Metallurgical production significantly contributes to the global economy, concomitantly however, it produces waste as slag. Although some is used as an aggregate in construction, most slag is discarded. However, with Ni-Co slag, leaching supplemented with removal of impurities together with regulation of ratio of Ni-Co-Mn, can be used to produce Ni-Co-Mn sulfate solution. Significantly, this can be used in preparation of LiNixCoyMn1_ x_ yO2 cathode material(s) in which it is important to remove metal hetero ions and regulate concentration of salt ions including, Na+, NH4+ and SO4 2_ . To establish the effect of NH4+ on synthesis, we report carbonate co-precipitation to synthesize LiNi1/3Co1/3Mn1/3O2 and use (NH4)2SO4 to balance precipitation and coordination reactions to regulate crystal nucleation and growth of the microstructure and composition of LiNi1/3Co1/3Mn1/3O2. We evidence that the material (N-0.5), obtained at a (NH4)2SO4 concentration of 0.5 mol L_ 1, exhibited 'best' specific capacity, cycling performance and rate capability. We confirm that this is a result of the combination of intergranular pores favorable for penetration of electrolyte, together with a compact structure to inhibit the structural fragmentation during cycling and lower degree of Li/Ni mixing. We conclude findings can be applied for recycling of waste slag into valuable electrode material(s). Findings will benefit environmental sustainability in repurposing waste for a circular economy.

Polymer interphase on Zn anodes obviates dendrite growth and significant side reactions including corrosion and hydrogen evolution in aqueous zinc ion batteries (AZIBs), however has drawbacks of slow kinetics and large overpotential for Zn plating/stripping that prevent practical application especially under high-rate conditions. Here, a multifunctional polymer interphase with fast kineticsis reported, using poly(phenazine-alt-pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π-conjugated structure and enriched polar pyridine (conjugated cyclic −C=N−) and carbonyl (C=O) groups, preferentially adsorbs on the Zn anode to form a stable solid-electrolyte interphase (SEI) layer in situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π-conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn 2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de-solvation and diffusion of Zn 2+ . As a result, the Zn metal anode with PPPA/ZnSO 4 electrolyte exhibits high Coulombic efficiency of 98.3 % at current density of 20 mA  cm −2 , and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm −2 and plating/stripping capacity of 5 mAh cm −2 . The Zn||MnO 2 full battery exhibited a discharge capacity of 74.4 mAh g −1 after 5000 cycles at the current density of 2000 mA g −1 , demonstrating practical feasibility. It is concluded that judicious engineering of polymer additives and interphase will benefit the development of commercial AZIBs with fast kinetics for high-rate applications.

Aqueous zinc batteries are practically promising for large-scale energy storage because of cost-effectiveness and safety. However, application is limited because of an absence of economical electrolytes to stabilize both the cathode and anode. Here, we report a facile method for advanced zinc-iodine batteries via addition of a trace imidazolium-based additive to a cost-effective zinc sulfate electrolyte, which bonds with polyiodides to boost anti-self-discharge performance and cycling stability. Additive aggregation at the cathode improves the rate capacity by boosting the I-2 conversion kinetics. Also, the introduced additive enhances the reversibility of the zinc anode by adjusting Zn2+ deposition. The zinc-iodine pouch cell, therefore, exhibits industrial-level performance evidenced by a similar to 99.98% Coulombic efficiency under ca. 0.4C, a significantly low self-discharge rate with 11.7% capacity loss per month, a long lifespan with 88.3% of initial capacity after 5000 cycles at a 68.3% zinc depth-of-discharge, and fast-charging of ca. 6.7C at a high active-mass loading >15 mg cm(-2). Highly significant is that this self-discharge surpasses commercial nickel-metal hydride batteries and is comparable with commercial lead-acid batteries, together with the fact that the lifespan is over 10 times greater than reported works, and the fast-charging performance is better than commercial lithium-ion batteries.

