Patent Application
20160322663
The present invention is generally directed to fuel cell components, and to solid oxide fuel cell electrolyte materials in particular.
Fuel cells are electrochemical devices which can convert energy stored in fuels to electrical energy with high efficiencies. Electrolyzer cells are electrochemical devices which can use electrical energy to reduce a given material, such as water, to generate a fuel, such as hydrogen. The fuel and electrolyzer cells may comprise reversible cells which operate in both fuel cell and electrolysis mode.
In a high temperature fuel cell system, such as a solid oxide fuel cell (SOFC) system, an oxidizing flow is passed through the cathode side of the fuel cell while a fuel flow is passed through the anode side of the fuel cell. The oxidizing flow is typically air, while the fuel flow can be a hydrocarbon fuel, such as methane, natural gas, pentane, ethanol, or methanol. The fuel cell, operating at a typical temperature between 650° C. and 950° C., enables the transport of negatively charged oxygen ions from the cathode flow stream to the anode flow stream, where the ion combines with either free hydrogen or hydrogen in a hydrocarbon molecule to form water vapor and/or with carbon monoxide to form carbon dioxide. The excess electrons from the negatively charged ion are routed back to the cathode side of the fuel cell through an electrical circuit completed between anode and cathode, resulting in an electrical current flow through the circuit. A solid oxide reversible fuel cell (SORFC) system generates electrical energy and reactant product (i.e., oxidized fuel) from fuel and oxidizer in a fuel cell or discharge mode and generates the fuel and oxidant using electrical energy in an electrolysis or charge mode.
Scandia stabilized zirconia (SSZ) SOFC electrolyte material exhibits a high oxygen ion conductivity. Typically, zirconia is doped with between 8 and 11 mol % scandia (Sc2O3) in order to stabilize the cubic phase zirconia at high SOFC operating temperature of 650-850° C.
However, there are two problems with SSZ electrolyte materials: 1) they exhibit a cubic to rhombohedral phase transformation at around 580° C., and 2) the ionic conductivity slowly decreases with time, which is known as ageing.
Others have shown that co-doping SSZ with one secondary rare earth oxide will suppress the cubic to rhombohedral phase transformation. For example, 10ScCe zirconia (10 mol % Sc2O3—1 mol % CeO2—zirconia) and 10Sc1Y (1 mol % Sc2O3—1 mol % Y2O3—zirconia) are examples of co-doped zirconia compositions that do not exhibit the cubic to rhombohedral phase transformation.
However, both of these zirconia compositions still experience ageing (i.e., the a slow decrease in ionic conductivity with time at the SOFC operating temperatures of 800-850 C). Although the actual mechanism of this ageing degradation in ionic conductivity with time is not agreed upon in the scientific literature, one hypothesis is that the cubic phase is not stable and slowly decomposes into a tetragonal phase which has a lower ionic conductivity. The resulting material consists of a two-phase mixture primarily of cubic phase with small domains (e.g., 2-5 nm) of tetragonal phase. As shown in
One embodiment of the invention provides an electrolyte and/or electrode composition for a solid oxide fuel cell which includes zirconia stabilized with (i) scandia, (ii) ceria, and (iii) at least one of yttria and ytterbia. Preferably, the at least one of yttria and ytterbia is present in an amount greater than 0 and equal to or less than 2.5 mol %.
Another embodiment of the invention provides a scandia stabilized zirconia electrolyte composition for a solid oxide fuel cell, comprising a formula (ZrO2)1-w-x-z(Sc2O3)w(CeO2)x(Y2O3)a(Yb2O3)b, where 0.09≦w≦0.11; 0<x≦0.025; a+b=z; 0≦z≦0.025; and x+z≧0.02. Another embodiment of the invention provides a scandia stabilized zirconia electrolyte composition for a solid oxide fuel cell, comprising a formula (ZrO2)1-w-x-z(Sc2O3)w(CeO2)x(Y2O3)a(Yb2O3)b, where 0.09≦w≦0.11; 0≦x≦0.0125; a+b=z, and 0.0025≦z≦0.02; and x+z≦0.02.
Another embodiment of the invention provides a method of operating a solid oxide fuel cell comprising a zirconia electrolyte stabilized with scandia and ceria. The method comprises operating the solid oxide fuel cell for at least 4000 hrs such that an electrolyte of the fuel cell does not experience a degradation of ionic conductivity of greater than 15%.
