Liquid Metal Electrodes for Energy Storage Batteries

The increasing demands for integration of renewable energy into the grid and urgently needed devices for peak shaving and power rating of the grid both call for low‐cost and large‐scale energy storage technologies. The use of secondary batteries is considered one of the most effective approaches to solving the intermittency of renewables and smoothing the power fluctuations of the grid. In these batteries, the states of the electrode highly affect the performance and manufacturing process of the battery, and therefore leverage the price of the battery. A battery with liquid metal electrodes is easy to scale up and has a low cost and long cycle life. In this progress report, the state‐of‐the‐art overview of liquid metal electrodes (LMEs) in batteries is reviewed, including the LMEs in liquid metal batteries (LMBs) and the liquid sodium electrode in sodium‐sulfur (Na–S) and ZEBRA (Na–NiCl₂) batteries. Besides the LMEs, the development of electrolytes for LMEs and the challenge of using LMEs in the batteries, and the future prospects of using LMEs are also discussed.     

Darwin at High Temperature: Advancing Solar Cell Material Design Using Defect Kinetics Simulations and Evolutionary Optimization

Material defects govern the performance of a wide range of energy conversion and storage devices, including photovoltaics, thermoelectrics, and batteries. The success of large‐scale, cost‐effective manufacturing hinges upon rigorous material optimization to mitigate deleterious defects. Material processing simulations have the potential to accelerate novel energy technology development by modeling defect‐evolution thermodynamics and kinetics during processing of raw materials into devices. Here, a predictive process optimization framework is presented for rapid material and process development. A solar cell simulation tool that models defect kinetics during processing is coupled with a genetic algorithm to optimize processing conditions in silico. Experimental samples processed according to conditions suggested by the optimization show significant improvements in material performance, indicated by minority carrier lifetime gains, and confirm the simulated directions for process improvement. This material optimization framework demonstrates the potential for process simulation to leverage fundamental defect characterization and high‐throughput computing to accelerate the pace of learning in materials processing for energy applications.     

Anodes and Sodium‐Free Cathodes in Sodium Ion Batteries

The increase in electricity generation poses growing demands on energy storage systems, thus offering a chance for the success of the reliable and cost‐effective energy storage technologies. Sodium ion batteries are emerging as such a technology, which is however not yet mature enough to enter the market. At the crux of building practical sodium ion batteries is the development of electrode materials that promise sufficient cost‐ and performance‐competitiveness. As such, herein, all typical sodium storage materials are discussed, considering their fabrication methods and sodiation mechanisms in detail. A comprehensive cross‐literature and cross‐material comparison, which also includes the related thermodynamic analysis of their sodiation products, is also provided. The review focusses particularly on anodes and sodium‐free cathodes, as they both play the role of the acceptor rather than the donor of sodium ions in their operation in batteries; their difference lies in the (de‐)sodiation voltage. In the discussion, special attention is paid to contradictory observations and interpretations in contemporary sodium ion battery research, since debates on these controversies are likely to fuel future sodium battery research.     

Estimation of Waste Battery Generation and Analysis of the Waste Battery Recycling System in China

China produces and consumes a large amount of batteries annually, which leads to many waste batteries needing to be recycled. The collection and recycling system of primary, alkaline secondary, and lithium‐ion secondary batteries in China is particularly poor, and waste battery recycling enterprises generally sustain economic losses if they solely use waste batteries as raw materials. Increasing the profits of waste battery recycling systems is a key problem that needs to be considered. This article quantitatively analyzes waste battery generation in China by using annual sales data and probable lifetime distribution of various batteries. The results show that the rapid growth of battery usage has led to an increased generation of waste batteries and the percentage of different types of waste batteries is changing over time. In 2013, the total quantity of all waste batteries in the medium lifetime scenario reached 570 kilotons, of which primary, alkaline secondary, and lithium‐ion secondary waste batteries accounted for approximately 36%, 28%, and 35%, respectively. Based on a real‐world case study of a typical domestic waste battery recycling enterprise in China, material flow analysis and cost‐benefit analysis were conducted to study the development of the recycling process of comingled waste batteries. Through scenario analysis, we conclude that increasing the use of waste batteries as raw materials and the recycling of other materials that are less valuable reduces the profits of the waste battery recycling enterprise. Higher profits can be achieved by adding the production of high value‐added downstream products and government support. At the same time, the essential role of the government in developing a waste battery recycling system was identified. Finally, relevant suggestions are made for improvements in both the government and enterprise sectors.     

