic is selected from the group consisting of: scandia stabilized zirconia (ScSZ), yttria stabilized zirconia (YSZ), scandia ceria co-stabilized zirconia (ScCeSZ), scandia yttria co-stabilized zirconia (ScYSZ), ytterbia stabilized zirconia (YbSZ) samarium-doped ceria (SDC), gadolinium-doped ceria (GDC), praseodymium doped ceria (PDC), and samaria-gadolinia doped ceria (SGDC).

[0058] In an example, the soluble salt precursor is selected from at least one of the group consisting of: zirconium acetylacetonate, scandium nitrate, and yttrium nitrate, cerium nitrate, ytterbium nitrate, cerium acetylacetonate and gadolinium nitrate.

[0059] In an example, the solvent for said soluble salt precursor is selected from at least one of the group consisting of: methanol, ethanol, propanol, methoxypropanol, ethyl acetate, acetic acid, acetone and butyl carbitol.

[0060] In an example, the prior to step iii the step of allowing said solution deposited onto said surface to stand for a period of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60 seconds.

[0061] In an example, the method of forming an at least one layer of an air separation device electrolyte.

[0062] In an example, having deposited upon it at least one layer of metal oxide crystalline ceramic comprising nanoparticles according to the process of any of claims 1-21.

[0063] These and other features of the present disclosure will now be described in further detail, by way of various embodiments, and just by way of example, with reference to the accompanying drawings (which drawings are not to scale, and in which the height dimensions are generally exaggerated for clarity), in which:

[0064] FIG. 1 shows an example solid oxide cell layer structure that can be achieved with the method of the present disclosure.

[0065] FIG. 2a is a high magnification top down SEM image of an interlayer and FIG. 2b is a high magnification cross sectional SEM image of an interlayer achieved with the method of the present disclosure.

[0066] A ferritic stainless steel foil substrate 202 (as shown in e.g. FIG. 1) defining a perforated region 201 surrounded by a non-perforated region is provided upon which has been deposited an anode layer 210 and a gas impermeable, dense, CGO electrolyte layer 220 which is 10-15 micron thick on top of the anode layer, as taught in GB2434691 (foil substrate 4, anode layer 1 a and electrolyte layer 1e) and WO 02/35628. In other embodiments (not shown) perforated foil substrates upon which is deposited an anode layer and a gas impermeable, dense electrolyte layer are used (GB2440038, GB2386126, GB2368450, U.S. Pat. No. 7,261,969, EP1353394, and U.S. Pat. No. 7,045,243). In a further embodiment (not shown) the graded metal substrate of US20070269701 is used.

[0067] The results of the method detailed above are shown in the following figures. FIG. 1 illustrates position of an interlayer in a metal-supported electrochemical cell, suitable for use as a SOFC or SOEC.

[0068] A nanocomposite crystalline layer comprising nanoparticles, is then formed on top of the CGO layer by performing steps (a)-(f) below. The interlayer 250 may also comprise crystalline ceramic scandia yttria co-stabilized zirconia (10Sc1YSZ; (Sc.sub.2O.sub.3).sub.0.1(Y.sub.2O.sub.3).sub.0.01(ZrO.sub.2).sub.0.89) The addition of 1% Yttria stabilizes the material in the desired cubic fluorite crystal structure and helps avoid the crystallite phase instability which can occur in the ScSZ system, particularly a tendency to form rhombohedral crystals at around 500° C. which have much lower oxygen ion conductivity that cubic ones.

[0069] The steps may be:

[0070] (a) air atomized spraying, jetting or ink-jet printing of a layer of base interlayer solution. The base interlayer solution being of 0.1 M cation concentration solution of Sc(NO.sub.3).sub.3 and Y(NO.sub.3).sub.3 and Zr(C.sub.5H.sub.7O.sub.2) in 90% volume ethanol and 10% volume methoxypropanol (soluble salt precursors which will form the scandia yttria co-stabilized zirconia), and comprising 8YSZ or 10Sc1YSZ nanoparticles such that the final crystallized layer comprises 5-30% 8YSZ or 10Sc1YSZ nanoparticles by volume, at RTP onto the CGO layer. The base interlayer solution may comprise a solution of a soluble salt precursor of a metal oxide (crystalline) ceramic and crystalline nanoparticles at 5-30 mol %.

[0071] (b) drying the base interlayer solution at RTP in air for 60 seconds during which period the soluble salt precursor and nanoparticles even out across the surface, followed by further drying at 100° C. for 30 seconds. In an alternative, the step of drying may be undertaken at a slightly elevated temperature (e.g., 30-50° C.) but for longer than 30 seconds.

[0072] (c) heating the base interlayer solution to >500° C. over a total period of 60 seconds using an infra-red (IR) heating lamp which decomposes and semi-crystallizes the base soluble salt precursor it to form a layer about 200-400 nm thick of a semi-crystalline scandia yttria co-stabilized zirconia film comprising 8YSZ or 10Sc1YSZ nanoparticles.

[0073] (d) optionally repeating steps (a)-(c), the substrate and metal oxide film being cooled to a temperature of 35-80° C. prior to each repeat of step (a), to give a metal oxide and semi-crystalline film having a total thickness of about 500-600 nm. This film does not have any cracks in it and is suitable for further processing.