Without wishing to be bound by a particular theory, the present inventors believe that the 10Sc1Ce composition is slightly under-doped and is not fully stable (i.e., not sufficiently stabilized), and thus is prone to ageing due to the slow cubic to tetragonal phase decomposition or transformation at high temperature.
According to a first embodiment of the invention, the SSZ composition contains at least 2 molar percent of the additional stabilizing oxide (such as ceria, yttria and/or ytterbia) to provide sufficient stabilization to the SSZ composition to reduce or prevent the ageing decomposition. The stabilizing oxide provides the stabilization of the cubic phase of SSZ and thus the suppression of the cubic to tetragonal phase transformation. According to a second embodiment, both ceria and at least one of yttria and ytterbia are added to the SSZ composition to reduce or prevent the ageing decomposition. The addition of both ceria and at least one of yttria and ytterbia provides the stabilization of the cubic phase of SSZ and thus the suppression of the cubic to tetragonal phase transformation. One exemplary composition of these embodiments is zirconia has been co-doped with at least two additional elements: 10Sc1Ce1Y (10 mol % Sc2O3—1 mol % CeO2—1 mol % Y2O3—zirconia). According to a third embodiment, the SSZ composition has a coefficient of thermal expansion (“CTE”) close to that of interconnects which will be used in a fuel cell stack with the SSZ electrolyte SOFCs. The interconnects may comprise chromium alloy interconnects having at least 94 wt % Cr, 4-6 wt % Fe and 0-1 wt % Y. In a first aspect of the third embodiment, the SSZ composition contains greater than zero but less than 2 mol % total of ceria, yttria and/or ytterbia, such as 1-2 mol % total of ceria and at least one of yttria and/or ytterbia. By slightly reducing the amount of at least one of ceria, yttria and/or ytterbia, the CTE of the electrolyte is increased such that it differs from the CTE of the interconnect by 10% or less, such as 5% or less, such as 0-1%, without decreasing the stability or ageing degradation resistance of the electrolyte. In a second aspect of the third embodiment, the yttria is replaced with ytterbia. It is believed that replacing yttria with ytterbia should increase the CTE and ion conductivity of the electrolyte material. Thus, the electrolyte compositions of the third embodiment are believed to exhibit improved beginning of life ionic conductivity, low degradation and higher CTE that is the same as or slightly different from a CTE of a Cr alloy interconnect. A decrease in difference in CTE between SOFC electrolytes and interconnects in a SOFC stack should result in decreased thermally induced stress and damage to the stack components. Preferably, the electrolyte composition of all three embodiments is homogeneous throughout its height, width and thickness rather than being a heterogeneous composite of yttria and scandia stabilized zirconias made by mixing of yttria and scandia stabilized zirconia powders.
Accordingly, the first embodiment of the invention provides a SOFC electrolyte composition which comprises zirconia stabilized with (i) scandia, (ii) ceria, and (iii) at least one of yttria and ytterbia. Scandia may be present in an amount equal to 9 to 11 mol %, such as 10 mol %, ceria may present in amount greater than 0 (e.g., at least 0.5 mol %) and equal to or less than 2.5 mol %, such as 1 mol %, and at least one of yttria and ytterbia may be present in an amount greater than 0 and equal to or less than 2.5 mol %, such as 1 mol %.
In one aspect of the first embodiment, the at least one of yttria and ytterbia comprises yttria. In another aspect of the first embodiment, the at least one of yttria and ytterbia comprises ytterbia. In yet another aspect of the first embodiment, the at least one of yttria and ytterbia comprises both yttria and ytterbia. In this aspect, yttria may comprise 0.5 to 1.5 mol % and ytterbia may comprise 1.5 to 0.5 mol % of the composition such that the total yttria and ytterbia content is greater than 0.5 mol % and less than 2.5 mol %. The amount of scandia is greater than the amount of ceria and the amount of the at least one of yttria and ytterbia. The amount of ceria may be equal to, less than or greater than the amount of the at least one of yttria and ytterbia.
In the second embodiment of the present invention, the amount of stabilizing oxide, such as ceria, is at least 2 mol % to provide sufficient stabilization to the SSZ composition to reduce or avoid ageing. In this embodiment, the yttria and/or ytterbia is optionally added to the composition and may be omitted.