Sodium‐Ion Batteries: From Academic Research to Practical Commercialization

Sodium‐ion batteries (SIBs) have been considered as the most promising candidate for large‐scale energy storage system owing to the economic efficiency resulting from abundant sodium resources, superior safety, and similar chemical properties to the commercial lithium‐ion battery. Despite the long period of academic research, how to realize sodium‐ion battery commercialization for market applications is still a great challenge. Thus, from the perspective of future practical application, this review will identify the factors that are restricting commercialization, and evaluate the existing active materials and sodium‐ion‐based full‐cell system. The design and development trends that are needed for SIBs to meet the requirements of practical applications in large‐scale energy storage will also be discussed in detail.     

Sodium‐Ion Batteries Paving the Way for Grid Energy Storage

The recent proliferation of renewable energy generation offers mankind hope, with regard to combatting global climate change. However, reaping the full benefits of these renewable energy sources requires the ability to store and distribute any renewable energy generated in a cost‐effective, safe, and sustainable manner. As such, sodium‐ion batteries (NIBs) have been touted as an attractive storage technology due to their elemental abundance, promising electrochemical performance and environmentally benign nature. Moreover, new developments in sodium battery materials have enabled the adoption of high‐voltage and high‐capacity cathodes free of rare earth elements such as Li, Co, Ni, offering pathways for low‐cost NIBs that match their lithium counterparts in energy density while serving the needs for large‐scale grid energy storage. In this essay, a range of battery chemistries are discussed alongside their respective battery properties while keeping metrics for grid storage in mind. Matters regarding materials and full cell cost, supply chain and environmental sustainability are discussed, with emphasis on the need to eliminate several elements (Li, Ni, Co) from NIBs. Future directions for research are also discussed, along with potential strategies to overcome obstacles in battery safety and sustainable recyclability.     

Metal–Air Batteries: From Static to Flow System

As an emerging battery technology, metal–air flow batteries inherit the advantageous features of the unique structural design of conventional redox flow batteries and the high energy density of metal–air batteries, thus showing great potential as efficient electrochemical systems for large‐scale electrical energy storage. This review summarizes the operating principles and recent progress of metal–air flow batteries from a materials and chemistry perspective, with particular emphasis on the latest advanced materials design and cell configuration engineering, which the authors divide into three categories based on the anode species: vanadium–air, zinc–air, and lithium–air flow batteries. Since some of the capabilities developed for metal–air static batteries can be leveraged for next‐generation flow systems, classical works on conventional metal–air batteries are selected and compared with the metal–air flow systems, highlighting the prominent advantages of the latter in achieving high energy capacity and long cycle performance. At the end, a general perspective on current challenges/opportunities and future research directions to promote the commercial application of the metal–air flow battery technology is provided. The aim is to provide a comprehensive overview and to set up a road map for guiding development from conventional static to advanced flow technologies of metal–air batteries.     

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition,Air Stability,and Performance

The increasing demand for replacing conventional fossil fuels with clean energy or economical and sustainable energy storage drives better battery research today. Sodium‐ion batteries (SIBs) are considered as a promising alternative for grid‐scale storage applications due to their similar “rocking‐chair” sodium storage mechanism to lithium‐ion batteries, the natural abundance, and the low cost of Na resources. Searching for appropriate electrode materials with acceptable electrochemical performance is the key point for development of SIBs. Layered transition metal oxides represent one of the most fascinating electrode materials owing to their superior specific capacity, environmental benignity, and facile synthesis. However, three major challenges (irreversible phase transition, storage instability, and insufficient battery performance) are known for cathodes in SIBs. Herein, a comprehensive review on the latest advances and progresses in the exploration of layered oxides for SIBs is presented, and a detailed and deep understanding of the relationship of phase transition, air stability, and electrochemical performance in layered oxide cathodes is provided in terms of refining the structure–function–property relationship to design improved battery materials. Layered oxides will be a competitive and attractive choice as cathodes for SIBs in next‐generation energy storage devices.     

