Stable Zinc Electrode Reaction Enabled by Combined Cationic and Anionic Electrolyte Additives for Non-Flow Aqueous Zn─Br Batteries.

Aqueous zinc-bromine batteries hold immense promise for large-scale energy storage systems due to their inherent safety and high energy density. However, achieving a reliable zinc metal electrode reaction is challenging because zinc metal in the aqueous electrolyte inevitably leads to dendrite growth and related side reactions, resulting in rapid capacity fading. Here, it is reported that combined cationic and anionic additives in the electrolytes using CeCl can simultaneously address the multiple chronic issues of the zinc metal electrode.

Colossal Reversible Barocaloric Effects in a Plastic Crystal Mediated by Lattice Vibrations and Ion Diffusion.

Solid-state methods for cooling and heating promise a sustainable alternative to current compression cycles of greenhouse gases and inefficient fuel-burning heaters. Barocaloric effects (BCE) driven by hydrostatic pressure (p) are especially encouraging in terms of large adiabatic temperature changes (|ΔT| ≈ 10 K) and isothermal entropy changes (|ΔS| ≈ 100 J K kg). However, BCE typically require large pressure shifts due to irreversibility issues, and sizeable |ΔT| and |ΔS| seldom are realized in a same material.

Understanding Ion Dynamics in Closoborate-Type Lithium-Ion Conductors on Different Time-Scales.

The lithium-ion transport mechanism in 0.7Li(CBH)-0.3Li(CBH) complex hydride solid electrolyte was studied over a wide time-scale (ns-ms) by choosing appropriate techniques for assessing ionic motion on the desired time-scale using nuclear magnetic resonance (NMR) relaxation, AC impedance, and pulsed field gradient-NMR (PFG-NMR) measurements.

Monocarborane cluster as a stable fluorine-free calcium battery electrolyte.

High-energy-density and low-cost calcium (Ca) batteries have been proposed as 'beyond-Li-ion' electrochemical energy storage devices. However, they have seen limited progress due to challenges associated with developing electrolytes showing reductive/oxidative stabilities and high ionic conductivities. This paper describes a calcium monocarborane cluster salt in a mixed solvent as a Ca-battery electrolyte with high anodic stability (up to 4 V vs.

Pseudo-ternary LiBH·LiCl·PS system as structurally disordered bulk electrolyte for all-solid-state lithium batteries.

The properties of the mixed system LiBH-LiCl-PS are studied with respect to all-solid-state batteries. The studied material undergoes an amorphization upon heating above 60 °C, accompanied with increased Li conductivity beneficial for battery electrolyte applications. The measured ionic conductivity is ∼10 S cm at room temperature with an activation energy of 0.

A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries.

All-solid-state batteries incorporating lithium metal anode have the potential to address the energy density issues of conventional lithium-ion batteries that use flammable organic liquid electrolytes and low-capacity carbonaceous anodes. However, they suffer from high lithium ion transfer resistance, mainly due to the instability of the solid electrolytes against lithium metal, limiting their use in practical cells. Here, we report a complex hydride lithium superionic conductor, 0.

Origin of unusual spinel-to-layered phase transformation by crystal water.

It is well known that many layered transition metal oxides can transform into a spinel structure upon repeated battery cycling, but a phase transition in the opposite direction is rare. Recently, the transformation from spinel MnO to layered MnO was observed during the operation of a Mg battery in aqueous conditions, resulting in high performance Mg batteries. We hereby use calculations to unveil the mechanism by which crystal water plays a critical role in this unique transformation.

Nanoscale Zirconium-Abundant Surface Layers on Lithium- and Manganese-Rich Layered Oxides for High-Rate Lithium-Ion Batteries.

Battery performance, such as the rate capability and cycle stability of lithium transition metal oxides, is strongly correlated with the surface properties of active particles. For lithium-rich layered oxides, transition metal segregation in the initial state and migration upon cycling leads to a significant structural rearrangement, which eventually degrades the electrode performance. Here, we show that a fine-tuning of surface chemistry on the particular crystal facet can facilitate ionic diffusion and thus improve the rate capability dramatically, delivering a specific capacity of ∼110 mAh g at 30C.

A stable lithium-rich surface structure for lithium-rich layered cathode materials.

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity.

Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation.

The phase transition of layered manganese oxides to spinel phases is a well-known phenomenon in rechargeable batteries and is the main origin of the capacity fading in these materials. This spontaneous phase transition is associated with the intrinsic properties of manganese, such as its size, preferred crystal positions, and reaction characteristics, and it is therefore very difficult to avoid. The introduction of crystal water by an electrochemical process enables the inverse phase transition from spinel to a layered Birnessite structure.

The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries.

Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions.

Epitaxial growth and lithium ion conductivity of lithium-oxide garnet for an all solid-state battery electrolyte.

Epitaxial thin films of Al-doped Li7La3Zr2O12 (LLZO) with a cubic garnet-type structure were successfully synthesized using pulsed laser deposition to investigate the lithium ion conduction in grains. Two orientations of the films were obtained depending on the Gd3Ga5O12 (GGG) substrate orientation, LLZO(001)/GGG(001) and LLZO(111)/GGG(111). The ionic conductivities in the grains of the (001) and (111) films were 2.