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DOE OSTI2016

3D Graphitic Foams Derived from Chloroaluminate Anion Intercalation for Ultrafast Aluminum-Ion Battery

We present that a 3D graphitic foam vertically aligned graphitic structure and a low density of defects is derived through chloroaluminate anion intercalation of graphite followed by thermal expansion and electrochemical hydrogen evolution. Such aligned graphitic structure affords excellent Al-ion battery characteristics with a discharge capacity of ≈60 mA h g -1 under a high charge and discharge current density of 12 000 mA g -1 over ≈4000 cycles.

25 ENERGY STORAGE↗

DOE OSTI2026

Achievement of a high-density, high-confinement, and high-beta tokamak plasma regime in DIII-D, and implications for a lower-current path for ITER and FPP

Experiments on DIII-D have demonstrated a density-confinement synergy that enables sustainment of high performance in a previously unattained parameter regime of simultaneous very high energy confinement quality (H 98y2 ≥ 1.5), very high line-average density Greenwald fraction (ƒ Gr = πa 2 < n >/I P ≥ 1.4), and high toroidal beta (β T ≥ 3%). Tokamak operation in this regime is essential for a compact steady-state FPP, as well as for Q=10 with 500 MW of fusion power in ITER at I P << 15 MA. These experiments leveraged the knowledge that, in the high-poloidal-beta (β P ) regime, impurity and density gradients can enhance turbulence stabilization caused by high α MHD (α MHD ~(dβ P )⁄dr). This was described by theoretical predictions and gyrokinetic transport simulations [M.T. Kotschenreuther et al, 2024 Nucl. Fusion, 64 076033], and later confirmed by experiments on DIII-D [S. Ding et al, 2024 Nature 629 555]. To increase both β P and β T , the new experiments increased the ideal-wall stability β N -limit by using a smaller plasma-outer wall distance and higher triangularity in the plasma cross section (top/bottom average δ~0.9), enabled by the recent “shape & volume rise” (SVR) modification to the DIII-D divertor. The higher triangularity also contributed to achieving higher ƒ Gr by enabling higher pedestal density. At high density, the pedestal is ballooning limited and exhibits small and frequent ELMs, while the divertor is near detachment even without any impurity seeding. High plasma performance was attained and sustained reproducibly, with the eventual terminations brought about by an MHD mode destabilized as the current profile slowly continued to evolve. A path to stationary fully noninductive operation might include ECH injection to reduce both core impurity accumulation and the electron collisionality, thus increasing the bootstrap current. These experiments provide the first experimental demonstration of the ƒ Gr , H 98y2 , and β T values required simultaneously for ITER Q = 10 at I P < 10 MA, pointing to practical ways to improve the energy confinement in a fusion reactor.

Garofalo, Andrea M. [General Atomics, San Diego, C↗

DOE OSTI2018

Engineering current density over 5 kA mm -2 at 4.2 K, 14 T in thick film REBCO tapes

We report on remarkably high in-field performance at 4.2 K achieved in >4 $μ$m thick rare earth barium copper oxide (REBCO) samples with Zr addition. Two different samples have been measured independently at Lawrence Berkeley National Laboratory and the National High Magnetic Field Laboratory, achieving critical current densities ( J c ) of 12.21 MA cm -2 and 12.32 MA cm -2 at 4.2 K, 14 T ($\small{B}$|| c ), respectively, which corresponds to equivalent critical current ( I c ) values of 2247 and 2119 A/4 mm. These I c values are about two times higher than the best reported performance of REBCO tapes to date and more than five times higher than the commercial HTS tapes reported in a recent study. The measured J c values, with a pinning force of ~1.7 T N m -3 are almost identical to the highest value reported for thin (~1 $μ$m thick) REBCO at the field and temperature, but extended to very thick (>4 μm) films. This results in an engineering current density ( J e ) above 5 kA mm -2 at 4.2 K, 14 T, which is more than five times higher than Nb 3 Sn and nearly four times higher than the highest reported value of all superconductors other than REBCO at this field and temperature. The reported results have been achieved by utilizing an advanced metal organic chemical vapor deposition system. This study demonstrates the remarkable level of in-field performance achievable with REBCO conductors at 4.2 K and strong potential for high-field magnet applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Design and synthesis of N-doped mesoporous carbon@ NiCo2O4 nanocomposites with various morphologies for high electrochemical performance applied in supercapacitors

