Organic molecules such as 9,10-phenanthrenequinone have shown promise as active materials for cathodes in aqueous rechargeable zinc-ion batteries. However, organic molecules are commonly prone to inactivation during charge and discharge that can result in substantial capacity fade, limiting their operational lifespan. One technique to stabilize quinone active materials is covalent grafting on a conductive carbon substrate via diazonium salt reactions. Although explored for other battery chemistries (e.g., Li-ion), this study applies the chemical grafting technique to stabilize 9,10-phenanthrenequinone on carbon black for rechargeable zinc-ion battery cathodes. In one example, cathodes with 9,10-phenanthrenequinone grafted to carbon black maintained a discharge capacity of 99 mAh g-1 (67 % capacity retention) after 1000 cycles of accelerated testing (200 mA g-1), a 12 % improvement in capacity retention compared to cathodes consisting of 9,10-phenanthrenequinone simply adsorbed on carbon black. Grafting was found to restrict quinone mobility and inactivation, leading to increased battery capacity retention and operational lifespan. Such an increase in capacity retention highlights how grafting can be a useful quinone stabilization tool, which could be applied to other organic cathode designs. This work not only emphasized the impact that different carbon substrates can have on organic cathode behaviour, but also demonstrated how grafting organic materials to a carbon substrate is a simple modification that improves organic cathode performance in zinc-ion batteries.

Currently explored rechargeable aqueous zinc-ion battery (RAZIB) cathode materials, such as α-MnO_2, suffer from severe capacity fade when cycling at rates appropriate for grid-scale operation. Mn dissolution has been previously identified as the cause of α-MnO_2 cathode degradation during RAZIB cycling, with conflicting evidence being found in support of the proposed Jahn-Teller effect-assisted charge disproportionation reaction as the mechanism behind Mn dissolution. In order to unveil the Mn dissolution mechanism in MnO_2 cathode cells under RAZIB operation conditions, the energetic feasibility for Mn vacancy formation was probed in both charged (MnO_2) and discharged (ZnMn_2O_4) phases of α and λ polymorphs of MnO_2 using density functional theory. The formation of a Mn vacancy, and consequently the dissolution of Mn as Mn^2+_(aq), was found to be thermodynamically feasible for the α-ZnMn_2O_4 phase due to the energetically unfavourable Zn bent coordination formed during the Zn^2+ intercalation process, indicating that Mn dissolution is promoted by an unstable Zn coordination environment. The theoretical calculations were then corroborated by operando ^1H nuclear magnetic resonance experiments which captured the Mn dissolution occurring throughout the RAZIB discharge, with subsequent electrochemical deposition of the Mn atoms on the electrode during charge. The combined computational and experimental analysis reveals the critical role of defect energetics and coordination environment in driving active material dissolution, and consequently capacity fade, with the proposed mechanism also relevant for understanding cathode degradation in other intercalating ion battery chemistries.

Rechargeable aqueous zinc-ion batteries (RAZIBs) attract major interest for deployment in grid-scale energy storage due to higher safety and lower cost when compared to lithium-ion batteries. However, currently studied cathode materials suffer from capacity fade when cycling at rates appropriate for grid-scale applications (< C/2). To address the present limitation on cathode material availability, more than 2000 previously synthesized oxides, chalcogenides, Prussian blue analogues, and polyanion materials were computationally screened for the discovery of highly stable RAZIB cathode materials. The structural, electrochemical, and chemical properties of the materials were respectively evaluated through an investigation of the available Zn^2+ percolation paths, the stability of the material in aqueous media under RAZIB operation conditions, and the attained transition metal oxidation state during cycling. The transition metal oxidation state and intercalating ion coordination environment were determined to govern the magnitude of the calculated Zn^2+ intercalation potential, with this finding guiding the development of batteries with high operation voltages. 12 materials previously unexplored as cathodes for RAZIBs were identified to have promising operational properties as cathodes, such as high Zn^2+ (de)intercalation potential, electrochemical stability, theoretical gravimetric capacity, and energy density. Finally, α-FePO_4 was experimentally tested as a RAZIB cathode, with a main redox peak observed from cyclic voltammetry matching previous results for amorphous FePO_4 as a cathode for RAZIB. However, the subpar charge storage performance highlights the necessity of further experimental investigations. Overall, the materials identified in this study present a guide for the experimental development of stable next-generation cathode materials for RAZIBs.