Advanced Carbon‐Based Anodes for Potassium‐Ion Batteries

The ever‐increasing demand for large‐scale energy storage systems requires novel battery technologies with low‐cost and sustainable properties. Due to earth‐abundance and cost effectiveness, the development of rechargeable potassium ion batteries (PIBs) has recently attracted much attention. Since carbon‐based materials are abundant, inexpensive, nontoxic, and safe, extensive feasibility investigations have suggested that they can become promising anode materials for PIBs. This review not only attempts to provide better understanding of the potassium storage mechanism, but also summarizes the availability of new carbon‐based materials and their electrochemical performance covering graphite, graphene, and hard carbon materials plus carbon‐based composites. Finally, the critical issues, challenges, and perspectives are discussed to demonstrate the developmental direction of PIBs.     

Recent Advances in Rechargeable Magnesium‐Based Batteries for High‐Efficiency Energy Storage

Benefiting from higher volumetric capacity, environmental friendliness and metallic dendrite‐free magnesium (Mg) anodes, rechargeable magnesium batteries (RMBs) are of great importance to the development of energy storage technology beyond lithium‐ion batteries (LIBs). However, their practical applications are still limited by the absence of suitable electrode materials, the sluggish kinetics of Mg²⁺ insertion/extraction and incompatibilities between electrodes and electrolytes. Herein, a systematic and insightful review of recent advances in RMBs, including intercalation‐based cathode materials and conversion reaction‐based compounds is presented. The relationship between microstructures with their electrochemical performances is comprehensively elucidated. In particular, anode materials are discussed beyond metallic Mg for RMBs. Furthermore, other Mg‐based battery systems are also summarized, including Mg–air batteries, Mg–sulfur batteries, and Mg–iodine batteries. This review provides a comprehensive understanding of Mg‐based energy storage technology and could offer new strategies for designing high‐performance rechargeable magnesium batteries.     

Theoretical versus Practical Energy: A Plea for More Transparency in the Energy Calculation of Different Rechargeable Battery Systems

Electrochemical energy storage at a large scale poses one of the main technological challenges of this century. The scientific community in academia and industry worldwide intensively is exploring various alternative rechargeable battery concepts beside state‐of‐the‐art lithium ion batteries (LIBs), for example, all‐solid‐state batteries, lithium/sulfur batteries, magnesium/sulfur batteries or dual‐ion batteries that could outperform LIBs in different aspects. Often, these concepts also promise very high theoretical energies per mass or volume. However, as theoretical values exclude numerous relevant parameters, they do not translate directly into practically achievable energy values: The gaps between practical capacities and voltages compared to the theoretical values differ for each system. In order to provide high transparency and to illustrate which cell components are most important in the limitation of the practical energy values, in this study, the specific energies and energy densities are calculated in six subsequent steps—from the theoretical energy values of the active materials alone to the practical energy values in an 18650 cylindrical cell. By providing a tool to calculate the energy values of six different battery technologies with different assumptions made evident, this study aims for more transparency and reliability in the comparison of different cell chemistries.     

From Lithium‐Oxygen to Lithium‐Air Batteries: Challenges and Opportunities

Lithium ‐ air batteries have become a focus of research on future battery technologies. Technical issues associated with lithium‐air batteries, however, are rather complex. Apart from the sluggish oxygen reaction kinetics which demand efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts, issues are also inherited from the nature of an open battery system and the use of reactive metal lithium as anode. Lithium‐air batteries, which exchange oxygen directly with ambient air, face more challenges due to the additional oxidative agents of moisture, carbon dioxide, etc. which degrade the metal lithium anode, deteriorating the performance of the batteries. In order to improve the cycling performance one must hold a full picture of lithium‐oxygen electrochemistry in the presence of carbon dioxide and/or moisture and fully understand the fundamentals of chemistry reactions therein. Recent advances in the exploration of the effect of moisture and CO₂ contaminants on Li‐O₂ batteries are reviewed, and the mechanistic understanding of discharge/charge process in O₂ at controlled level of moisture and/or CO₂ are illustrated. Prospects for development opportunities of Li‐air batteries, insight into future research directions, and guidelines for the further development of rechargeable Li‐air batteries are also given.     

Multi-scale modeling in biology: how to bridge the gaps between scales?