Highlights: • Various morphologies of N-doped mesoporous carbon@ NiCo{sub 2}O{sub 4}, such as sea urchins-like structure NiCo{sub 2}O{sub 4}, litchi chinensis-like structure of 0.1 g NC@ NiCo{sub 2}O{sub 4} and waxyberry-like structure of 0.2 g NC@ NiCo{sub 2}O{sub 4} are successfully synthesized by a facile hydrothermal method. • Waxberry-like structure of 0.2 g NC@ NiCo{sub 2}O{sub 4} shows the best electrochemical performancee among these three structures. • Waxberry-like structure of 0.2 g NC@ NiCo{sub 2}O{sub 4} has a considerable specific capacitance of 1624 F g{sup −1} at a current density of 1A g{sup −1} with superior electrochemical stability after 10000 cycles. - Abstract: Hybrid nanostructures of N-doped mesoporous carbon@NiCo{sub 2}O{sub 4} with controllable compositions are prepared by a facile hydrothermal method. Various morphologies of N-doped mesoporous carbon@NiCo{sub 2}O{sub 4} are successfully synthesized including sea urchins-like structure of free NiCo{sub 2}O{sub 4}, litchi chinensis-like structure of NC-100@ NiCo{sub 2}O{sub 4} and waxberry-like structure of NC-200@ NiCo{sub 2}O{sub 4}. All samples exhibit excellent rate capability and cycle stability. The incorporation of N-doped mesoporous carbon causes a dominant capacitance increase. Free NiCo{sub 2}O{sub 4} only possesses a specific capacitance of 1038 F g{sup −1} at 1 A g{sup −1}, while NC-200@ NiCo{sub 2}O{sub 4} renders a much higher specific capacitance of 1624 F g{sup −1}, which shows a distinct improvement of 56.4%. Moreover, NC-200@ NiCo{sub 2}O{sub 4} still performs a high specific capacitance of 1360 F g{sup -1} even at a high current density of 10 A g{sup −1}. Besides, the final capacitance can still maintain 94.3% of the initial capacitance even after 10,000 cycles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2016

Cr{sub 2}O{sub 5} as new cathode for rechargeable sodium ion batteries

Chromium oxide, Cr{sub 2}O{sub 5}, was synthesized by pyrolyzing CrO{sub 3} at 350 °C and employed as a new cathode in rechargeable sodium ion batteries. Cr{sub 2}O{sub 5}/Na rechargeable batteries delivered high specific capacities up to 310 mAh/g at a current density of C/16 (or 20 mA/g). High-resolution solid-state {sup 23}Na NMR both qualitatively and quantitatively revealed the reversible intercalation of Na ions into the bulk electrode and participation of Na ions in the formation of the solid-electrolyte interphase largely at low potentials. Amorphization of the electrode structure occurred during the first discharge revealed by both NMR and X-ray diffraction data. CrO{sub 3}-catalyzed electrolyte degradation and loss in electronic conductivity led to gradual capacity fading. The specific capacity stabilized at >120 mAh/g after 50 charge-discharge cycles. Further improvement in electrochemical performance is possible via electrode surface modification, polymer binder incorporation, or designs of new morphologies. - Graphical abstract: Electrochemical profile of a Cr{sub 2}O{sub 5}/Na battery cell and high-resolution solid-state {sup 23}Na MAS NMR spectrum of a Cr{sub 2}O{sub 5} electrode discharged to 2 V. - Highlights: • Cr{sub 2}O{sub 5} was synthesized and used as a new cathode in rechargeable Na ion batteries. • A high capacity of 310 mAh/g and an energy density of 564 Wh/kg were achieved. • High-resolution solid-state {sup 23}Na NMR was employed to follow the reaction mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