The implementation of renewable electricity into the grid requires efficient grid-energy storage systems for balancing supply and demand. Rechargeable zinc-ion batteries (ZIBs) are a low-cost, safe option for grid energy storage; however, challenges pertaining to energy storage capacity, round-trip efficiency, stability, and reliance on critical minerals still need to be addressed. Herein, 3,5-di-tert-butyl-ortho-benzoquinone (TBOBQ) was evaluated as an organic cathode material for ZIBs, achieving a maximum theoretical specific capacity of 246 mAh/g at 40 mA/g (C/4) with a 1 to 1 mass ratio of TBOBQ-to-acetylene black. The observed charge and discharge curves presented a voltage hysteresis of only 100 mV, resulting in a round-trip efficiency of 90 %. Degradation of the TBOBQ cathode was attributed to fractional dimerization and dissolution during discharge, as observed by nuclear magnetic resonance, mass spectroscopy, and rotating ring disk electrode. This work sets the stage for the development of organic ZIB cathodes based on TBOBQ with high discharge capacities and energy efficiency.

The implementation of renewable electricity generation, like wind and solar, is hindered by their strong dependence on weather conditions, which renders these energy sources unreliable for on-demand electricity grid supply. To address the intermittency of renewable energy sources, aqueous rechargeable zinc-ion batteries (ZIBs) offer attractive advantages such as safety, low cost, and recyclability. Currently, ZIBs face important technological challenges, particularly related to energy density and operational durability of the cathode materials conventionally used. Organic molecules offer advantages over metal-oxide based cathodes such as MnO 2 due to the flexibility in molecular structure design to tailor redox properties and stability. Additionally, organic materials can be synthesized as opposed to relying on extraction (mining) of raw mineral inputs, which can damage the environment. However, organic cathodes experience important drawbacks that primarily affect their capacity stability, like dissolution during battery cycling, and inactivating side reactions. In this work, we aim to enhance the discharge capacity and capacity retention of an organic cathode material with anhydride groups (parent molecule) through the chemical modification of its structure employing a scalable process. The product obtained (synthesized material) incorporates additional organic sites for energy storage and substitutes the anhydride groups for imide groups. Cyclic voltammetry of the synthesized material showed improved electrochemical stability compared to the parent molecule, which exhibited constant shifts in the number of redox peaks and peak voltage. In the galvanostatic cycling, the synthesized material delivered higher discharge capacity at the initial discharge, compared to its parent molecule. Additionally, the capacity retention over 200 cycles at 100 mA/g was 26% higher for the synthesized material compared to the parent molecule, reducing the capacity fade rate by 2.71 mAh/g per cycle. Using Fourier transform infrared spectroscopy it was possible to observe changes in the functional groups of the synthesized material at pristine state, after the first discharge and after the first charge. The possible degradation mechanisms were investigated through rotating ring disk electrode, X-ray diffraction spectroscopy, and solid-state 13 C nuclear magnetic resonance. No dissolution of the synthesized material was observed as a result of battery cycling. However, changes in the crystal structure of the parent and synthesized material were observed. This work achieved important improvement in the capacity retention of organic cathode materials and set the baselines for the future in the field.