In extreme environments people will have different needs for medicine(s), making it crucial to understand how such environments affect drug efficacy. Ibuprofen, commonly used in tablet formulation on Earth, could fail in space despite standard pharmaceutical packaging. We introduce the concept of ‘space medicines’, where solid-dosage forms protect the pharmaceutical from accelerated degradation in spaceflight. We simulate dose(s) in International Space Station (ISS) through radionuclide and photon experiments, and establish the impact of alpha, beta and gamma rays. We demonstrate that tablet formulation protects from impact of alpha and beta rays; however, gamma rays decompose ibuprofen even when ‘masked’. We systematically analyse 19 tablet compositions inside and outside the ISS to determine the effect of compositional changes in the tablet matrix. We confirm that the iron oxide-shielded tablets show minimal degradation (〈10%) inside the ISS, compared to moderate reductions (〉10%) for other formulations, with one exception. The tablets exhibited significantly greater ibuprofen degradation (〉 30-50%) outside ISS, due to harsh conditions. Significantly, we found that flavour have shielding potential by scavenging free radicals. We conclude that ibuprofen efficacy is adversely affected in space, and these effects are expected to worsen on missions to deeper space destinations.

Aqueous sodium-ion batteries are practically promising for large-scale energy storage, however energy density and lifespan are limited by water decomposition. Current methods to boost water stability include, expensive fluorine-containing salts to create a solid electrolyte interface and addition of potentially-flammable co-solvents to the electrolyte to reduce water activity. However, these methods significantly increase costs and safety risks. Shifting electrolytes from near neutrality to alkalinity can suppress hydrogen evolution while also initiating oxygen evolution and cathode dissolution. Here, we present an alkaline-type aqueous sodium-ion batteries with Mn-based Prussian blue analogue cathode that exhibits a lifespan of 13,000 cycles at 10 C and high energy density of 88.9 Wh kg −1 at 0.5 C. This is achieved by building a nickel/carbon layer to induce a H 3 O + -rich local environment near the cathode surface, thereby suppressing oxygen evolution. Concurrently Ni atoms are in-situ embedded into the cathode to boost the durability of batteries.

Multi-site catalysis of high-entropy hydroxides for co-production of glucaric acid and ammonia.

Growth in intermittent renewable sources including solar and wind has sparked increasing interest in electrical energy storage. Grid-scale energy storage integrated with renewable sources has significant advantages in energy regulation and grid security. Aqueous zinc-ion batteries (AZIBs) have emerged as a practically attractive option for electrical storage because of environmentally benign aqueous-based electrolytes, high theoretical capacity of Zn anode, and significant global reserves of Zn. However, application of AZIBs at the grid-scale is restricted by drawbacks in cathode material(s). Herein, a comprehensive summary of the features and storage mechanisms of the latest cathode materials is provided. The fundamental problems and corresponding in-depth causes for cathode materials is critically reviewed. It is also assess practical challenges, appraise their translation to commerce and industry, and systematically summarize and discuss the potential solutions reported in recent works. It is established necessary design strategies for Zn anodes and electrolytes that are matched with cathode materials for commercializing AZIBs. Finally, it is concluded with a perspective on the practical prospects for advancing the development of future AZIBs. Findings will be of interest and benefit to a range of researchers and manufacturers in the design and application of AZIBs for grid-scale energy storage.

Iron-based materials with significant physicochemical properties, including high theoretical capacity, low cost and mechanical and thermal stability, have attracted research attention as electrode materials for alkali metal-ion batteries (AMIBs). However, practical implementation of some iron-based materials is impeded by their poor conductivity, large volume change, and irreversible phase transition during electrochemical reactions. In this review we critically assess advances in the chemical synthesis and structural design, together with modification strategies, of iron-based compounds for AMIBs, to obviate these issues. We assess and categorize structural and compositional regulation and its effects on the working mechanisms and electrochemical performances of AMIBs. We establish insight into their applications and determine practical challenges in their development. We provide perspectives on future directions and likely outcomes. We conclude that for boosted electrochemical performance there is a need for better design of structures and compositions to increase ionic/electronic conductivity and the contact area between active materials and electrolytes and to obviate the large volume change and low conductivity. Findings will be of interest and benefit to researchers and manufacturers for sustainable development of advanced rechargeable ion batteries using iron-based electrode materials.