A multidimensional approach to quantum state tomography of photoelectron wavepackets

There is a growing interest in reconstructing the density matrix of photoelectron wavepackets, in particular in complex systems where decoherence can be introduced either by a partial measurement of the system or through coupling with a stochastic environment. To this end, several methods to reconstruct the density matrix, quantum state tomography protocols, have been developed and tested on photoelectrons ejected from noble gases following absorption of extreme ultraviolet (XUV) photons from attosecond pulses. It remains a challenge to obtain model-free, single scan protocols that can reconstruct the density matrix with high fidelities. Current methods require extensive measurements or involve complex fitting of the signal. Efficient single-scan reconstructions would be of great help to increase the number of systems that can be studied. We propose a new and more efficient protocol that is able to reconstruct the continuous variable density matrix of a photoelectron in a single time delay scan. It is based on measuring the coherences of a photoelectron created by absorption of an XUV pulse using a broadband infrared (IR) probe that is scanned in time and a narrowband IR reference that is temporally fixed to the XUV pulse. We illustrate its performance for a Fano resonance in He as well as mixed states in Ar arising from spin-orbit splitting. We show that the protocol results in excellent fidelities and near-perfect estimation of the purity.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

NASA NTRS2022

Stormtime Ring Current Heating of the Ionosphere and Plasmasphere

The energy deposition from ring current ions into the high density “cold” plasma of the ionosphere and plasmasphere is analyzed, based on a Comprehensive Inner Magnetosphere-Ionosphere simulation of the 2015 October 7 storm. In addition, the Naval Research Laboratory Sami3 is Also a Model of the Ionosphere ionosphere/plasmasphere code is used to simulate the effect of Coulomb-collision heating of plasmasphere and ionosphere electrons by ring current ions. We find that, during stormtime peaks in the Dst index, energy is deposited at altitudes as low as 100 km. Heating along the entirety of any given field line, both in the ionosphere and plasmasphere, contributes to increased temperatures in the ionosphere F layer and inner magnetosphere and to subsequent cold O + outflows. However, relative to the heating of the plasmasphere, the direct heating of the ionosphere by ring current ions produces only small effects. Qualitative model-data agreement on the N + /O + density ratio is consistent with the hypothesis that these outflows are driven by thermal forcing.

J. Krall↗

DOE OSTI2022

Comparative Analysis of Direct and Indirect Cooling of Wide-Bandgap Power Modules and Performance Enhancement of Jet Impingement-Based Direct Substrate Cooling

With the development of high-power and high-torque machines, requirements for high-power density electronics are increasing. Thermal management of such systems requires high heat extraction. Conventional air cooling based heat sinks and cold plate based liquid cooling have their own benefits for various applications but has limitations for high power density applications. The current study explores a jet impingement based direct substrate cooling system that was implemented for a SiC based direct bonded Cu substrate for various power losses. Numerical comparison between jet impingement cooling and conventional horizontal/indirect cooling (pin fin heat sink and genetic algorithm-optimized heat sink) showed that the area weighted average of the heat transfer coefficient (HTC) is high for both horizontal cooling designs, and the local HTC is higher for jet impingement. Design iterations were undertaken to resolve the bottleneck of this cooling system. Increasing the number of nozzles helped to cover more area at the direct bonded Cu bottom plate, which drops the chip temperature considerably. With a constant flow rate, increasing the number of nozzles would decrease local jet velocity, which reduces the heat extraction by jet impingement. This issue can be addressed by reducing the diameter of nozzle but doing so results in a high pressure drop where the design constraint is 2 psi. A flared nozzle design is proposed, which has a higher spreading angle of the jet that increases the flow coverage and reduces the pressure drop of the coolant loop.