Aqueous rechargeable zinc-ion batteries (ZIBs) are a promising addition to the energy storage landscape, particularly supporting the decarbonization of the power sector (i.e., deployment of wind and solar) as a low-cost, high-safety alternative to lithium-ion batteries. Unfortunately, wide-scale ZIB utilization is hindered in part by limited energy storage capacity and operational durability of state-of-the-art Mn oxide cathode materials. As such, we take a combined approach to investigate the impact of simultaneous inclusion of alkali metal (Li, Na, K, Rb, and Cs) and Ni additives on the structural and electrochemical properties of Mn oxide-based cathode materials for ZIBs. We used a facile, scalable synthesis approach to prepare 15 unique Mn oxide-based cathode materials and identified several materials capable of delivering a practical rate (i.e., C/10) discharge capacity of >150 mAh g-1 and a fast charge (i.e., 1C) capacity retention of >90% after 200 cycles. Detailed characterization of the prepared materials revealed the use of alkali metal additives during synthesis impacted both phase structure and electrochemical performance. Modifying the phase structure of Mn oxides resulted in an elevated Zn2+ diffusion coefficient for K-containing materials and a subsequent increase in deliverable capacity. Furthermore, the incorporation of Ni in the structure was shown to have no meaningful contribution to improved capacity within the aqueous electrolyte stability window, although a slight uptick in capacity retention was observed for all prepared materials as Ni content was increased. Considering the narrow range of reported cathodes for ZIBs, this work provides insight on the important interplay between structure, composition, and improved performance of Mn oxide-based cathodes, helping accelerate future material development efforts necessary for ZIB commercialization.

The rising concern towards the amount of anthropogenic carbon emissions and their effects on the environment has motivated the transition away from fossil fuels. The implementation of renewable energy sources has promoted the decarbonization of the power sector, but the variability of wind and solar energy necessitates the parallel deployment of high-performance energy storage infrastructure to ensure a reliable on-demand supply of green electricity to the grid. To this end, aqueous rechargeable zinc-ion batteries (ZIBs) are a promising new option for stationary energy storage owing to their high safety and low cost, when compared to established storage technologies like lithium-ion batteries. However, ZIBs are still limited by several technological challenges that hinder their uptake for commercial energy storage installations. In particular, the positive electrode materials, mostly comprised of metal oxides, are restraining the energy density and stability of the batteries and are yet under investigation. Low cost, long cycle life, and natural abundance are required properties of materials used in batteries for stationary energy storage. The search for materials with these properties has motivated the investigation of alternatives to metal oxides. One group of materials attracting considerable research attention is organic compounds which offer advantages like their natural abundance and high theoretical capacities. In this work, we developed an organic positive electrode for ZIBs using carbonyl groups as redox-active centers to provide energy storage capacity at round-trip energy efficiencies that are higher than the conventionally utilized manganese oxide electrodes. Furthermore, we investigated the effects of the conductive carbon additive on the deliverable capacity of the battery and elucidated the charge storage mechanism of this positive electrode material through detailed characterization. The results indicated that both Zn2+ and H+ are involved in the energy storage process of this organic electrode material. In addition to studying the energy storage process, degradation mechanisms were identified through nuclear magnetic resonance (NMR) and mass spectroscopy (MS). Both dissolution of the reduced form of the active material from the electrode and the formation of unwanted decomposition products are important contributors to the capacity fade of the battery. The technological and scientific insights provided in this presentation will thereby contribute towards the development of high-performance and naturally abundant electrode materials for the next generation of ZIBs to enable clean energy grid storage.

Rechargeable zinc-ion batteries (RZIBs) are a promising multivalent battery technology for grid-scale energy storage applications, thanks to their abundant materials, lower environmental impact, and higher safety due to the use of aqueous electrolytes as compared to lithium-based batteries. However, there is still a lack of cathode materials with suitable stability and performance for reliable implementation in these energy storage applications. In this study, we have utilized readily available thermodynamic properties obtained from first-principle atomistic simulations to calculate the intercalation potential of zinc in numerous potential candidate cathode materials. We confined our chemical space to simple transition metal oxides (MxOy, where M is a transition metal). While some materials in this class were previously experimentally studied (e.g., MnO2, V2O5, MoO3), a literature survey revealed multiple oxides for which no prior investigation on their use as cathodes for RZIBs had been performed. We considered previously reported structures with similar atomic arrangements for the charged and discharged phases, the feasibility of experimental realization of the materials, the electrochemical stability of the charged cathode in an aqueous environment, and the potential degradation of aqueous electrolytes in our analysis. We mapped the zinc intercalation potential for over 50 redox pairs involving oxides of 12 different elements. These calculated theoretical potentials were then compared to previously obtained experimental results, with the relatively small difference between them (approximately 0.2 V) demonstrating the predictive capabilities of the utilized methodology. Previously overlooked materials with high intercalation potential (above 1.6 V vs Zn/Zn2+) were then proposed as cathode materials for RZIBs. The Zn2+ intercalation potential mapping for the oxide redox pairs achieved in this study provides a roadmap for future experimental investigations of novel cathode materials for RZIBs.

