Degradation Mechanisms of Metal-Supported Solid Oxide Cells and Countermeasures: A Review
<p>Schematic diagram of the structure and operating principle of SOFCs and SOECs. (<b>a</b>) SOFC mode with an oxide-conducting and proton-conducting electrolyte, respectively; (<b>b</b>) SOEC mode. An energy conversion efficiency of 50–60% can be achieved in SOFC mode [<a href="#B1-materials-14-03139" class="html-bibr">1</a>] and 90% in SOEC mode [<a href="#B8-materials-14-03139" class="html-bibr">8</a>].</p> "> Figure 2
<p>Schematic diagram of the development of SOFCs [<a href="#B9-materials-14-03139" class="html-bibr">9</a>,<a href="#B22-materials-14-03139" class="html-bibr">22</a>]. Note the thinner electrolyte allows a lower operating temperature, and the low operating temperature allows the use of metal supports.</p> "> Figure 3
<p>(<b>a</b>) Diagram of MSCs stack’s structure, reproduced with permission from Ref. [<a href="#B35-materials-14-03139" class="html-bibr">35</a>]; (<b>b</b>) 1 kW MSCs stack manufactured by Ceres Power, reproduced with permission from Ref. [<a href="#B36-materials-14-03139" class="html-bibr">36</a>].</p> "> Figure 4
<p>Two-dimensional slices from a spatially registered sub-dataset at identical locations in the electrode in the pristine (<b>a</b>), annealed for 3 h (<b>b</b>) and 8 h (<b>c</b>) states. Three different grey levels are present: black (pore), grey (YSZ), and white (nickel). (<b>d</b>) The nickel particle morphology at the same position before and after the annealing (in dry hydrogen at 850 °C). Reproduced with permission from Ref. [<a href="#B40-materials-14-03139" class="html-bibr">40</a>].</p> "> Figure 5
<p>(<b>a</b>) Operation of tubular metal-supported SOFCs at 700 °C with moist hydrogen fuel and oxygen as oxidant. Dashed line: as-infiltrated Ni anode, 300 m Acm<sup>−2</sup>; solid line: Ni anode was pre-coarsened at 800 °C, 100 mA cm<sup>−2</sup>, reproduced with permission from Ref. [<a href="#B23-materials-14-03139" class="html-bibr">23</a>]. (<b>b</b>) X-ray diffraction patterns for SDCN<sub>40</sub> anode catalyst upon reduction at 700 °C for 1 h (black) and after 100 h of thermal annealing at 700 °C in 3% humidified hydrogen (blue). (<b>c</b>) SDCN40 catalyst anode via thermal annealing at 700 °C and continuous electrochemical operation at 0.7 V for 100 h (corresponding to (<b>b</b>)). (<b>b</b>,<b>c</b>) are reproduced with permission from Ref. [<a href="#B52-materials-14-03139" class="html-bibr">52</a>].</p> "> Figure 6
<p>Schematic of the diffusion barrier layer method in metal-supported cells, reproduced with permission from Ref. [<a href="#B57-materials-14-03139" class="html-bibr">57</a>].</p> "> Figure 7
<p>(<b>a</b>) SEM image showing the polished cross-section of the planar metal-supported half-cell. The electrolyte is shown at the top, followed by the cermet layer and the metal support, reproduced with permission from Ref. [<a href="#B65-materials-14-03139" class="html-bibr">65</a>]. (<b>b</b>) Schematic diagram of the loss of conductivity of the metal support due to oxidation adapted from Ref. [<a href="#B9-materials-14-03139" class="html-bibr">9</a>]. (<b>c</b>) Cross-sectional SEM images of the metal support with a grown outer oxide layer in darker grey at different exposure times at 800 °C and 50%H<sub>2</sub>-50%H<sub>2</sub>O fuel atmospheres, reproduced with permission from Ref. [<a href="#B90-materials-14-03139" class="html-bibr">90</a>].</p> "> Figure 8
<p>SEM image of porous ITM support after La acetate coating with the. indication of area (<b>a</b>) thick and area (<b>b</b>) thin LaCrO<sub>3</sub>-coating, reproduced with permission from Ref. [<a href="#B95-materials-14-03139" class="html-bibr">95</a>].</p> "> Figure 9
<p>(<b>a</b>) Schematic representation of the mechanism of metal dusting corrosion of nickel, adapted from Ref. [<a href="#B43-materials-14-03139" class="html-bibr">43</a>]. (<b>b</b>) The interface between the Ni particle (lower part) and the YSZ electrolyte (upper part) close to the gas inlet area of the cell and (<b>c</b>) showing the carbon nanofibers and nanoparticles at the Ni-YSZ|YSZ interface, reproduced with permission from Ref. [<a href="#B96-materials-14-03139" class="html-bibr">96</a>].</p> "> Figure 10
<p>(<b>a</b>) Schematic diagram of the degradation mechanism caused by H<sub>2</sub>S poisoning reproduced with permission from Ref. [<a href="#B102-materials-14-03139" class="html-bibr">102</a>]. (<b>b</b>) Sulfur poisoning and regeneration or desulphurization processes of Ni-YSZ anodes in a fuel mixture with 50 ppm H<sub>2</sub>S, reproduced with permission from Ref. [<a href="#B101-materials-14-03139" class="html-bibr">101</a>].</p> "> Figure 11