Barua, Himel↗

DOE OSTI2024

Antiferroelectric Ceramics for Energy–Efficient Capacitors by Theory–Guided Discovery

Antiferroelectric ceramics, via the electric-field-induced antiferroelectric (AFE)–ferroelectric (FE) phase transitions, show great promise for high-energy-density capacitors. Yet, currently, only 70–80% energy release is found during a charge–discharge cycle. Here, for PbZrO 3 -based oxides, geometric nonlinear theory of martensitic phase transitions is applied (first used to guide supercompatible shape-memory alloys) to predict the reversibility of the AFE–FE transition by using density-functional theory to assess AFE/FE interfacial lattice-mismatch strain that assures ultralow electric hysteresis and extended fatigue lifetime. A good correlation of mismatch strain with electric hysteresis, hence, with energy efficiency of AFE capacitors is observed. Here, guided by theory, high-throughput material search is conducted and AFE compositions with a near-perfect charge–discharge energy efficiency (98.2%), i.e., near-zero hysteresis are discovered. And the fatigue life of the capacitor reaches 79.5 million charge–discharge cycles, a factor of 80 enhancement over AFE ceramics with large electric hysteresis.

36 MATERIALS SCIENCE↗

DOE OSTI2018

A scalable 3D lithium metal anode

A scalable 3D electrode to serve as a lithium metal host is developed to enable stable lithium metal cycling. The electrode is simply fabricated by coating a slurry of well mixed LiNO 3 , carbon black, and PVDF on the Cu foil. The pores in the electrode serve as lithium metal hosts while the LiNO 3 particles act both as a structural skeleton and an electrolyte additive. Micron-level dense Li chunks are deposited into the 3D electrode at a current density of 2 mA cm -2 . Moreover, high coulombic efficiencies of 98.4% and 97.1% are achieved in carbonate-based electrolytes at current densities of 0.25 mA cm -2 and 2 mA cm -2 , respectively. The 3D electrode is tested in an anode free cell with LiFePO 4 , which exhibits a good capacity retention of 49.1% after 100 cycles and correspond to an average efficiency of 99.3% per cycle. This work provides a facile and scalable method to fabricate multi-functional 3D electrodes for dendrite-free and high coulombic efficiency Li metal anodes.

25 ENERGY STORAGE↗

DOE OSTI2016

The importance of band tail recombination on current collection and open-circuit voltage in CZTSSe solar cells

Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) solar cells typically exhibit high short-circuit current density (J{sub sc}), but have reduced cell efficiencies relative to other thin film technologies due to a deficit in the open-circuit voltage (V{sub oc}), which prevent these devices from becoming commercially competitive. Recent research has attributed the low V{sub oc} in CZTSSe devices to small scale disorder that creates band tail states within the absorber band gap, but the physical processes responsible for this V{sub oc} reduction have not been elucidated. In this paper, we show that carrier recombination through non-mobile band tail states has a strong voltage dependence and is a significant performance-limiting factor, and including these effects in simulation allows us to simultaneously explain the V{sub oc} deficit, reduced fill factor, and voltage-dependent quantum efficiency with a self-consistent set of material parameters. Comparisons of numerical simulations to measured data show that reasonable values for the band tail parameters (characteristic energy, capture rate) can account for the observed low V{sub oc}, high J{sub sc}, and voltage dependent collection efficiency. These results provide additional evidence that the presence of band tail states accounts for the low efficiencies of CZTSSe solar cells and further demonstrates that recombination through non-mobile band tail states is the dominant efficiency limiting mechanism.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2017