Aqueous rechargeable zinc-ion batteries (ZIBs) are a promising addition to the current energy storage landscape, particularly supporting the decarbonization of the power sector as a low-cost, high safety alternative to lithium-ion batteries. Unfortunately, the relative infancy of ZIBs means that there are a limited number of reported cathode materials, and a divisive understanding of the operating principles for those which have been reported including Mn- and V-oxides. The large solvation shell of the working cation (Zn2+) imparts several design requirements for cathode material development, specifically the need for sufficient void space for Zn2+ intercalation, further limiting the materials which have been reported. Looking to other well-established battery chemistries, we considered the use of layered mixed metal oxides (MMOs) with Mn due to its known electrochemical activity within the operating voltage of aqueous ZIBs. We developed several MMO cathodes with tuned interlayer distance to achieve the larger void spacing capable of accommodating Zn2+. We investigated the impact of composition on the structural and electrochemical properties of 15+ different MMO materials. We determined that interlayer spacing plays critical role in electrochemical performance and that there is an optimal composition to provide enhanced specific capacity to the battery. Considering the narrow range of reported ZIBs cathodes, in this study we proposed several new materials that expand the scope of viable cathodes for next generation ZIBs and provides direction for future researchers to accelerate new material development for this technology.

The development of safe, inexpensive, and long service life stationary energy storage infrastructure is critical to support the decarbonization of the power and automotive sectors. While lithium-ion batteries are considered the industry standard of excellence for applications requiring high energy density, they may not be the best choice for all applications, particularly stationary energy storage. This study presents rechargeable Zn-ion batteries (ZIBs) as a promising technology primed for greater utilization in stationary applications. We consider the main benefits and challenges of ZIBs by comparing key characteristics such as cost, safety, environmental impact, and lifetime with pumped hydro, compressed air, lithium-ion, lead-acid, and redox-flow batteries. The low projected manufacturing costs, high safety, and excellent recyclability of ZIBs highlight the potential success of the technology. However, commercialization efforts are bottlenecked by active material dissolution, a lack of realistic performance demonstrations, and the need for manufacturing validation and cost analysis at the pilot scale. Considering recent advancements to lifetime and capacity of ZIBs, we propose a modified research approach including performance analysis of high-loading electrodes, in situ/operando characterization of reaction mechanisms, and standardized testing protocols and reporting to move beyond the benchtop battery and better facilitate ZIB commercialization.

We propose a comprehensive set of indicators (including methods to obtain and analyse them) for computational screening of candidate cathode materials for rechargeable Zn-ion aqueous batteries relying on Zn$^{2+}$ intercalation processes. The indicators capture feasibility of Zn$^{2+}$ intercalation and transport within the material, the thermodynamic stability of charged and discharged material structures, electrochemical stability of the cathode material and electrolyte, volume expansion, and energy storage capacity. The approach was applied to well-known cathode materials ($\alpha$-MnO$_2$ and V$_2$O$_5$) as well as some potential alternatives (MoS$_2$, ZrP$_2$O$_7$, MoO$_3$, and FeO$_2$) to demonstrate the screening workflow and the decision making process. We show that selection of cathode materials for Zn-ion aqueous rechargeable batteries is a multifaceted problem, and first principle calculations can help to narrow down the search. Despite us being unable to identify a particularly successful cathode material, tools and techniques developed in this work can be applied more broadly to screen a wider array of potential material compositions and structures, with the goal of identifying next generation cathode materials for aqueous rechargeable batteries with the intercalation energy storage mechanism not limited to Zn$^{2+}$ ions.