<p>(<b>a</b>) Schematic illustration of the protonic ceramic fuel cell (PCFC) and mechanism of hydrocarbon reforming, water-gas shift reaction, sulfur cleaning, and carbon cleaning; (<b>b</b>) Mechanism of carbon cleaning. C<sub>ad</sub> indicates carbon absorbed on the surface of Ni. Reproduced with permission from Ref. [<a href="#B50-materials-14-03139" class="html-bibr">50</a>]. (<b>c</b>) Ionic conductivities of BZCYYb, BZCY, GDC, and YSZ measured at 400 to 750 °C in wet oxygen (with ~3 vol % H<sub>2</sub>O). (<b>d</b>) Typical current-voltage characteristics and the corresponding power densities measured at 750 °C for a cell with a configuration of Ni-BZCYYb|BZCYYb|BZCY-LSCF when ambient air was used as oxidant and hydrogen as fuel (with or without 20 ppm H<sub>2</sub>S contamination), and for another cell with a configuration of Ni-BZCYYb|SDC|LSCF when dry propane was used as fuel. Reproduced with permission from Ref. [<a href="#B51-materials-14-03139" class="html-bibr">51</a>]. Note BZY: BaZr<sub>0.9</sub>Y<sub>0.1</sub>O<sub>3−δ</sub>; BZCY: Ba(Zr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.2</sub>)O<sub>3−δ</sub>; BZCYYb: BaZr<sub>0.1</sub>Ce<sub>0.7</sub>Y<sub>0.1</sub>Yb<sub>0.1</sub>O<sub>3−δ</sub>.</p> "> Figure 12
<p>Candidate materials for MSCs, adapted from Ref. [<a href="#B9-materials-14-03139" class="html-bibr">9</a>]. Lanthanum strontium manganite (LSM); Lanthanum nickel ferrite (LNF); Lanthanum strontium cobalt ferrite (LSCF); Strontium samarium cobaltite (SSC); Lanthanum Strontium Cobaltite (LSC); Scandia-ceria-stabilized zirconia (SCSZ); Lanthanum strontium gallium magnesium oxide (LSGM).</p> "> Figure 13
<p>(<b>a</b>) Structure diagram of the MSC with infiltrated electrodes. (<b>b</b>) SEM micrographs of the cross-section of the MSC showing the “metal-support/SCSZ backbone/SCSZ dense electrolyte/SCSZ backbone/metal-support” symmetric structure. (<b>c</b>) Cross-section of porous backbones and dense electrolyte. (<b>d</b>) Hydrogen electrode catalyst (Ni-SDC) infiltrated on SCSZ backbone (<b>e</b>) Oxygen electrode catalyst (Pr<sub>6</sub>O<sub>11</sub>) infiltrated on SCSZ backbone. Reproduced with permission from Ref. [<a href="#B118-materials-14-03139" class="html-bibr">118</a>].</p> "> Figure 14
<p>(<b>a</b>) Powder X-ray diffraction on PrOx cathode catalyst calcined at 600 °C (black) and after thermal annealing at 700 °C (blue) in the air for 100 h; (<b>b</b>) Impact of in situ catalyst pre-coarsening. MS-SOFC durability at 700 °C and 0.7 V before and after in situ catalyst pre-coarsening at 750 °C for 4 h; (<b>c</b>) Cr transport at the cathode side of a SOFC; (<b>d</b>) Bars represent quantified power retention (percentage of remaining power density after 100 h of operation vs. the beginning of life) observed for the post-sintering fabrication processes, individually and combined. Each process is associated with different colours and marking. Experimental results from whole cells are overlaid (blue stars). (<b>e</b>) Long-term durability for baseline and improved cell (after the cathode pre-coarsening, metal support pre-oxide, and ALD process) at 700 °C and 0.7 V. (<b>a</b>,<b>b</b>,<b>d</b>,<b>e</b>) were reproduced with permission from Ref. [<a href="#B52-materials-14-03139" class="html-bibr">52</a>]; (<b>c</b>) was adapted with permission from Ref. [<a href="#B116-materials-14-03139" class="html-bibr">116</a>].</p> "> Figure 15
<p>Images of TF-MSC. (<b>a</b>) structure diagram; (<b>b</b>) morphology and size; (<b>c</b>–<b>e</b>) Microstructure of the corresponding positions in (<b>a</b>). Reproduced with permission from Ref. [<a href="#B19-materials-14-03139" class="html-bibr">19</a>].</p> "> Figure 16
<p>(<b>A</b>). Low-tortuosity gas channels have higher gas diffusion efficiency, adapted from Ref. [<a href="#B81-materials-14-03139" class="html-bibr">81</a>]; (<b>B</b>). Gradient-porosity anodes facilitate electrochemical reactions, resulting in a higher power density, reproduced with permission from Ref. [<a href="#B152-materials-14-03139" class="html-bibr">152</a>]; (<b>C</b>). Regular-shaped and -distributed pores avoid the formation of small necks, increasing the lifetime of MSCs.</p> ">
Abstract
:1. Introduction
2. Degradation Mechanism and Countermeasures
2.1. The Degradation of the Anode
2.1.1. Coarsening and Migration of Nickel
2.1.2. Metal Support Issues
2.1.3. Carbon Deposition and Sulfur Poisoning
2.2. The Degradation of the Cathode
- (1)
- (2)
- (3)
- (4)
- (5)
3. The Degradation of Cell Stacks
4. Thin-Film Electrolyte Metal-Supported SOCs and Issues
5. R&D Opportunities and Recommendations
6. Conclusions
- (a)
- The use of infiltrated anode completely avoids the coarsening during the co-sintering.
