Beyond Lithium‐Ion Batteries

Rechargeable lithium-ion batteries (LIBs), commercially pioneered by SONY 33 years ago, have emerged as the preferred power source for portable electric devices, electric vehicles (EVs), and LIBs-based grid storage systems. This preference is attributed to their exceptional characteristics, including high electromotive force, lightweight design, and impressive energy density. LIBs are now even being explored for potential use in electric flight applications. Over several decades, significant progress has been made in developing mature electrode materials and cell architectures, such as olivine LiFePO4, layered oxides, Li-rich Mn-based materials, and graphite anodes. Generally, there remains an urgent need to continuously reduce costs, enhance safety measures, and increase energy density associated with LIBs. This demand is particularly crucial in the EVs market, where lower costs and greater energy density are required to extend the travel distance. Thus far, Li(Ni,Mn,Co)O2 (NMC) and Li(Ni,Mn,Co)O2 (NCA) compounds have been extensively studied and identified as promising cathode materials. However, the major challenges for large-scale applications are safety concerns arising from structural and thermal instability at high states-of-charge and the availability of metal resources. Another potential high-energy cathode, the Li-rich Mn-based cathode material, offers a high capacity of 378 mA h g−1 for 1.2 Li+ extraction. However, it also presents inherent issues such as low initial Coulombic efficiency, poor rate capacity, and severe voltage fading. As the materials development for LIBs is approaching its limits, the demand for lower costs, enhanced safety, resource sustainability, and higher energy density have propelled the research and development of “beyond Li-ion” battery technologies. To further promote the advancement of “beyond Li-ion” battery technologies and highlight the latest developments in this field, we have curated this special issue on “beyond Li-ion” battery technologies for Advanced Functional Materials. This special issue features cutting-edge research and advancements in the field of “beyond Li-ion” battery technologies, such as sodium-ion batteries (SIBs), potassium-ion batteries (PIBs), aqueous zinc ion batteries (AZIBs), Li/Na-S batteries, aqueous flow batteries, Li-O2 batteries, and others. This issue includes 27 peer-reviewed research articles and 8 review articles, focusing on the newest reviews and research progress in advanced “beyond Li-ion” batteries. The sub-topics include new electrode materials, high-performance electrolytes, in-situ characterization techniques, electrochemical mechanism analysis, etc. With a focus on aqueous zinc-ion batteries, Guo et al. (article number 2301291) present a comprehensive review summarizing the characteristics and storage mechanisms of the latest cathode materials and an analysis of the fundamental issues related to these materials. Zhang et al. (article number 2214538) introduce a dual-functional organic electrolyte additive, tripropylene glycol, with the aim of greatly enhancing the reversibility of AZIBs. Yu et al. (article number 2301925) present a Zn-H2O battery utilizing a heterostructured Mo2C-Ru/C as the catalyst. This alkaline-acid battery configuration demonstrates impressive performance characteristics. Wang et al. (article number 2214506) introduce a composite material consisting of MXene and Bi as the (de)intercalation cathode for AZIBs. Hu et al. (article number 2301734) present a remarkable 3D thick-network electrode with a thickness of 351 µm, achieved by utilizing exclusively 1D nanomaterials. Zhu et al. (article number 2303590) introduce a promising strategy for the atomically gradient solid electrolyte interphase (SEI) in AZIBs. To tackle the challenges of Zn dendrite formation and water-induced parasitic reactions, Zhou et al. (article number 2214033) introduce a porous polyaniline interfacial layer on the surface of the Zn metal anode. This interfacial layer effectively regulates the transport and deposition of Zn2+, resulting in an ultra-stable and highly reversible Zn anode. Chen et al. (article number 2213882) propose silicon nanoparticles as electrolyte additives to regulate the uniform electrodeposition of Zn by forming Si-O-Zn bonds. Wu et al. (article number 2301912) propose a multifunctional sieve (MS) consisting of