Purpose:The advent of total wrist arthroplasty has allowed for motion-sparing surgical treatment for wrist arthritis. The Integra Freedom Total Wrist Arthroplasty recently incorporated locking caps into its distal component fixation to minimize implant micromotion and improve osseous integration. The purpose of this study was to assess the kinematic effect of locking caps in a cadaveric model.Methods:The Integra Freedom was implanted in 4 matched-pair cadavers and tested with and without the use of the locking caps, with the testing order randomized. Each specimen was tested on a custom testing system in a position of 15° of radial deviation, neutral position, and 15° of ulnar deviation with 25 N, 50 N, 75 N, and 100 N of compressive force. The rotation of the capitate, trapezoid, and hamate at all positions was measured using a 3-dimensional digitizer.Results:Statistical analysis showed no difference in carpal rotation between the nonlocking cap and locking cap groups at all testing loads and wrist positions. The absolute motion of the distal row was minimal. However, of the total 216 loads/positions tested, only 4 (1.8%) showed a rotation of greater than 2° and only 34 (15.7%) showed a rotation of greater than 1°.Conclusions:This study shows that in a time zero cadaveric model, the initial osseous fixation of the distal component in the Integra Freedom is robust with or without locking caps. The addition of locking caps did not have a kinematic effect on distal carpal row fixation. However, further investigation into its clinical role is necessary.Clinical Relevance:At time zero, there is minimal carpal motion after implantation of the Integra Freedom Total Wrist with functional loading. The addition of locking caps did not lead to any decrease in carpal motion.

This study reports the phase transformation behaviour associated with electrolytic manganese dioxide (EMD) utilized as the positive electrode active material for aqueous zinc-ion batteries. Electrochemical techniques, including galvanostatic charge–discharge and rotating ring-disk electrode measurements, and microstructural techniques, using X-ray powder diffraction, scanning electron microscopy, and transmission/scanning transmission electron microscopy, were utilized to characterize the positive electrode at different stages of discharge and charge of zinc-ion cells. The results indicate that, during discharge, a fraction of EMD undergoes a transformation to ZnMn 2 O 4 (spinel-type) and Zn 2+ is intercalated into the tunnels of the γ- and ε-MnO 2 phases, forming Zn x MnO 2 (tunnel-type). When a critical concentration of Mn 3+ in the intercalated Zn x MnO 2 species is reached, a disproportionation/dissolution reaction is triggered leading to the formation of soluble Mn 2+ and hydroxide (OH – ) ions; the latter precipitates as zinc hydroxide sulfate (ZHS, Zn 4 (OH) 6 (SO 4 )·5H 2 O) by combination with the ZnSO 4 /H 2 O electrolyte. During charge, Zn 2+ is reversibly deintercalated from the intergrown tunneled phases (γ-/ε-Zn x MnO 2 ), Mn 2+ is redeposited as layered chalcophanite (ZnMn 3 O 7 ·3H 2 O), and ZHS is decomposed by protons (H + ) formed during the electrochemical deposition of chalcophanite.

Tremendous work has been made in a relatively short period of time on developing the rechargeable aqueous zinc-ion battery (ZIB). The ZIB using inexpensive/abundant raw active materials is a cheaper and safer alternative to Li-ion batteries (LIBs), particularly where portability is not of primary importance. The ZIB is also considered by many to be the most promising rechargeable zinc battery technology because it addresses many of the short-comings of traditional zinc battery chemistries. By using a near-neutral pH electrolyte as compared to a strong alkaline solution, cycling of the zinc metal electrode is improved drastically. The coulombic efficiency of zinc plating/stripping is increased and internal short circuits due to dendritic growth of zinc metal are suppressed. The slightly acidic (pH 4-6) electrolyte also allows for new reversible (de)intercalation mechanisms to occur at the positive electrode. This has led to the development of several novel classes of electrode materials which store zinc cations. One such electrode material which is capable of intercalating Zn2+ cations is manganese dioxide. Compared to the alkaline Zn-MnO2 battery in which both the zinc negative electrode and the manganese dioxide positive electrodes undergo conversion reactions, the chemistry of the ZIB is simplified. Zn2+ is stripped from the negative electrode and intercalates into the positive electrode during discharge. Upon charge, Zn2+ cations de-intercalate from the positive electrode active material and plate back onto the negative electrode as zinc metal. In this work, various forms of manganese dioxide were explored in detail for use as the positive electrode active material for zinc intercalation. Different crystal structures of MnO2 were studied and several additional factors, such as particle size and morphology were found to impact the performance of Zn2+ intercalation. The diffusion coefficients were calculated and each material was cycled in a zinc-ion battery to determine its suitability as a Zn2+ intercalation electrode in a near-neutral aqueous system. Through this structure-properties correlation, general material design rules can be drawn, guiding future R&D efforts on ZIB chemistry. Figure 1