Hydrodynamic model of a dielectric-barrier discharge in pure chlorine

A one-dimensional hydrodynamic model of a dielectric-barrier discharge (DBD) in pure chlorine is developed, and the properties of the discharge are modeled. The discharge is excited in an 8-mm-long discharge gap between 2-mm-thick dielectric quartz layers covering metal electrodes. The DBD spatiotemporal characteristics at gas pressures of 15–100 Torr are modeled for the case in which a 100-kHz harmonic voltage with an amplitude of 8 kV is applied to the electrodes. The average power density deposited in the discharge over one voltage period is 2.5–5.8 W/cm{sup 3}. It is shown that ions and electrons absorb about 95 and 5% of the discharge power, respectively. In this case, from 67 to 97% of the power absorbed by electrons is spent on the dissociation and ionization of Cl{sub 2} molecules. Two phases can be distinguished in the discharge dynamics: the active (multispike) phase, which follows the breakdown of the discharge gap, and the passive phase. The active phase is characterized by the presence of multiple current spikes, a relatively high current, small surface charge density on the dielectrics, and large voltage drop across the discharge gap. The passive phase (with no current spikes) is characterized by a low current, large surface charge density on the dielectrics, and small voltage drop across the discharge gap. The peak current density in the spikes at all pressures is about 4 mA/cm{sup 2}. In the multispike phase, there are distinct space charge sheaths with thicknesses of 1.5–1.8 mm and a mean electron energy of 4.3–7 eV and the central region of quasineutral plasma with a weak electric field and a mean electron energy of 0.8–3 eV. The degree of ionization of chlorine molecules in the discharge is ~0.02% at a pressure of 15 Torr and ~0.01% at 100 Torr. The DBD plasma is electronegative due to the fast attachment of electrons to chlorine atoms: e + Cl{sub 2} → Cl + Cl{sup –}. The most abundant charged particles are Cl{sub 2}{sup +} and Cl{sup −} ions, and the degree of ionization during current spikes in the active phase is (4.1–5.5) × 10{sup –7}. The mechanism of discharge sustainment is analyzed. The appearance of a series of current spikes in the active phase of the discharge is explained.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2025

High Power Density, Carbon Neutral Electrical Power Generation for Air Vehicles

The synergistic integration of a Solid Oxide Fuel Cell-Combustor (SOFC-C) with a turbogenerator (TG) will provide a very high fuel-to-electricity conversion efficiency while maintaining high power-to-weight ratio during high-altitude flight. The proposed SOFC-C-TG power generation technology exceeds the REEACH technical performance targets (TPT). This unique concept addresses many of the challenges faced in all electric propulsion-based aviation. The system has high part-load efficiency (more than 65% lower heating value (LHV)) during long cruise times, load following capability, high-power capacity at high altitudes adapting to low temperatures and pressures, rapid startup time of less than 30 minutes (proven with current SOFC technology), high power density (more than 3.2 kW/kg), efficient thermal management, and a foundation for a compact, efficient electrical storage and power generation system (ESPG). The SOFC-C concept achieves the technology targets by reducing the complexity of traditional fuel cell-gas turbine hybrid systems (FC-GT). The SOFC-C does not require heat exchangers and dramatically reduces the balance of plant increasing power density and performance in efficiency. The reduction in mass through elimination of heat exchangers, external reformer, and other components dramatically decreases the overall thermal dampening of the system which enables rapid startup and load following capability. Direct control of the cathode inlet temperature of the SOFC-C enables rapid warm-up of the SOFC tubes with the ability to reach operating temperature and full power in less than 30 minutes.

03 NATURAL GAS↗

DOE OSTI2023

Interpretable design of Ir-free trimetallic electrocatalysts for ammonia oxidation with graph neural networks

