Frustrated magnets provide a platform for exploring exotic phases beyond conventional ordering, with potential relevance to functional materials and information technologies. In this work, we use Monte Carlo simulations to map the thermodynamic phase diagram of pyrochlore iridates R2Ir2O7 (R = Dy, Ho) with three stable magnetic ground-state stable phases: frustrated spin-ice 2 in 2 out (2I2O) phase, frustrated fragmented 3 in 1 out/1 in 3 out (3I1O/1I3O) phase, and antiferromagnetic all in all out (AIAO) phase without frustration. We discovered two additional emergent metastable phases at finite temperatures, located between the boundaries separating those stable phases. These metastable phases exhibit high magnetic susceptibility and high entropy without long-range order. Their stabilization arises from entropic minimization of the free energy, where the entropy dominates energetic competition near phase boundaries at finite temperatures. Our results demonstrate a platform to engineer highly susceptible and degenerated states through frustration and thermal activation, offering a foundation for entropy-based design of metastable phases in correlated systems.

Batteries composed of CFx cathodes have high theoretical specific capacities (>860 mA h g-1). Attempts at realizing such batteries coupled with Li anodes have failed to deliver on this promise, however, due to a discharge voltage plateau below the theoretical maximum lowering the realized energy density and difficulties with recharging the system. In this study, we use first-principles calculations to investigate novel carbon allotropes for these battery systems: graphdiyne and "holey" graphene. We first identify stable flourination structures and calculate their band gaps. We demonstrate that the holes in these carbon allotropes can induce the formation of an amorphous LiF network within the carbon and that this formation may, in fact, be kinetically favored. For structures where amorphous LiF forms within the carbon, we predict it is easier to recharge and higher discharge voltages can be achieved. If the LiF forms outside the carbon product, however, it will be crystalline in form and lead to lower discharge voltages and more difficulty in recharging the systems. Finally, we simulate XPS spectra of representative cases, demonstrating an experimental pathway for determining the reaction pathway of these systems. Our work suggests CFx allotropes with holes in them as potential targets for high capacity, rechargeable cathodes for Li batteries, provided they lead to the formation of amorphous LiF within the C structure.

Rechargeable alkaline Zn/CuO batteries are a promising candidate for energy storage applications due to their high capacity and low cost. Recent studies have shown that the addition of Bi2O3 and the implementation of carbon coating on CuO cathodes enhances the performance and improves the cyclability of Zn/CuO batteries. However, the mechanism of influence of Bi2O3 on the electrochemical performance of CuO cathodes in rechargeable Zn/CuO batteries is not fully understood. We apply density functional computational methods to investigate the electrochemical discharge of CuO cathodes modified with a Bi2O3 additive. Our calculations suggests that the improved performance of Zn/CuO-Bi2O3 cells could be partially attributed to the formation of stable mixed Cu-Bi oxides, such as CuBi2O4, which suppress the accumulation of highly resistive Cu2O in the battery cathode. The results of our study are consistent with the experimental observations that confirm the presence of CuBi2O4 in CuO cathodes modified with Bi2O3.

Manganese dioxide is a promising cathode material for energy storage applications because of its high redox potential, large theoretical energy density, abundance, and low cost. It has been shown that the performance of MnO2 electrodes in rechargeable alkaline Zn/MnO2 batteries could be improved by nanostructuring and by increasing the concentration of defects in MnO2. However, the underlying mechanism of this improvement is not completely clear. We used an ab initio density functional computational approach to investigate the influence of nanostructuring and crystal defects on the electrochemical properties of the MnO2 cathode material. The mechanism of electrochemical discharge of MnO2 in Zn/MnO2 batteries was studied by modeling the process of H ion insertion into the structures of pyrolusite, ramsdellite, and nsutite polymorphs containing oxygen vacancies, cation vacancies, and open surfaces. Our calculations showed that the binding energies of H ions inserted into the structures of MnO2 polymorphs were strongly affected by the presence of surfaces and bulk defects. In particular, we found that the energies of H ions inserted under the surfaces and attached to the surfaces of MnO2 crystals were significantly lower than those for bulk MnO2. The results of our study provide an explanation for the influence of crystal defects and nanostructuring on the electrochemical reactivity of MnO2 cathodes in rechargeable alkaline Zn/MnO2 batteries.