Thus, the SSZ electrolyte composition of both the first and the second embodiment may have the formula (1):
(ZrO2)1-w-x-z(Sc2O3)w(CeO2)x(Y2O3)a(Yb2O3)b (1),
where w is from about 0.09 to 0.11, x is from greater than 0 to 0.025, the total of a and b equal to z, and z is from 0 to 0.025, and the total of x plus z is greater than or equal to 0.02. In other words, 0.09≦w≦0.11; 0<x≦0.025; a+b=z, and 0≦z≦0.025; and x+z≧0.02. Preferably, x ranges from 0.005 to 0.025, z ranges from 0.005 to 0.025, and the total of x and z is greater than or equal to 0.02 and less than or equal to 0.03. In other words, 0.005≦x≦0.025; 0.005≦z≦0.025; and 0.02≦(x+z)≦0.03. More preferably, w=0.1; x=0.01; and z=0.01. Thus, w may be about 10 mol %, x may be about 1 mol %, and z may be about 1 mol %. In formula (1), b may be less than a (i.e., b<a), a may be less than b (i.e., a<b), a may be equal to zero (i.e. a=0), b may be equal to zero (i.e., b=0), or a may be equal to b (i.e., a=b)
According to the third embodiment, the SSZ composition has a relatively higher coefficient of thermal expansion (“CTE”) close to that of interconnects which will be used in a fuel cell stack with the SSZ electrolyte SOFCs. The interconnects may comprise chromium alloy interconnects having at least 94 wt % Cr, 4-6 wt % Fe and 0-1 wt % Y. In a first aspect of the third embodiment, the SSZ composition contains greater than zero but less than 2 mol % total of ceria and at least one of yttria and/or ytterbia. For example, the SSZ composition contains 0.5 to 1.75 mol % total, such as 0.5 to 1.5 mol % total, including 1 to 1.5 mol % total of ceria and at least one of yttria and/or ytterbia. The SSZ composition may contain 0.25 to 1.25 mol % ceria, such as 0.5 to 1 mol % ceria, and 0.25 to 1.25 mol %, such as 0.5 to 1 mol % of yttria, ytterbia or a combination of yttria and ytterbia. In a second aspect of the third embodiment, the yttria is replaced with ytterbia such that the composition contains substantially no yttria (e.g., an unavoidable trace amount of yttria or less than 0.1 mol % yttria). It is believed that replacing yttria with ytterbia should increase the CTE and ion conductivity of the electrolyte material. The SSZ composition may contain 0 to 1.25 mol % ceria, such as 0.5 to 1 mol % ceria, and 0.25 to 2 mol %, such as 0.5 to 1 mol % of ytterbia. The SSZ composition may contain substantially no ceria (e.g., an unavoidable trace amount of ceria or less than 0.1 mol % ceria) if the composition contains at least 0.75 mol % ytterbia, such as 1 to 2 mol % ytterbia, including 1 to 1.5 mol % ytterbia. Thus, in the second aspect of the third embodiment, the electrolyte composition for a solid oxide fuel cell includes zirconia stabilized with: (i) scandia present in an amount equal to 9 to 11 mol %, and (ii) ytterbia present in an amount equal to 1 to 2 mol %.