The electrochemical ammonia oxidation to dinitrogen as a means for energy and environmental applications is a key technology toward the realization of a sustainable nitrogen cycle. The state-of-the-art metal catalysts including Pt and its bimetallics with Ir show promising activity, albeit suffering from high overpotentials for appreciable current densities and the soaring price of precious metals. Herein, the immense design space of ternary Pt alloy nanostructures is explored by graph neural networks trained on ab initio data for concurrently predicting site reactivity, surface stability, and catalyst synthesizability descriptors. Among a few Ir-free candidates that emerge from the active learning workflow, Pt 3 Ru-M (M: Fe, Co, or Ni) alloys were successfully synthesized and experimentally verified to be more active toward ammonia oxidation than Pt, Pt 3 Ir, and Pt 3 Ru. More importantly, feature attribution analyses using the machine-learned representation of site motifs provide fundamental insights into chemical bonding at metal surfaces and shed light on design strategies for high-performance catalytic systems beyond the d-band center metric of binding sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Ternary Phosphides Ba M 2 P 2 : Tailoring Crystal and Electronic Structures Enables Highly Efficient HER Electrocatalysis

Binary transition metal phosphides and their solid solutions have emerged as promising hydrogen evolution reaction (HER) catalysts. Although many research endeavors have adopted strategies to vary compositions to optimize catalytic performance, they mainly focus on binary structures, which represent only a small fraction of the abundant phase space of structure types among transition metal phosphides. Here, the largely unexplored class of ternary and multinary ordered phosphides in catalysis comprises two or more metals with quite different chemical nature, concealing the structure–property relationships essential for advancing catalyst design. Here, we explored phosphides crystallizing in one of the most abundant ordered intermetallic structure types, —the ThCr 2 Si 2 type, —where square nets of 3d transition metal M and P atoms are separated by layers of electropositive Ba cations. Four ternary BaM 2 P 2 (M = Fe, Fe/Cu, Fe/Ni, Ni) catalysts were synthesized and characterized. BaNi 2 P 2 showed high HER activity in acidic electrolyte, which required an overpotential, η 10 , of only 62 mV to drive current density j = –10 mA/cm 2 and high stability with a potential drop rate of 0.25 mV/h. BaNi 2 P 2 outperformed other Ni-based catalysts, such as Ni 2 P and Ni 5 P 4 . Notably, at current densities above –170 mA/cm 2 , BaNi 2 P 2 outperformed the standard Pt electrode measured under identical conditions. Electronic structure analysis revealed a volcano-type activity trend among the four BaM 2 P 2 catalysts based on their d-band center positions, highlighting the role of electropositive Ba cations in shifting the Ni-3d orbitals into an optimal position.

BaNi2P2↗

DOE OSTI2024

Corrosion Engineering of Part‐Per‐Million Single Atom Pt 1 /Ni(OH) 2 Electrocatalyst for PET Upcycling at Ampere‐Level Current Density

The plastic waste issue has posed a series of formidable challenges for the ecological environment and human health. While conventional recycling strategies often lead to plastic down-cycling, the electrochemical strategy of recovering valuable monomers enables an ideal, circular plastic economy. Here a corrosion synthesized single atom Pt 1 /Ni(OH) 2 electrocatalyst with part-per-million noble Pt loading for highly efficient and selective upcycling of polyethylene terephthalate (PET) into valuable chemicals (potassium diformate and terephthalic acid) and green hydrogen is reported. Electro-oxidation of PET hydrolysate, ethylene glycol (EG), to formate is processed with high Faraday efficiency (FE) and selectivity (>90%) at the current density close to 1000 mA cm −2 (1.444 V vs RHE). The in situ spectroscopy and density functional theory calculations provide insights into the mechanism and the understanding of the high efficiency. Remarkably, the electro-oxidation of EG at the ampere-level current density is also successfully illustrated by using a membrane-electrode assembly with high FEs to formate integrated with hydrogen production for 500 h of continuous operation. In conclusion, this process allows valuable chemical production at high space-time yield and is highly profitable (588–700 $\$$ ton −1 PET), showing an industrial perspective on single-atom catalysis of electrochemical plastic upcycling.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Carbonate Management to Enable Energy- and Carbon-Efficient CO 2 Electrolysis (Final Technical Report)