Batteries are easy to use, remotely monitorable, not fuel dependent, easily permitted and installed, and start automatically and reliably during an electrical outage. This makes them optimal for stationary storage and power assurance applications. Within battery-based grid storage, as of mid-2017, lithium-ion, sodium-ion, and lead-acid systems are the leaders, comprising 59% (~1.1 GW), 8% (0.15 GW), and 3% (0.06 GW) of global operational electrochemical storage, respectively.However, these batteries suffer from low energy density, high cost, poor safety, environmental concerns, and/or cycle life. Existing battery options on the market also do not meet the required market needs for long-duration backup power. For example, lead-acid batteries require too much space, are heavy, and contain toxic materials. Lithium-ion batteries, while compact and capable of excellent cycle life, are too expensive to serve long outages and have notable flammability and environmental risks. Alkaline Zn batteries are a strong candidate for electrical grid storage applications due to Zn’s high capacity (820 mAh/g), established materials supply chain and low cost. To realize the highest energy dense batteries, Zn needs to be coupled with a similarly low cost, abundant and high-capacity cathode. CuO (674 mAh/g) is an intriguing high-capacity cathode when paired with Zn in alkaline electrolyte, a battery that until recently has been relegated to the history books as a primary system. In 2021 Schorr et al. reported a rechargeable Zn/CuO battery that utilized a Bi additive to help facilitate the electrochemical reversibility of the Cu conversion electrode. Bi2O3, a species with comparable redox potentials to Cu2O, promoted reversibility and minimized passivation in the historically non-reversible system. The battery cycled without any observable Cu and Bi mixed oxide phases, cycling between metallic Cu and Bi and Cu2O/Cu(OH)2 and Bi2O3, respectively. Although the Bi additive did not eliminate capacity fade completely, limiting the cells to a 30% depth of discharge (relative to CuO) enabled 250 cycles at > 124 Wh/L. Alternatively, compensating for capacity loss with additional Cu metal provided for very high areal capacities (∼40 mA h/cm2) and energy densities (∼260 W h/L), despite only 65% active material cathode loadings and ∼10% Zn anode utilization; preliminary tests indicated these batteries were prone to shorting. Seeking to improve performance and minimize the spatial segregation of Cu- and Bi-phases observed upon cycling in the prior system, D. Arnot et al. prepared nanoscale carbon coated (Cu/Bi) particles, where the coating partially minimized dissolution and diffusion of soluble cuprate and bismuthate complexes, where ~ 200 cycles at 300 mAh/g was demonstrated (@ ~ 100 Wh/L). CuBi2O4 and CuO phases were formed upon oxidation, indicating carbon coatings can affect the battery cycling mechanism and may have future roles increasing performance. Data collected from a variety of experimental techniques, including cyclic voltammetry, rotating ring-disk electrode voltammetry, electrochemical impedance spectroscopy, electron microscopy, transmission electron microscopy, Raman spectroscopy, operando energy-dispersive X-ray diffraction measurements, battery cycling along with recent DFT modeling will be presented to help elucidate the role of additives, carbon coatings, and ion selective polymers in enabling reversible Zn/Cu based batteries. In addition, the general challenges of achieving a highly reversible energy dense battery based on two conversion electrodes operating in highly alkaline environment will be discussed. The goal is to demonstrate a Zn/CuO battery with long lifetime, at appreciable energy densities (> 200 Wh/L), with excellent safety, lower toxicity and sufficiently low cost to be manufactured and installed on the grid. While the laboratory scale Zn/CuO battery builds have very promising characteristics to date they have not been optimized or adapted for consumer or market-based needs in terms of power performance, energy density, cycle life or stability in terms of shelf life and the ability to tolerate partial state of charge. Progress towards these goals may also be discussed. N. B. Schorr et al. Rechargeable Alkaline Zinc/Copper Oxide Batteries. ACS Applied Energy Mater. 2021, 4, 7, 7073–7082. https://doi.org/10.1021/acsaem.1c01133. D. J. Arnot et al. Rechargeable Alkaline Zn-Cu Batteries Enabled by Carbon Coated Cu/Bi Particles. J. Power Sources 2022, 529, 231168. https://doi.org/10.1016/j.jpowsour.2022.231168. This work was supported by the U.S. Department of Energy, Office of Electricity, and the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525. The views expressed herein do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Rechargeable alkaline Zn/MnO2 batteries are an attractive solution for large-scale energy storage applications. Recently, Bi and Cu additives have been used to increase the cycle life and capacity of rechargeable Zn/MnO2 batteries, with an equivalent of the full two-electron capacity realized for many cycles, in the absence of zinc. However, the mechanism of the effect of Bi and Cu on the performance of rechargeable Zn/MnO2 batteries has not been investigated in detail. We apply first-principles density functional computational methods to study the discharge mechanisms of the unmodified and Bi/Cu-modified γ-MnO2 electrodes in rechargeable alkaline Zn/MnO2 batteries. Using the results of our calculations, we analyze the possible redox reaction pathways in the γ-MnO2 electrode and identify the electrochemical processes leading to the formation of irreversible discharge reaction products, such as hausmannite and hetaerolite. Our study demonstrates the possibility of formation of intermediate Bi-Mn and Cu-Mn oxides in deep-cycled Bi/Cu-modified MnO2 electrodes. The formation of intermediate Bi-Mn and Cu-Mn oxides could reduce the rate of accumulation of irreversible reaction products in the MnO2 electrode and improve the rechargeability and cyclability of Zn/MnO2 batteries.

We utilize polarized neutron reflectometry (PNR) in consort with ab initio based density functional theory (DFT) calculations to study magnetoelectric coupling at the interface of a ferroelectric PbZr0.2Ti0.8O3 (PZT) and magnetic La0.67Sr0.33MnO3 (LSMO) heterostructure grown on a Nb-doped SrTiO3 (001) substrate. Functional device working conditions are mimicked by gating the heterostructure with a Pt top electrode to apply an external electric field, which alters the magnitude and switches the direction of the ferroelectric (FE) polarization, across the PZT layer. PNR results show that the gated PZT/LSMO exhibits interfacial magnetic phase modulation attributed to ferromagnetic (FM) to A-antiferromagnetic (A-AF) phase transitions resulting from hole accumulation. When the net FE polarization points towards the interface (positive), the interface doesn't undergo a magnetic phase transition and retains its global FM ordered state. In addition to changes in the interfacial magnetic ordering, the global magnetization of LSMO increases while switching the polarization from positive to negative and decreases vice versa. DFT calculations indicate that this enhanced magnetization also correlates with an out of plane tensile strain, whereas the suppressed magnetization for positive polarization is attributed to out of plane compressive strain. These calculations also show the coexistence of FM and A-AF phases at zero out of plane strain. Charge modulations throughout the LSMO layer appear to be unaffected by strain, suggesting that these charge mediated effects do not significantly change the global magnetization. Our PNR results and DFT calculations are in consort to verify that the interfacial magnetic modulations are due to co-action of strain and charge mediated effects with the strain and charge effects dominant at different length scale.