Thus, the SSZ electrolyte composition of the third embodiment may have the formula (2):
(ZrO2)1-w-x-z(Sc2O3)w(CeO2)x(Y2O3)a(Yb2O3)b (2),
where w is from about 0.09 to 0.11, x is from 0 to 0.0125, a is from 0 to 0.0125, b is from 0 to 0.02, the total of a and b equal to z, and z is from 0.0025 to 0.02, and the total of x plus z is less than or equal to 0.02. In other words, 0.09≦w≦0.11; 0≦x≦0.0125; a+b=z, and 0.0025≦z≦0.02; and x+z≦0.02. Preferably, in the first aspect of the third embodiment, x ranges from 0.0025 to 0.0125, such as 0.005 to 0.01, z ranges from 0.0025 to 0.0125, such as 0.005 to 0.01, and the total of x and z is greater than or equal to 0.005 and less than or equal to 0.0175, such as greater than or equal to 0.01 and less than or equal to 0.015. In other words, 0.0025≦x≦0.0125, such as 0.005≦x≦0.01; 0.0025≦z≦0.0125, such as 0.005≦z≦0.01, and 0.005≦(x+z)≦0.0175, such as 0.01≦(x +z)≦0.015. More preferably, w=0.1; x=0.01 when z=0.005, and x =0.005 when z =0.01. Thus, w may be about 10 mol %, x may be about 0.5 to 1 mol %, and z may be about 0.5 to 1 mol %. Preferably in the second aspect of the third embodiment, x ranges from 0 to 0.0125, such as 0.005 to 0.01, 0≦a≦0.001 (preferably a=0), and b and z range from 0.0025 to 0.02, such as 0.005 to 0.01, and the total of x and z is greater than or equal to 0.005 and less than or equal to 0.02, such as 0.01 to 0.015. In formula (2), b may be less than a (i.e., b<a), a may be less than b (i.e., a<b), a may be equal to zero (i.e. a=0), b may be equal to zero (i.e., b=0), or a may be equal to b (i.e., a=b). Preferably, only one of a or b equals zero. Exemplary compositions according to the third embodiment include: 10Sc1Ce1Y (10 mol % Sc2O3+1 mol % CeO2+1 mol % Y2O3), remainder zirconia; 10Sc1Ce0.5Y (10 mol % Sc2O3+1 mol % CeO2+0.5 mol % Y2O3), remainder zirconia; 10Sc1Ce1Yb (10 mol % Sc2O3+1 mol % CeO2+1 mol % Yb2O3), remainder zirconia; 10Sc1Ce0.5Yb (10 mol % Sc2O3+1 mol % CeO2+0.5 mol % Yb2O3), remainder zirconia; 10Sc0.5Ce0.5Y (10 mol % Sc2O3+0.5 mol % CeO2+0.5 mol % Y2O3), remainder zirconia; 10Sc0.5Ce0.5Yb (10 mol % Sc2O3+0.5 mol % CeO2+0.5 mol % Yb2O3), remainder zirconia; 10Sc0.5Ce1Y (10 mol % Sc2O3+0.5 mol % CeO2+1 mol % Y2O3), remainder zirconia; 10Sc0.5Ce1Yb (10 mol % Sc2O3+0.5 mol % CeO2+1 mol % Yb2O3), remainder zirconia; and 10Sc1Yb (10 mol % Sc2O3+1 mol % Yb2O3), remainder zirconia.
Embodiments of the electrolyte compositions have a high starting ionic conductivity of 0.14 S/cm or greater, preferably 0.15 S/cm or greater, such as 0.16 to 0.17 S/cm. The compositions of the present invention may experience less than 15% degradation in ionic conductivity with time, such as 0-15%, for example 0-10%, including 1-5%, in an air and/or in a H2 containing environment after 4000 hours. Such minimization in ionic conductivity degradation may be due to stabilization of the cubic phase leading to suppression of the cubic to tetragonal phase transformation. Additionally, at least one of the embodiments of the present invention provides an electrolyte composition wherein the composition does not experience a cubic to rhombohedral phase transition at a temperature of about 25 to 850° C. In other words, the composition is cubic from room temperature to about 850° C. (i.e., the composition remains in the cubic phase from room to the SOFC operating temperature without generating tetragonal domains over time or transforming to the rhombohedral phase). Therefore, compositions of the present invention do not experience a degradation of ionic conductivity of greater than 15% after 4000 hrs and at a temperature of 850° C.
For example, as shown in
The embodiments of the present invention may be utilized as an electrolyte layer of a planar solid oxide fuel cell. In other words, the composition can be utilized as an electrolyte layer of a planar solid oxide fuel cell comprising an anode and a cathode. Preferably, the composition is used in an electrolyte supported cell where the electrolyte layer supports the anode and cathode. For example,
A method of forming the planar, electrolyte supported SOFC 1 shown in
As shown in
In another embodiment of the invention, the composition of the first, second and/or third embodiment comprising a zirconia stabilized with scandia, ceria, and at least one of yttria and ytterbia may be used in an anode electrode, a cathode electrode, or both electrodes of the solid oxide fuel cell. Thus, the composition of the first, second and third embodiments may be used in any one, two or all three of the SOFC anode, cathode and electrolyte. In the composite anode and/or cathode electrodes, the stabilized zirconia of the first, second or third embodiments is used as the solid oxide ionic conducting phase, while an electrically conductive material, such as a metal (e.g., nickel, copper, cobalt, platinum, palladium, etc. or their alloys) or an electrically conductive ceramic (e.g., lanthanum strontium manganite (LSM), lanthanum strontium cobaltite (La,Sr)CoO3, lanthanum strontium cobalt ferrite (La,Sr)(Co,Fe)O3, etc.,) is used as the electrically conducting phase. The degradation of ionic conductivity in the solid oxide ionic conducting phase of a composite electrode, such as the anode or cathode, will result in a degradation of the performance of the electrode. Therefore, composite electrodes containing a solid oxide ionic conducting phase with low ionic conductivity degradation, such as 10Sc1Ce1Y, will exhibit lower degradation as compared to composite electrodes containing a ceramic material having a higher degradation rate.