The rapid growth and plummeting cost of solar energy have spurred growing interest in using CO 2 electrolysis to produce chemicals and fuels as an alternative to conventional petrochemical processes. High-temperature (>800 °C) solid oxide electrolyzers that convert CO 2 into CO and O 2 have recently become commercially available. Low-temperature electrolysis cells offer the prospect of more convenient and flexible operation, which is critical for utilizing intermittent solar energy, and provide access to more valuable C 2+ products such as ethylene, ethanol, and propanol. Over the past 10 years, research in this area has yielded substantial progress in both fundamental understanding of the requisite electrocatalytic reactions and design of prototype devices. Leveraging insights from fuel cells and membrane water electrolyzers, researchers have developed electrolysis cells with gas diffusion electrodes (GDE) that have demonstrated high CO 2 electrolysis current densities (>100 mA cm –2 ) as well as promising selectivity and stability. Despite these advances, the energy efficiency (electrical energy-to-product) and carbon efficiency (CO 2 -to-product) of low-temperature CO 2 electrolysis remain far too low for large-scale deployment. A preponderance of evidence indicates that the principal source of efficiency losses is the rapid and thermodynamically favorable reaction of CO 2 with hydroxide (OH – ) to form carbonate (CO 3 2– ). Carbonate formation imposes steady-state electrolysis conditions that result in large voltage and CO 2 losses for all known (photo)electrochemical CO 2 cells. While much current research remains focused on CO 2 reduction catalyst design, this largely overlooked CO 3 2– problem presents a fundamental scientific barrier to creating a viable electrochemical option for converting solar energy into chemicals and fuels. The project pursues an integrated, multi-PI research effort that establishes a fundamental science of CO 3 2– management. PI Kanan and Co-PI Mani’s contribution to the project is to evaluate strategies to mitigate the CO 3 2– problem by changing the properties of the electrolyte and the environment in which CO 2 reduction catalysis takes place. Experimental studies showed that electrolytes composed of a high concentration of both CO 3 2– and HCO 3 – , which serve as moderately alkaline buffers, improved the cell voltage by compared to all-HCO 3 – electrolytes, but these buffered systems still show substantial CO 2 uptake that reduces pH over time. Computational studies developed a homogenized model of a CO 2 reduction catalyst layer that permits a low-cost exploration of the high-dimensional parameter space associated with catalyst layers on gas diffusion electrodes. The model was validated by accurately reproducing experimental data for the related but simpler reaction of CO reduction and then used to probe the effects of catalyst layer architecture on CO 2 reduction. Minimizing the size of catalyst and hydrophobic domains in the catalyst layer is predicted to mitigate CO 3 2– formation and thereby enable prolonged operation at elevated pH. In support of the CO 2 electrolysis studies, a new method for rapidly prototyping electrochemical cells was developed and validated. The method uses a combination of 3D printing and electroless plating to generate conductive cell components for evaluating new cell designs. The carbonate problem encompasses mass transport processes and acid-base reactions that are relevant to many other electrochemical systems. Investigation of strategies to address the carbonate problem led to an additional line of inquiry into the physicochemical phenomena that determine the efficiency of electrochemical acid-base production, which has numerous applications in the broader field of carbon management. New strategies for using the supporting electrolyte to inhibit H + /OH – recombination in electrochemical acid-base production were evaluated, leading to the development of a novel acid-base producing system that eliminates the need for ion exchange membranes and exhibits promising efficiency and current densities for scalable applications.

25 ENERGY STORAGE↗

DOE OSTI2016

The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

The effect due to systematic substitution of cobalt by iron in La 0.6 Ca 0.4 Co 1-x Fe x O 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order towards OH- near unity were achieved for the unsubstituted La 0.6 Ca 0.4 CoO 3 . Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6 Ca 0.4 Co 0.2 Fe 0.8 O 3 and La 0.6 Ca 0.4 Co 0.1 Fe 0.9 O 3 showed higher area specific activity towards OER than La 0.6 Ca 0.4 CoO 3 or La 0.6 Ca 0.4 FeO 3 . Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