Catalytic upcycling of plastic wastes offers a sustainable circular economy. Selective conversion of the most widely used polyester, polyethylene terephthalate (PET), under ambient conditions is practically attractive because of low energy consumption and carbon footprint. Here, we report selective, aerobic conversion of PET in a flow reactor using TiO2 photocatalyst modified with atomic Pd and metallic PdCu (Pd1Cu0.4-TiO2) under ambient conditions. We demonstrate that atomically synergistic Pd1Cu0.4-TiO2 exhibits a formate evolution of 4707 mu mol g-1 h-1 with a selectivity of 92.3% together with trace CO x released. Importantly, we show that this corresponds to 10-103 times greater activity than reported photocatalytic systems. We confirm that synergy between atomic Pd and metallic PdCu boosts directional charge transfer and oxygen-induced C-C cleavage and inhibits product decomposition. We conclude that photocatalytic waste plastic-to-chemical conversion is sustainable via targeted engineering of atomically synergistic catalysts and reaction systems.

Nanoparticle-based products are stable at high pressure and temperature and subjected to advanced quality controls used during food production, processing, and packaging. For that, a critical review for the first time, on the integration of nano-dimension materials including, nano-based filter membranes, nano-based sensors, and nano-coating(s), and the impact of these materials on food quality control during the selected production phase(s) is reported here. The paper focuses on appraising different nanomaterials and methods for improving antibacterial capability, detection thresholds, and product freshness and quality to improve the physical, biochemical, and active function of foods. Furthermore, examining obstacles to nanomaterial development(s) provides a perspective on future trends for increasing nanoparticle integration with food quality processes and packaging. The review evidence that the use of nanomaterials as packaging additives has resulted in improved food preservation and shelf-life and low environmental impact, which critically assesses limitations for the application of nano-dimension materials because of practical challenges in nanomaterial safety risks, sensitivity, uniformity, dispersion, solubility, homogeneity and suitability for mass production. Environmental safety assessment and consumer perception on the application of nanomaterials for food packaging and quality are then discussed in detail at different aspects and perceptions. It concluded that the nanoscale filter membrane has significant nanometric pore and surface functionalization that provides a practical platform for more biomolecules on biosensor surfaces to boost overall specificity and sensitivity. Findings will be of interest and benefit to a range of researchers in food nanotechnology and manufacturers of equipment for food quality, safety, and control of food processing.

The activity of electrocatalysts for the sulfur reduction reaction (SRR) can be represented using volcano plots, which describe specific thermodynamic trends. However, a kinetic trend that describes the SRR at high current rates is not yet available, limiting our understanding of kinetics variations and hindering the development of high-power Li||S batteries. Here, using Le Chatelier’s principle as a guideline, we establish an SRR kinetic trend that correlates polysulfide concentrations with kinetic currents. Synchrotron X-ray adsorption spectroscopy measurements and molecular orbital computations reveal the role of orbital occupancy in transition metal-based catalysts in determining polysulfide concentrations and thus SRR kinetic predictions. Using the kinetic trend, we design a nanocomposite electrocatalyst that comprises a carbon material and CoZn clusters. When the electrocatalyst is used in a sulfur-based positive electrode (5 mg cm −2 of S loading), the corresponding Li||S coin cell (with an electrolyte:S mass ratio of 4.8) can be cycled for 1,000 cycles at 8 C (that is, 13.4 A g S −1 , based on the mass of sulfur) and 25 °C. This cell demonstrates a discharge capacity retention of about 75% (final discharge capacity of 500 mAh g S −1 ) corresponding to an initial specific power of 26,120 W kg S −1 and specific energy of 1,306 Wh kg S −1 .

Anode-free sodium batteries (AFSBs) with high energy density and cost-efficiency are practically promising for the transition to clean-energy society. However, application is limited because of low coulombic efficiency (CE) and limited cycle-life, together with a lack of understanding in device energy density and cost. Here we report a critical assessment of selected AFSBs with lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) from energy density and cost perspectives, based on commercial 4680 cylindrical construction. We establish reasons for low cycle-life of AFSBs and summarize current research in AFSBs. We confirm energy density range, materials cost, and potential demand for AFSBs via computation based on 4680 battery devices. We show the impact of active sodium ions and cathode active sites on cycle life. We compare the improvements in cycle-life achieved though electrolyte innovation, artificial solid electrolyte interphase (SEI) engineering, current collector modification, and pre-sodiation, along with the resulting energy density. We provide perspectives on likely future research to boost practical application of AFSBs. We conclude that findings will be of benefit in design for anode-free sodium batteries for clean energy storage and of interest therefore to a range of researchers in electrochemistry, materials and device engineering.

