A Tellurium-Boosted High-Areal-Capacity Zinc-Sulfur Battery.

Aqueous rechargeable zinc-sulfur (Zn-S) batteries are a promising, cost-effective, and high-capacity energy storage technology. Still, they are challenged by the poor reversibility of S cathodes, sluggish redox kinetics, low S utilization, and unsatisfactory areal capacity. This work develops a facile strategy to achieve an appealing high-areal-capacity (above 5 mAh cm-2) Zn-S battery by molecular-level regulation between S and high-electrical-conductivity tellurium (Te). The incorporation of Te as a dopant allows for manipulation of the Zn-S electrochemistry, resulting in accelerated redox conversion, and enhanced S utilization. Meanwhile, accompanied by the S-ZnS conversion, Te is converted to zinc telluride during the discharge process, as revealed by ex-situ characterizations. This additional redox reaction contributes to the S cathode's total excellent discharge capacity. With this unique cathode structure design, the carbon-confined TeS cathode (denoted as Te1S7/C) delivers a high reversible capacity of 1335.0 mAh g-1 at 0.1 A g-1 with a mass loading of 4.22 mg cm-2, corresponding to a remarkable areal capacity of 5.64 mAh cm-2. Notably, a hybrid electrolyte design uplifts discharge plateau, reduces overpotential, suppresses Zn dendrites growth, and extends the calendar life of Zn-Te1S7 batteries. This study provides a rational S cathode structure to realize high-capacity Zn-S batteries for practical applications.

Unveiling the Mysteries: Acetonitrile's Dance with Weakly-Solvating Electrolytes in Shaping Gas Evolution and Electrochemical Performance of Zinc-ion Batteries.

Aqueous Zn-metal battery (AZMB) is a promising candidate for future large-scale energy storage with commendable capacity, exceptional safety characteristics, and low cost. Acetonitrile (AN) has been widely used as an effective electrolyte constituent to improve AZMBs' performance. However, its functioning mechanisms remain unclear. In this study, we unveiled the critical roles of AN in AZMBs via comparative in situ electrochemical, gaseous, and morphological analyses. Despite its limited ability to solvate Zn ions, AN-modulated Zn-ion solvation sheath with increased anions and decreased water achieves a weakly-solvating electrolyte. As a result, the Zn||Zn cell with AN addition exhibited 63 times longer cycle life than cell without AN and achieved a 4 Ah cm-2 accumulated capacity with no H2 generation. In V2O5||Zn cells, for the first time, AN suppressing CO2 generation, elevating CO2-initiation voltage from 2→2.44 V (H2: 2.43→2.55 V) was discovered. AN-impeded transit and Zn-side deposition of dissolved vanadium ions, known as "crosstalk," ameliorated inhomogeneous Zn deposition and dendritic Zn growth. At last, we demonstrated an AN-enabled high-areal-capacity AZMB (3.3 mAh cm-2) using high-mass-loading V2O5 cathode (26 mg cm-2). This study shed light on the strategy of constructing fast-desolvation electrolytes and offered insights for future electrolyte accommodation for high-voltage AZMB cathodes.

Coulombic Efficiency for Practical Zinc Metal Batteries: Critical Analysis and Perspectives.

Climate change and energy depletion are common worries of this century. During the global clean energy transition, aqueous zinc metal batteries (AZMBs) are expected to meet societal needs due to their large-scale energy storage capability with earth-abundant, non-flammable, and economical chemistries. However, the poor reversibility of Zn poses a severe challenge to AZMB implementation. Coulombic efficiency (CE) is a quantitative index of electrode reversibility in rechargeable batteries but is not well understood in AZMBs. Thus, in this work,  the state-of-art CE to present the status quo of AZMB development is summarized.  A fictional 120 Wh kg-1 AZMB pouch cell is also proposed and evaluated revealing the improvement room and technical goal of AZMB chemistry. Despite some shared mechanisms between AZMBs and lithium metal batteries, misconceptions prevalent in AZMBs are clarified. Essentially, AZMB has its own niche in the market with unique merits and demerits. By incorporating academic and industrial insights, the development pathways of AZMB are suggested.

Ultra-stable Zinc Metal Anodes at -20 °C through Eutectic Solvation Sheath in Chlorine-functionalized Eutectic Electrolytes with 1,3-Dioxolane.

The brain-storm of designing low-cost and commercialized eutectic electrolytes for zinc (Zn)-based electrochemical energy storage (ZEES) remains unresolved and attractive, especially when implementing it at low temperatures. Here, we report an appealing layout of advancing chlorine-functionalized eutectic (Cl-FE) electrolytes via exploiting Cl anion-induced eutectic interaction with Zn acetate solutions. This novel eutectic liquid shows high affinity to collaborate with 1,3-dioxolane (DOL) and is prone to constitute Cl-FE/DOL-based electrolytes with a unique inner/outer eutectic solvation sheath for the better regulation of Zn-solvating neighboring and reconstruction of H-bonding. The side reactions are effectively restricted on Zn anodes and a high Coulombic efficiency of 99.5 % can be achieved over 1000 cycles at -20 °C with Zn//Cu setups. By prototyping scale-up Zn-ion pouch cells using the optimal eutectic liquid of 3ZnOAc1.2 Cl1.8 -DOL, we obtain improved electrochemical properties at -20 °C with a high capacitance of 203.9 F g-1 at 0.02 A g-1 in a range of 0.20-1.90 V and long-term cycling ability with 95.3 % capacitance retention at 0.2 A g-1 over 3,000 cycles. Overall, the proposal of ideal Cl-FE/DOL-based electrolytes guides the design of sub-zero and endurable aqueous ZEES devices and beyond.