Human physiological functions are regulated across many orders of magnitude in space and time. Integrating the information and dynamics from one scale to another is critical for the understanding of human physiology and the treatment of diseases. Multi-scale modeling, as a computational approach, has been widely adopted by researchers in computational and systems biology. A key unsolved issue is how to represent appropriately the dynamical behaviors of a high-dimensional model of a lower scale by a low-dimensional model of a higher scale, so that it can be used to investigate complex dynamical behaviors at even higher scales of integration. In the article, we first review the widely-used different modeling methodologies and their applications at different scales. We then discuss the gaps between different modeling methodologies and between scales, and discuss potential methods for bridging the gaps between scales.     

Na3V2(PO4)3 as the Sole Solid Energy Storage Material for Redox Flow Sodium‐Ion Battery

Redox flow batteries have considerable advantages of system scalability and operation flexibility over other battery technologies, which makes them promising for large‐scale energy storage application. However, they suffer from low energy density and consequently relatively high cost for a nominal energy output. Redox targeting–based flow batteries are employed by incorporating solid energy storage materials in the tank and present energy density far beyond the solubility limit of the electrolytes. The success of this concept relies on paring suitable redox mediators with solid materials for facilitated reaction kinetics and lean electrolyte composition. Here, a redox targeting‐based flow battery system using the NASICON‐type Na₃V₂(PO₄)₃ as a capacity booster for both the catholyte and anolyte is reported. With 10‐methylphenothiazine as the cathodic redox mediator and 9‐fluorenone as anodic redox mediator, an all‐organic single molecule redox targeting–based flow battery is developed. The anodic and cathodic capacity are 3 and 17 times higher than the solubility limit of respective electrolyte, with which a full cell can achieve an energy density up to 88 Wh L^?1. The reaction mechanism is scrutinized by operando and in‐situ X‐ray and UV–vis absorption spectroscopy. The reaction kinetics are analysed in terms of Butler–Volmer formalism.     

Occupancy versus colonization–extinction models for projecting population trends at different spatial scales

Understanding spatiotemporal population trends and their drivers is a key aim in population ecology. We further need to be able to predict how the dynamics and sizes of populations are affected in the long term by changing landscapes and climate. However, predictions of future population trends are sensitive to a range of modeling assumptions. Deadwood‐dependent fungi are an excellent system for testing the performance of different predictive models of sessile species as these species have different rarity and spatial population dynamics, the populations are structured at different spatial scales, and they utilize distinct substrates. We tested how the projected large‐scale occupancies of species with differing landscape‐scale occupancies are affected over the coming century by different modeling assumptions. We compared projections based on occupancy models against colonization–extinction models, conducting the modeling at alternative spatial scales and using fine‐ or coarse‐resolution deadwood data. We also tested effects of key explanatory variables on species occurrence and colonization–extinction dynamics. The hierarchical Bayesian models applied were fitted to an extensive repeated survey of deadwood and fungi at 174 patches. We projected higher occurrence probabilities and more positive trends using the occupancy models compared to the colonization–extinction models, with greater difference for the species with lower occupancy, colonization rate, and colonization:extinction ratio than for the species with higher estimates of these statistics. The magnitude of future increase in occupancy depended strongly on the spatial modeling scale and resource resolution. We encourage using colonization–extinction models over occupancy models, modeling the process at the finest resource‐unit resolution that is utilizable by the species, and conducting projections for the same spatial scale and resource resolution at which the model fitting is conducted. Further, the models applied should include key variables driving the metapopulation dynamics, such as the availability of suitable resource units, habitat quality, and spatial connectivity.     

Recent Progress of the Solid‐State Electrolytes for High‐Energy Metal‐Based Batteries

Secondary batteries based on metal anodes (e.g., Li, Na, Mg, Zn, and Al) are among the most sought‐after candidates for next‐generation mobile and stationary storage systems because they are able to store a larger amount of energy per unit mass or volume. However, unstable electrodeposition and uncontrolled interfacial reactions occuring in liquid electrolytes cause unsatisfying cell performance and potential safety concerns for the commercial application of these metal anodes. Solid‐state electrolytes (SSEs) having a higher modulus are considered capable of inhibiting difficulties associated with the anodes and may enable building of safe all‐solid‐state metal batteries, yet several challenges, such as insufficient room‐temperature ionic conductivity and poor interfacial stability between the electrode and the electrolyte, hinder the large‐scale development of such batteries. Here, research and development of SSEs including inorganic ceramics, organic solid polymers, and organic–inorganic hybrid/composite materials for metal‐based batteries are reviewed. The comparison of different types of electrolytes is discussed in detail, in the context of electrochemical energy storage applications. Then, the focus of this study is on recent advances in a range of attractive and innovative battery chemistries and technologies that are enabled by SSEs. Finally, the challenges and future perspectives are outlined to foresee the development of SSEs.     