- (b)
- The application of DBL removes the limitation of the use of ferritic stainless-steel supports, and replacing nickel supports with ferritic stainless steels results in improved oxidation resistance and improved compatibility with ceramics.
- (c)
- The use of thin-film electrolytes reduces the operating temperature to below 600 °C.
- (d)
- The cermet anodes such as nano Ni/CGO and Ni/SDC are designed to suppress the nano-nickel coarsening, which improves the stability of infiltrated anodes during the operation.
- (e)
- Proton conductors such as BZY, BZCY, and BZCYYb are highly resistant to chromium and sulfur poisoning, which are promising to be used in MSCs.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Metal | CTE (ppm/K) | Relative Oxidation Resistance |
---|---|---|
Ni | 16.5 | Poor |
Ni-Fe (1:1) | 13.7 | Poor |
400-series stainless steel | 10–12 | Good |
Family | Candidate | Representative Composition | Survives Sintering in Reducing Atmosphere? | Survives Re-Oxidation? | React with Metal? | Densifies at 1450 °C or Lower? | Evaporation during Sintering? |
---|---|---|---|---|---|---|---|
Pyrochlore | LCZ | La1.95Ca0.05Zr2O7 | No | No | - | - | - |
LCO | La2Ce2O7 | No | Yes | Yes-Cr, Si | - | - | |
Perovskite | BCN | Ba3Ca1.18Nb1.82O9 | Yes | Yes | Yes-Cr, Si | Falls apart | Yes |
BZCY | BaZr0.7Ce0.2Y0.1O3 | Yes | Yes | Yes-Cr, Si | Marginal | Yes | |
SZCY | SrZr0.5Ce0.4Y0.1O3 | Yes | Yes | Yes-Si | Yes | Yes | |
Acceptor doped rare-earth Orthoniobate | LCN | La0.99Ca0.01NbO4 | Yes | Yes | No | Yes | No |
Interconnects | Coating | Testing Conditions | KP (g2 cm−4 s−1) | ASR (mΩ) | Year/Ref. |
---|---|---|---|---|---|
SUS430 | Mn-Co/PVD | 800 °C/air/1250 h | 1.22 × 10−14 | 28.6 | 2019/[91] |
Crofer22APU | MnCo1.7Fe0.3O4/APS | 700 °C/air/1000 h | No data | 50 | 2014/[136] |
Crofer22APU | MnCo1.7Fe0.3O4/EPD | 800 °C/air/5000 h | 0.34 × 10−14 | No data | 2017/[145] |
Sanergy HT | (Mn,Co)3O4/Screen priting | 800 °C/air/1500 h | 2 × 10−14 | No data | 2011/[146] |
AISI 430 | Mn-Co/DGPA | 800 °C/air | 0.25 × 10−14 (750 h) | 29 (408 h) | 2019/[147] |
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Zhou, Z.; Nadimpalli, V.K.; Pedersen, D.B.; Esposito, V. Degradation Mechanisms of Metal-Supported Solid Oxide Cells and Countermeasures: A Review. Materials 2021, 14, 3139. https://doi.org/10.3390/ma14113139
Zhou Z, Nadimpalli VK, Pedersen DB, Esposito V. Degradation Mechanisms of Metal-Supported Solid Oxide Cells and Countermeasures: A Review. Materials. 2021; 14(11):3139. https://doi.org/10.3390/ma14113139
Chicago/Turabian StyleZhou, Zhipeng, Venkata Karthik Nadimpalli, David Bue Pedersen, and Vincenzo Esposito. 2021. "Degradation Mechanisms of Metal-Supported Solid Oxide Cells and Countermeasures: A Review" Materials 14, no. 11: 3139. https://doi.org/10.3390/ma14113139