inorganic nanolayers and organic molecule layers to solve these issues faced by Zn anode based on its trifunctional roles (accelerating Zn2+, repelling H2O, and binding OH−). Chao et al. (article number 2305621) propose utilizing the magnetoresistance effect to enhance the oxygen evolution reaction in Zn-Air batteries. Lai et al. (article number 2301964) summarize the recent development of multifunctional additives for stable and dendrite-free Li/Na/Zn anodes. SIBs and PIBs represent two promising beyond Li-ion batteries that hold the potential to address the resource limitations encountered by LIBs. By exploring these innovative solutions, we can tackle the resource challenges associated with LIBs and expand the possibilities for sustainable energy storage. Chou et al. (article number 2302281) introduce tris(pentafluorophenyl)-borane additive as ClO4− anion receptor to construct robust NaF-rich cathode-electrolyte interphase (CEI) for high-voltage SIBs at 60°C. Fan et al. (article number 2214904) introduce a co-engineering strategy to customize the internal structure of Na0.67Mn2/3Fe1/3O2 and enhance the stability of the cathode interface. Zhou et al. (article number 2302045) report the synthesis of a V-doped NASICON-type material, Na3.1MnTi0.9V0.1(PO4)3, and the advantages of using V doping. Yang et al. (article number 2301996) present interconnected micro-sheets consisting of carbon nanotubes and sulfur-doped TiO2 (CNT/S-TiO2) as high-performance anode material for SIBs. Zhan et al. (article number 2301670) report a self-formed interphase to stabilize the anode interface of Na3Zr2Si2PO12 solid electrolyte, thus improving the interphase compatibility and limiting the dendrite growth. Wang et al. (article number 2302026) introduce a defect-rich O-containing carbon fiber cloth with a superwetting property toward Na–K liquid metal via an enthalpy-driven wetting process. Chou et al. (article number 2302277) present a comprehensive summary encompassing the reasons behind the unsatisfactory initial Coulombic efficiency in hard carbon, recent advancements, and prospects. Jiao et al. (article number 2301554) present a flexible 3D hollow porous carbon nanofiber framework embedded with Sb nanoparticles (Sb@HPCNF) to control dendrite-free sodium deposition effectively. Sun et al. (article number 2303211) propose a Na5V12O32 nanobelts-based heterostructure to boost the sodium-ion kinetic characteristics for wearable SIBs. Ma et al. (article number 2214195) introduce perfluorobenzene as an additive to facilitate the formation of a NaF-rich solid electrolyte interphase (SEI) in sodium metal batteries (SMBs). Li et al. (article number 2302062) propose using an active/inactive Co-Sn alloy interface to effectively inhibit the growth of sodium dendrites under harsh test conditions for SMBs. Wu et al. (article number 2213584) summarize the recent development of the latest progress of the state-of-the-art inorganic and polymer SSEs for solid-state sodium metal batteries. Zhang et al. (article number 2301987) report mesoporous N, S-rich carbon hollow nanospheres with significantly improved charge transfer kinetics and reversible capacity in PIBs. Na/Li-S batteries suffer from the parasitic shuttle effect and sluggish redox kinetics, hindering the achievement of optimal battery performance. Chen et al. (article number 2303357) introduce a novel nanoreactor of heterometal-doped Fe–Co3O4 nanosheets for Li–S batteries. Fe atoms in the Co3O4 matrix tailor the local chemical environment and electronic structure, enhancing polysulfides adsorbability and facilitating conversion kinetics. Li et al. (article number 2301736) utilize an optical fiber Bragg grating (FBG) in sulfurized polyacrylonitrile cathode films to enable real-time assessment of the electrochemo-mechanical behaviors using different binders. Zhang et al. (article number 2304541) fabricat an organic-rich SEI to mitigate the parasitic reactions of lithium polysulfides for stabilizing Li metal anodes and achieving long-cycling Li–S batteries. Zheng et al. (article number 2214353) present a flexible carbon film implanted with single-atomic Zn−N2 moiety (Zn-N2/CF) as the S host material to effectively improve the redox kinetics and electrical conductivity for room-temperature Na-S batteries. Zhang et al. (article number 2302626) summarize the design of the host materials, mechanism, and prospects for