The practical utilization of Li metal anodes has been significantly plagued by the challenges of uncontrollable dendritic Li growth and poor interphase instability. Here, the study reports a novel strategy to strengthen interphase and give highly efficient active seeds concurrently to stabilize Li metal via a highly lithiophilic In2O3 decorated porous scaffold. In situ configurated fast-ion-transport Li2O-strengthened interphase layer cooperatively with highly efficient Li13In3 nucleation induction can endow the uniform Li nucleation/growth and high Li utilization efficiency. As a result, the achieved modified Li metal manifests high Coulombic efficiency, ultrahigh rate performance (5 mA cm-2), and ultra-long lifespan cycling durability (7975 cycles). Importantly, the established Li|LiFePO4 cells exhibit long-term cycling durability over 600 cycles at 1 C with an ultralow decay rate of ca. 0.017% per cycle. Moreover, the Li|LiCoO2 pouch cells with ultrahigh areal capacity of ca. 3.89 mAh cm-2 also exhibit extraordinarily prolonged cycling performance with excellent capacity retention despite extremely harsh cycling conditions of low negative-to-positive-capacity (N/P) ratio of ca. 1.7 and lean electrolyte of ca. 4.9 g Ah-1. This work enlightens a facile and effective avenue toward highly stable Li metal anode toward reliable practicability. A highly stable Li metal anode via interphase regulation coordinated with nucleation induction using robust In2O3 modified scaffold has successfully been prepared. An in situ configured fast-ion-transport Li2O-strengthened interphase with highly efficient Li13In3 nucleation induction synergistically enables highly reversible Li plating/stripping and homogeneous Li nucleation/growth. This work demonstrates a simple, efficient, and promising strategy paving Li metal toward more practicability. image

Electrolysis of natural seawater driven by renewable energy is practically attractive for green hydrogen production. However, because precipitation initiated by an increase in local pH near to the cathode deactivates catalysts or blocks electrolyzer channels, limited catalysts are capable of operating with untreated, natural seawater (viz., pH 8.2 to 8.3 and ca. 35 g salts L-1); most are used in strongly alkaline or acidic seawater. Here, we report a new natural seawater electrolysis cathode with precipitation-suppression via a Pt/WO2 catalyst to create a dynamically local acid-like environment. The in situ formed hydrogen tungsten bronze (HxWOy) phase via continuous hydrogen insertion from water acts as a proton reservoir. As a result, dynamically stored protons create a local acid-like environment near the Pt active sites. We evidence that this tailored acid-like environment boosts the hydrogen evolution reaction in natural seawater splitting and neutralizes generated OH- species to restrict precipitation formations. Consequently, a long-term stability of >500 h at 100 mA cm-2 was exhibited in direct seawater electrolysis.

This review highlights deep-eutectic solvents for green recycling of spent Li-ion battery cathodes towards future commercialization.

C-C coupling is important in electrocatalytic CO2 reduction for production of green chemicals. However, understanding of the underlying coupling mechanism(s) is poor because of the complexity of the reaction network. Here, we report a method to establish the structure-activity relationship in C-C coupling reactions via statistical analyses on a big dataset. The dataset contains a total of 45,738 adsorption data, which are generated through a combination of quantum chemical computations and machine-learning and encompasses 378 active site structures formed by 27 transition metals together with 6 potential coupling precursors. Analyses of these data establishes that, 1) asymmetric coupling mechanisms exhibit potential for greater efficiency compared with symmetric coupling, agreeing well with reported experiment, and 2) C-C coupling selectivity of Cu-based catalysts can be boosted through bimetallic doping. The three-component combination of CuAgNb exhibited superior coupling selectivity compared with both Cu and CuAg catalysts. Importantly, we experimentally substantiate the CuAgNb catalyst selected based on data screening, to demonstrate actual boosted performance in C-C coupling. We conclude that this finding evidences practicality of our theoretical model, and that combining big data with complex catalytic reaction mechanisms will become a basis or a new paradigm for accelerating optimal catalyst design for multi-carbon chemicals production.

