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1. Advanced oxygen-electrode-supported solid oxide electrochemical cells with Sr(Ti,Fe)O 3−δ -based fuel electrodes for electricity generation and hydrogen production

   https://doi.org/10.1039/d0ta06678h  

   Zhang, Shan-Lin ; Wang, Hongqian ; Yang, Tianrang ; Lu, Matthew Y. ; Li, Cheng-Xin ; Li, Chang-Jiu ; Barnett, Scott A. ( December 2020 , Journal of Materials Chemistry A)

   null (Ed.)

   Sr(Ti 0.3 Fe 0.7 )O 3−δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3−δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3−δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3−δ –Zr 0.92 Y 0.16 O 2−δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3−δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm −2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than the same cell made with a Ni-YSZ electrode. Electrolysis current density as high as −1.72 A cm −2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. The STF fuel electrodes also provide good stability during redox cycling. 

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2. Enhancement of Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 fuel electrode performance by infiltration of Ce 0.8 Gd 0.2 O 2−δ nanoparticles

   https://doi.org/10.1039/c9ta12316d  

   Park, Beom-Kyeong ; Scipioni, Roberto ; Cox, Dalton ; Barnett, Scott A. ( February 2020 , Journal of Materials Chemistry A)

   This paper addresses the use of Ce 0.8 Gd 0.2 O 2−δ (GDC) infiltration into the Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 (YSZ) fuel electrode of solid oxide cells (SOCs) for improving their electrochemical performance in fuel cell and electrolysis operation. Although doped ceria infiltration into Ni–YSZ has recently been shown to improve the electrode performance and stability, the mechanisms defining how GDC impacts electrochemical characteristics are not fully delineated. Furthermore, the electrochemical characteristics have not yet been determined over the full range of conditions normally encountered in fuel cell and electrolysis operation. Here we present a study of both symmetric and full cells aimed at understanding the electrochemical mechanisms of GDC-modified Ni–YSZ over a wide range of fuel compositions and temperatures. Single-step GDC infiltration at an appropriate loading substantially reduced the polarization resistance of Ni–YSZ electrodes in electrolyte-supported cells, as measured using electrochemical impedance spectroscopy (EIS) at various temperatures (600–800 °C) in a range of H 2 O–H 2 mixtures (3–90 vol% H 2 O). Fuel-electrode-supported cells had significant concentration polarization due to the thick Ni–YSZ supports. A distribution of relaxation times approach is used to develop a physically-based electrochemical model; the results show that GDC reduces the reaction resistance associated with three-phase boundaries, but also appears to improve oxygen transport in the electrode. Increasing the H 2 O fraction in the H 2 –H 2 O fuel mixture reduced both the three-phase boundary resistance and the gas diffusion resistance for Ni–YSZ; with GDC infiltration, the electrode resistance showed less variation with fuel composition. GDC infiltration improved the performance of fuel-electrode-supported full cells, which yielded a maximum power density of 2.28 W cm −2 in fuel cell mode and an electrolysis current density at 1.3 V of 2.22 A cm −2 , both at 800 °C. 

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3. An Unbalanced Battle in Excellence: Revealing Effect of Ni/Co Occupancy on Water Splitting and Oxygen Reduction Reactions in Triple‐Conducting Oxides for Protonic Ceramic Electrochemical Cells

   https://doi.org/10.1002/smll.202201953  

   Tang, Wei ; Ding, Hanping ; Bian, Wenjuan ; Regalado Vera, Clarita Y. ; Gomez, Joshua Y. ; Dong, Yanhao ; Li, Ju ; Wu, Wei ; Fan, WeiWei ; Zhou, Meng ; et al ( June 2022 , Small)

   Porous electrodes that conduct electrons, protons, and oxygen ions with dramatically expanded catalytic active sites can replace conventional electrodes with sluggish kinetics in protonic ceramic electrochemical cells. In this work, a strategy is utilized to promote triple conduction by facilitating proton conduction in praseodymium cobaltite perovskite through engineering non‐equivalent B‐site Ni/Co occupancy. Surface infrared spectroscopy is used to study the dehydration behavior, which proves the existence of protons in the perovskite lattice. The proton mobility and proton stability are investigated by hydrogen/deuterium (H/D) isotope exchange and temperature‐programmed desorption. It is observed that the increased nickel replacement on the B‐site has a positive impact on proton defect stability, catalytic activity, and electrochemical performance. This doping strategy is demonstrated to be a promising pathway to increase catalytic activity toward the oxygen reduction and water splitting reactions. The chosen PrNi_0.7Co_0.3O_3−δoxygen electrode demonstrates excellent full‐cell performance with high electrolysis current density of −1.48 A cm⁻²at 1.3 V and a peak fuel‐cell power density of 0.95 W cm⁻²at 600 °C and also enables lower‐temperature operations down to 350 °C, and superior long‐term durability.

    

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4. Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas‐Diffusion Electrodes

   https://doi.org/10.1002/eem2.12307  

   Zhang, Jianfang ; Li, Zhengyuan ; Cai, Rui ; Zhang, Tianyu ; Yang, Shize ; Ma, Lu ; Wang, Yan ; Wu, Yucheng ; Wu, Jingjie ( April 2022 , ENERGY & ENVIRONMENTAL MATERIALS)

   Regulating the selectivity toward a target hydrocarbon product is still the focus of CO₂electroreduction. Here, we discover that the original surface Cu species in Cu gas‐diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C₁or C₂hydrocarbons. The selectivity toward C₂H₄progressively increases, while CH₄decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas‐diffusion electrode with the highest Cu^δ+/Cu⁰ratio favors the pathways of hydrogenation to form CH₄with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm⁻²at −0.83 V vs RHE. At 2.0 V, the Cu gas‐diffusion electrode with the lowest Cu^δ+/Cu⁰ratio prefers C–C coupling to form C₂₊products with Faradaic efficiency topping 80.1% at −0.75 V vs RHE, where the Faradaic efficiency of C₂H₄accounts for 46.4% and the partial current density of C₂H₄achieves 279 mA cm⁻². This work demonstrates that the selectivity from CH₄to C₂H₄is switchable by tuning surface Cu species composition of Cu gas‐diffusion electrodes.

    

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5. RTD Light Emission around 1550 nm with IQE up to 6% at 300 K

   https://doi.org/10.1109/DRC50226.2020.9135175  

   Brown, E. R. ; Zhang, W-D. ; Fakhimi, P. ; Growden, T. A. ; Berger, P.R. ( June 2020 , IEEE Device Research Conference (DRC), Columbus, OH (June 22-24, 2020))

   Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at  = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K. The spectral peaks for VB = 2.8 and 3.0 V both occur around  = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at  =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). 

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