[0074] (e) firing at 800° C. for 60 minutes in air, the metal oxide film of scandia yttria co-stabilized zirconia forms a fully crystalline ceramic layer 250 of scandia yttria co-stabilized zirconia comprising nanoparticles, having a thickness of about 400-600 nm.

[0075] (f) optionally repeating steps (a)-(e) once more to achieve a final layer thickness of about 800-1200 nm

[0076] The next steps may be: (g) the repeating of steps (a)-(e) once more but this time depositing a layer 260 of CGO on top of the previously deposited crystalline ceramic layer of scandia yttria co-stabilized zirconia comprising nanoparticles. Example specific conditions are: 0.1 M cation concentration Ce(C.sub.5H.sub.7O.sub.2) and gadolinium nitrate in 70% volume ethanol and 30% volume methoxypropanol and spraying, depositing and processing as before but using a final crystallization firing temperature of 980° C. to achieve a CGO layer with a final thickness of around 250 nm. This layer acts as a barrier layer between the scandia yttria co-stabilized zirconia layer and a subsequently deposited cathode layer 270.

[0077] (h) finally, a cathode layer 270 is then deposited on top of the previously deposited interlayer 250 or CGO layer 260. This may be done by screen-printing an LSCF cathode and processing it in accordance with WO2006/079800. This layer may have a thickness of about 50 μm.

[0078] The method may be used to manufacture the cell unit of FIG. 1. The cell unit may be a SOFC or SOEC. In FIG. 1 there is provided a ferritic stainless steel metal substrate 200 with an anode layer 210 on top of it and an electrolyte layer 220 are provided. Electrolyte layer 220 surrounds anode layer 210 in order to prevent gas flowing through anode 210 between fuel side 230 and oxidant side 240. Interlayer comprising nanoparticles (i.e. a nanocomposite interlayer) 250 is then deposited on top of ceramic CGO layer 220. The interlayer comprising nanoparticles may be Scandia yttria co-stabilized zirconia crystalline ceramic layer with yttria stabilized zirconia (YSZ) or 10Sc1YSZ nanoparticles. CGO crystalline ceramic layer 260 may then be deposited on top of interlayer 250. The spraying steps used in the deposition of layers 250 and 260 results in a “layer cake” type structure. Subsequent to the deposition of layers 250 and 260, the cell unit is completed with the addition of cathode assembly 270. If the cell unit is operated as a SOFC, the 240 represents the oxidant side and 230 represents the fuel side.

[0079] The nanoparticles may be 8YSZ or 10Sc1YSZ nanoparticles having average particle size, as measured by TEM, of 1-10 nm. The nanoparticles are generally spherical, but need not be, the size quoted is the characteristic diameter of the particles. The nanoparticles may be 3-5 nm in size. Equally, they may be 3-6 nm, 1-10 nm, 1-50 nm, or 50-150 nm in size. Nanoparticles may, for example, be 8YSZ or 10Sc1YSZ particles formed by solvothermal processing supplied as a dispersion in isopropanol, which can be added directly to the interlayer salt solution to form a solution for deposition.

[0080] In other possible examples the nanoparticles could be 8YSZ or 10Sc1YSZ particles made by hydrothermal synthesis supplied in an acidified aqueous suspension. In this case it is necessary to perform a solvent exchange to transfer the particles to an organic solvent system before mixing them with the interlayer salt solution for deposition.

[0081] There are a number of possible methods for achieving a solvent exchange, but one of the simplest ones is to add a low-volatility polar solvent such as ethylene glycol or propylene glycol to the aqueous suspension and then heat the suspension to drive off the water, leaving the nanoparticles suspended in a gel with the glycol. The resulting gel can then be dispersed into the interlayer salt solution using high energy ultrasound before deposition.

[0082] Thus, the deposition method allows: [0083] deposition of 200-400 nm thickness interlayers in a single pass free of cracks and no obvious porosity. [0084] Starting from an already crystalline material (the nanoparticles) reduces the shrinkage/stress therefore reduce chances of cracking.

[0085] It is known that nanoparticles can be hard to densify especially at lower temperatures however the method results in a layer of higher density than prior art technique.

[0086] Comparison, by SEM, of an interlayer formed in accordance with the disclosure using just 4 passes (each sublayer being around 200 nm thick after firing given that total interlayer is 800 nm after firing) with interlayers formed using a prior art technique show pores (which are voids in the interlayer) . Many more pores are evident using the prior art technique. Thus, because of the pores, the prior art interlayers are of lower density than the interlayer formed with the method of the present disclosure. A dense interlayer is desired to improve the gas-impermeability of the electrolyte and interlayer, to prevent mixing of gasses on either side of the solid oxide cell. For example, in the case of a SOFC and with reference to FIG. 1, a high density interlayer prevents mixing of oxidant 240 with fuel 230.

[0087] FIG. 2 shows an interlayer achieved using the present disclosure. FIG. 2a shows top down image of the interlayer. FIG. 2a appears to show many dimples. However these are only apparent at very high magnification. FIG. 2b is the same interlayer in cross section. FIG. 2b demonstrates that the dimples are constrained to the surface and do not penetrate through the layer. Nanoporosity was observed, however, the pores are closed. This film has a film thickness of 750 nm, achieved by a single pass (ie only one sublayer forms the interlayer). There are no cracks or defects that penetrated through the layer exposing the electrolyte.

[0088] These and other features of the present disclosure have been described above purely by way of example. Modifications in detail may be made to the disclosure within the scope of the claims.