For example, the zirconia stabilized with scandia, ceria, and at least one of yttria and ytterbia may be used in a single layer or a multi-layer composite anode electrode. For example, the zirconia stabilized with scandia, ceria, and at least one of yttria and ytterbia may be used in the first portion 13 and/or the second portion 23 of the anode electrode 3 described above. The first portion 13 of the anode electrode may contain nickel and the stabilized zirconia ceramic phase. The second portion 23 of the anode electrode may also contain nickel and the stabilized zirconia ceramic phase. The first portion 13 may contain a lower ratio of the nickel containing phase to the ceramic phase than the second portion 23 of the anode electrode. For example, the first portion 13 of the anode electrode may contain a porosity of 5-30 volume percent and a nickel phase content of 1 to 20 volume percent and remainder the stabilized zirconia ceramic phase. The second portion 23 of the anode electrode may contain a higher porosity of 31 to 60 volume percent, a nickel phase content of 21 to 60 volume percent and remainder the stabilized zirconia ceramic phase. The nickel containing phase may optionally contain between 1 and 50 atomic percent, such as 5-30 at % of an additional metal, such as cobalt and/or copper, and the balance nickel.
In another example, the cathode electrode 7 may comprise a composite cathode containing the electrically conductive phase, such as an electrically conductive perovskite material (e.g., LSM) of 10 to 70 volume percent and remainder porosity and the stabilized zirconia ionically conductive phase.
In another embodiment of the present invention, a method of operating a solid oxide fuel cell, for example, the fuel cell 1 of
Fuel cell stacks are frequently built from a multiplicity of SOFC's 1 in the form of planar elements, tubes, or other geometries. Fuel and air has to be provided to the electrochemically active surface, which can be large. The stack may comprise a plurality of planar or plate shaped fuel cells. The fuel cells may have other configurations, such as tubular. The stacks may be vertically oriented stacks or the fuel cells may be stacked horizontally or in any other suitable direction between vertical and horizontal. A plurality of interconnects are located in the stack, such that each fuel cell is located between two interconnects, and each interconnect acts as a gas separator plate, as described in the above mentioned U.S. application Ser. Nos. 11/907,204 and 11/785,034.
Frequently, the interconnect 9 which electrically connects the fuel electrode 3 of one cell to the air electrode 7 of the adjacent cell is also used as the gas flow separator plate 9, as shown in
The term “fuel cell stack,” as used herein, means a plurality of stacked fuel cells which share a common fuel inlet and exhaust passages or risers. The “fuel cell stack,” as used herein, includes a distinct electrical entity which contains two end plates which are connected to power conditioning equipment and the power (i.e., electricity) output of the stack. Thus, in some configurations, the electrical power output from such a distinct electrical entity may be separately controlled from other stacks. The term “fuel cell stack” as used herein, also includes a part of the distinct electrical entity. For example, the stacks may share the same end plates. In this case, the stacks jointly comprise a distinct electrical entity, such as a column. In this case, the electrical power output from both stacks cannot be separately controlled.
The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents.
This application is a continuation of U.S. application Ser. No. 14/055,557, filed Oct. 16, 2013, which is a continuation of U.S. application Ser. No. 13/009,085, filed Jan. 19, 2011, now U.S. Pat. No. 8,580,456, which claims the benefit of U.S. Provisional Application No. 61/298,468, filed Jan. 26, 2010, which are all incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61298468 | Jan 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14055557 | Oct 2013 | US |
| Child | 15205852 | US | |
| Parent | 13009085 | Jan 2011 | US |
| Child | 14055557 | US |