Elucidating the Irreversible Mechanism and Voltage Hysteresis in Conversion Reaction for High‐Energy Sodium–Metal Sulfide Batteries

Irreversible electrochemical behavior and large voltage hysteresis are commonly observed in battery materials, in particular for materials reacting through conversion reaction, resulting in undesirable round‐trip energy loss and low coulombic efficiency. Seeking solutions to these challenges relies on the understanding of the underlying mechanism and physical origins. Here, this study combines in operando 2D transmission X‐ray microscopy with X‐ray absorption near edge structure, 3D tomography, and galvanostatic intermittent titration techniques to uncover the conversion reaction in sodium–metal sulfide batteries, a promising high‐energy battery system. This study shows a high irreversible electrochemistry process predominately occurs at first cycle, which can be largely linked to Na ion trapping during the first desodiation process and large interfacial ion mobility resistance. Subsequently, phase transformation evolution and electrochemical reaction show good reversibility at multiple discharge/charge cycles due to materials' microstructural change and equilibrium. The origin of large hysteresis between discharge and charge is investigated and it can be attributed to multiple factors including ion mobility resistance at the two‐phase interface, intrinsic slow sodium ion diffusion kinetics, and irreversibility as well as ohmic voltage drop and overpotential. This study expects that such understandings will help pave the way for engineering design and optimization of materials microstructure for future‐generation batteries.     

Multi‐Scale Investigations of δ‐Ni0.25V2O5·nH2O Cathode Materials in Aqueous Zinc‐Ion Batteries

Cost‐effective and environment‐friendly aqueous zinc‐ion batteries (AZIBs) exhibit tremendous potential for application in grid‐scale energy storage systems but are limited by suitable cathode materials. Hydrated vanadium bronzes have gained significant attention for AZIBs and can be produced with a range of different pre‐intercalated ions, allowing their properties to be optimized. However, gaining a detailed understanding of the energy storage mechanisms within these cathode materials remains a great challenge due to their complex crystallographic frameworks, limiting rational design from the perspective of enhanced Zn²⁺ diffusion over multiple length scales. Herein, a new class of hydrated porous δ‐Ni_0.25V₂O₅.nH₂O nanoribbons for use as an AZIB cathode is reported. The cathode delivers reversibility showing 402 mAh g^?1 at 0.2 A g^?1 and a capacity retention of 98% over 1200 cycles at 5 A g^?1. A detailed investigation using experimental and computational approaches reveal that the host “δ” vanadate lattice has favorable Zn²⁺ diffusion properties, arising from the atomic‐level structure of the well‐defined lattice channels. Furthermore, the microstructure of the as‐prepared cathodes is examined using multi‐length scale X‐ray computed tomography for the first time in AZIBs and the effective diffusion coefficient is obtained by image‐based modeling, illustrating favorable porosity and satisfactory tortuosity.     

Challenges in Developing Electrodes,Electrolytes, and Diagnostics Tools to Understand and Advance Sodium‐Ion Batteries

Considering the natural abundance and low cost of sodium resources, sodium‐ion batteries (SIBs) have received much attention for large‐scale electrochemical energy storage. However, smart structure design strategies and good mechanistic understanding are required to enable advanced SIBs with high energy density. In recent years, the exploration of advanced cathode, anode, and electrolyte materials, as well as advanced diagnostics have been extensively carried out. This review mainly focuses on the challenging problems for the attractive battery materials (i.e., cathode, anode, and electrolytes) and summarizes the latest strategies to improve their electrochemical performance as well as presenting recent progress in operando diagnostics to disclose the physics behind the electrochemical performance and to provide guidance and approaches to design and synthesize advanced battery materials. Outlook and perspectives on the future research to build better SIBs are also provided.