Carbon-carbon (C-C) coupling is essential in the electrocatalytic reduction of CO2 for the production of green chemicals. However, due to the complexity of the reaction network, there remains controversy regarding the underlying reaction mechanisms and the optimal direction for catalyst material design. Here, we present a global perspective to establish a comprehensive data set encompassing all C-C coupling precursors and catalytic active site compositions to explore the reaction mechanisms and screen catalysts via big data set analysis. The 2D-3D ensemble machine learning strategy, developed to target a variety of adsorption configurations, can quickly and accurately expand quantum chemical calculation data, enabling the rapid acquisition of this extensive big data set. Analyses of the big data set establish that (1) asymmetric coupling mechanisms exhibit greater potential efficiency compared to symmetric coupling, with the optimal path involving the coupling CHO with CH or CH2, and (2) C-C coupling selectivity of Cu-based catalysts can be enhanced through bimetallic doping including CuAgNb sites. Importantly, we experimentally substantiate the CuAgNb catalyst to demonstrate actual boosted performance in C-C coupling. Our finding evidence the practicality of our big data set generated from machine learning-accelerated quantum chemical computations. We conclude that combining big data with complex catalytic reaction mechanisms and catalyst compositions will set a new paradigm for accelerating optimal catalyst design.

Owing to continuing global use of lithium-ion batteries (LIBs), in particular in electric vehicles (EVs), there is a need for sustainable recycling of spent LIBs. Deep eutectic solvents (DESs) are reported as "green solvents" for low-cost and sustainable recycling. However, the lack of understanding of the coordination mechanisms between DESs and transition metals (Ni, Mn and Co) and Li makes selective separation of transition metals with similar physicochemical properties practically difficult. Here, it is found that the transition metals and Li have a different stable coordination structure with the different anions in DES during leaching. Further, based on the different solubility of these coordination structures in anti-solvent (acetone), a leaching and separation process system is designed, which enables high selective recovery of transition metals and Li from spent cathode LiNi1/3Co1/3Mn1/3O2 (NCM111), with recovery of acetone. Recovery of spent LiCoO2 (LCO) cathode is also evidenced and a significant selective recovery for Co and Li is established, together with recovery and reuse of acetone and DES. It is concluded that the tuning of cation-anion coordination structure and anti-solvent crystallization are practical for selective recovery of critical metal resources in the spent LIBs recycling.

Operation of rechargeable batteries at ultralow temperature is a significant practical problem because of poor kinetics of the electrode. Here, we report for the first time stabilized multiphase conversions for fast kinetics and long-term durability in ultralow-temperature, organic-sodium batteries. We establish that disodium rhodizonate organic electrode in conjunction with single-layer graphene oxide obviates consumption of organic radical intermediates, and demonstrate as a result that the newly designed organic electrode exhibits excellent electrochemical performance of a highly significant capacity of 130 mAh g(-1 )at -50 C-degrees. We evidence that the full-cell configuration coupled with Prussian blue analogues exhibits exceptional cycling stability of >7000 cycles at -40 C-degrees while maintaining a discharge capacity of 101 mAh g(-1 )at a high current density 300 mA g(-1). We show this is among the best reported ultralow-temperature performance for nonaqueous batteries, and importantly, the pouch cell exhibits a continuous power supply despite conditions of -50 C-degrees. This work sheds light on the distinct energy storage characteristics of organic electrode and opens up new avenues for the development of reliable and sustainable ultralow-temperature batteries.

Aqueous zinc (Zn) batteries have attracted global attention for energy storage. Despite significant progress in advancing Zn anode materials, there has been little progress in cathodes. The predominant cathodes working with Zn2+/H+ intercalation, however, exhibit drawbacks, including a high Zn2+ diffusion energy barrier, pH fluctuation(s) and limited reproducibility. Beyond Zn2+ intercalation, alternative working principles have been reported that broaden cathode options, including conversion, hybrid, anion insertion and deposition/dissolution. In this review, we report a critical assessment of non-intercalation-type cathode materials in aqueous Zn batteries, and identify strengths and weaknesses of these cathodes in small-scale batteries, together with current strategies to boost material performance. We assess the technical gap(s) in transitioning these cathodes from laboratory-scale research to industrial-scale battery applications. We conclude that S, I-2 and Br-2 electrodes exhibit practically promising commercial prospects, and future research is directed to optimizing cathodes. Findings will be useful for researchers and manufacturers in advancing cathodes for aqueous Zn batteries beyond Zn2+ intercalation.