Regulating Zinc Nucleation Sites and Electric Field Distribution to Achieve High-Performance Zinc Metal Anode via Surface Texturing.

Understanding zinc (Zn) deposition behavior and improving Zn stripping and plating reversibility are significant in developing practical aqueous Zn ion batteries (AZIBs). Zn metal is abundant, cost-effective, and intrinsically safe compared with Li. However, their similar inhomogeneous growth regime harms their practicality. This work reports a facile, easily scalable, but effective method to develop a textured Zn with unidirectional scratches on the surface that electrochemically achieves a high accumulated areal capacity of 5530 mAh cm-2 with homogenized Zn deposition. In symmetric cells, textured Zn presents a stable cycling performance of 1100 hours (vs 250 h of bare Zn) at 0.5 mA cm-2 for 0.5 mAh cm-2 and lower nucleation and plating overpotentials of 120.5 and 41.8 mV. In situ optical microscopy and COMSOL simulation disclose that the textured surface topography can 1) homogenize the electron field distribution on the Zn surface and regulate Zn nucleation and growth, and 2) provides physical space to accommodate Zn deposits, prevent the detachment of "dead" Zn, and improve the structural sufficiency of Zn anode. Moreover, differential electrochemical mass spectrometry analysis find that the textured Zn with regulated interfacial electron activity also presents a higher resistance toward hydrogen evolution and other parasitic reactions.

Enhanced Potassium Storage Performance for K-Te Batteries via Electrode Design and Electrolyte Salt Chemistry.

Potassium batteries are an emerging energy storage technology due to the large abundance of potassium, low cost, and potentially high energy density. However, it remains challenging to find suitable electrode materials with high energy density and good cycling stability due to the structural instability and kinetics issues resulting from large size K+. Herein, a durable and high-capacity K-Te battery was developed by rational design of a Te/C electrode and electrolyte salt chemistry. A well-confined Te/C cathode structure was prepared by using a commercially available activated carbon as the Te host via a melt-diffusion method. Compared to bulky Te, the confined Te/C electrode exhibited greatly improved cycling stability, specific capacity, and rate capability in K-Te batteries. Moreover, it was found that the electrolyte salts (KPF6 and KFSI) had significant impacts on the electrochemical performance of K-Te batteries. The Te/C electrode in the KPF6-based carbonate electrolyte exhibited higher specific capacity and better rate performance than the Te/C electrode in the KFSI-based one. Mechanism studies revealed that the KPF6 salt resulted in an organic species-rich solid-electrolyte interphase (SEI) on the Te/C electrode, allowing for fast electron transfer and K-ion diffusion and enhanced K-ion storage performance in K-Te batteries. In contrast, KFSI salt led to the formation of KF-rich SEI layers, which had much higher resistances for electron and K-ion transport and was less effective for the well-confined Te/C electrode. Our work finds that the Te electrode and electrolyte chemistry need to be simultaneously optimized and tailored toward K-ion storage in K-Te batteries. It is expected that the finding reported herein might be inspirable for the future development of K-chalcogen (S/Se/Te) batteries.

Pseudocapacitive Crystalline MnCo2O4.5 and Amorphous MnCo2S4 Core/Shell Heterostructure with Graphene for High-Performance K-Ion Hybrid Capacitors.

Potassium-ion capacitors (KICs) have received a surge of interest because of their higher reserves and lower costs of potassium than lithium. However, the cycle performance and capacity of potassium devices have been reported to be unsatisfactory. Herein, a unique crystalline MnCo2O4.5 and amorphous MnCo2S4 core/shell nanoscale flower structure grown on graphene (MCO@MCS@rGO) was synthesized by a two-step hydrothermal process and demonstrated in KICs. The MCO@MCS@rGO exhibits improved electrical conductivity and excellent structural integrity during the charging and discharging process. The reasons could be attributed to the cavity structure of MCO, the mechanical buffer and high electrolyte diffusion rate of MCS, and the auxiliary effect of graphene. The electrical conductivity of MCO@MCS shows a specific capacity of 272.3 mA h g-1 after 400 cycles at 1 A g-1 and a capacity of 125.6 mA h g-1 at 2 A g-1. Besides, the MCO@MCS@rGO and high-surface-area activated carbon in KICs exhibit a relative energy density of 85.3 W h kg-1 and a power density of 9000 W kg-1 and outstanding cycling stability with a capacity retention of 76.6% after 5000 cycles. Moreover, the reaction mechanism of MCO@MCS@rGO in the K-ion cell was investigated systematically using X-ray diffraction and transmission electron microscopy, providing guidance on the further development of pseudocapacitive materials.