The distal radioulnar joint is inherently unstable, relying primarily on ligaments for stability. Disruption of the joint-stabilizing structures can occur in isolation or concomitantly with osseous trauma. Instability can result from dislocations, fractures, ligament injuries, or malunions. Untreated instability alters wrist and forearm kinematics, leading to pain, weakness, and possibly arthritis. In chronic instability, the native ligaments may not be reparable, necessitating a reconstructive procedure.

High-voltage (>4.3 V) rechargeable lithium (Li) metal batteries (LMBs) face huge obstacles due to the high reactivity of Li metal with traditional electrolytes. Despite their good stability with Li metal, conventional ether-based electrolytes are typically used only in <4.0 V LMBs because of their limited oxidation stability. Here we report high-concentration ether electrolytes that can induce the formation of a unique cathode electrolyte interphase via the synergy between the salt and the ether solvent, which effectively stabilizes the catalytically active cathodes and preserves their structural integrity under high voltages. Eventually, LMBs can retain 92% capacity after 500 cycles at 4.3 V with very limited Li consumption. More importantly, such ether electrolytes enable stable battery cycling not only under voltages as high as 4.5 V but also on highly demanding Ni-rich layered cathodes. These findings significantly expand knowledge of ether electrolytes and provide new perspectives of electrolyte design for high-energy-density LMBs.

Purpose Intraoperative assessment of distal radioulnar joint (DRUJ) alignment is often based on lateral radiographs whose interpretation is dependent upon positioning the forearm in neutral rotation. The dorsal tangential view (DTV) is a near-axial view of the dorsal wrist used in assessing dorsal screw penetration during radius fixation. The purpose of this study was to determine whether the DTV can also reliably assess DRUJ alignment in multiple forearm positions. Methods Four transhumeral cadaveric specimens were used to simulate an unstable DRUJ. The stabili7ing soft tissue structures of the DRUJ were sectioned. Fluoroscopic DTV images were obtained with the DRUJ of each specimen held in 5 positions: dorsally dislocated, dorsally subluxated, reduced, volarly subluxated, and volarly dislocated. In each position, images were taken with the forearm in neutral rotation, full pronation, and full supination. Three observers independently assessed DRUJ position on DTV images. Intra- and interobserver reliability were assessed in each forearm position. Results Observers correctly identified DRUJ position as reduced, volarly malreduced, or dorsally malreduced on 94% of the DTV images (97%, 95%, and 92% in the neutral, supinated, and pronated forearm positions, respectively). Weighted kappa values for intraobserver reliability were 0.965, 0.964, and 0.965 for the 3 observers. The mean kappas for intraobserver reliability were 1.000, 0.967, and 0.930 with the forearm in neutral, supinated, and pronated positions, respectively. Weighted kappa values for interobserver reliability between paired observers were 0.948, 0.912, and 0.929. The mean kappa for interobserver reliability was 0.926, 0.931, and 0.930 for the forearm in neutral, supinated, and pronated positions, respectively. Conclusions The DTV reliably demonstrated the position of the DRUJ independent of forearm rotation in a cadaveric model. Copyright (C) 2020 by the American Society for Surgery of the Hand. All rights reserved.