room-temperature Na-S batteries and analyzed the electrocatalysis. Li-O2 batteries arguably possess extremely high theoretical energy among all existing battery chemistries. In this issue, Peng et al. (article number 2302000) introduce the research paradigm and summarize their applications to probe both primary and parasitic reactions of Li-O2 batteries. Lithium-metal batteries have emerged as promising candidates for enabling beyond-Li-ion batteries with significantly enhanced energy storage capabilities. Guo et al. (article number 2301638) introduce a functional separator decorated with Mg3N2 on the Li-metal surface, stabilizing the anode electrochemistry and enabling high-energy batteries with extended cycle life and enhanced safety. Additionally, two new types of batteries, including all-iron aqueous redox flow batteries and Ca-ion batteries, are promising modern alternatives to post-lithium ion batteries. Zhang et al. (article number 2302077) report an in-depth overview of current research and offers perspectives on designing the next generation of all-iron aqueous redox flow batteries. Cheng et al. (article number 2302397) propose a solvation regulation strategy based on donor number (DN) to achieve easy-desolvation and rapid storage of Ca2+ in sodium vanadate for Ca-ion batteries. To overcome the poor cycle stability and low initial coulomb efficiency of traditional Li-ion batteries, Huo et al. (article number 2301217) introduce a method to in situ generate a protective layer of MgF2 on the surface of Si during the first lithiation process. This approach leads to the formation of a durable solid electrolyte interface (SEI), resulting in outstanding cycling stability. Chou et al. (article number 2303457) analyze the role of initial Coulombic efficiency in LIBs, and reported the recent progress on effective electrolyte optimization strategies. These novel ideas allow the battery to outperform conventional Li-ion batteries. We appreciate all authors' efforts and their significant contributions to this special issue. In particular, we would like to extend our deepest gratitude to Dr. Muxian Shen for her invaluable editorial support. She has consistently displayed remarkable enthusiasm, professionalism, and attentiveness throughout this process. We sincerely hope that this special issue will serve as a source of inspiration, fostering creativity and innovation among the readers of Advanced Functional Materials. The authors declare no conflict of interest. Chaofeng Zhang is currently a professor at the Institutes of Physical Science and Information Technology, Anhui University, Hefei, China. He received his B.Sc. and M.Sc. from Lanzhou University and Fudan University, respectively. Then, he obtained his Ph.D. degree in 2013 from the University of Wollongong, Australia. Additionally, he experienced a post-doc at the National Institute of Advanced Industrial Science and Technology (AIST), Japan. His research focuses on electrochemistry for batteries, especially organic battery materials and electrolytes of aqueous zinc-ion batteries. Shulei Chou is a Professor and the founding director at the Institute for Carbon Neutralization, College of Chemistry and Materials Engineering, Wenzhou University. He obtained his Bachelor's degree (1999) and Master's degree (2004) from Nankai University, China. He received his Ph.D. from the University of Wollongong in 2010. His research focuses on energy storage materials for battery applications, especially on novel composite materials, new binders, and new electrolytes for Li/Na batteries. Zaiping Guo is an Australian Laureate Fellow at the School of Chemical Engineering, The University of Adelaide. She received her Ph.D. from the University of Wollongong in 2003 and was elected to Fellow of the Australian Academy of Science in 2023. Her research focuses on the design and application of electrode materials and electrolyte for energy storage and conversion, including rechargeable batteries, hydrogen storage, and fuel cells. Her research achievements have been recognized through numerous awards, including an ARC Queen Elizabeth II Fellowship in 2010, an ARC Future Professorial Fellowship in 2015, an ARC Laureate Fellowship (2021), and the Clarivate Analytics Highly Cited Researcher Award in 2018, 2019, 2020, 2021, and 2022. She was also awarded 2020 NSW Premier's Prizes for Science & Engineering for Excellence in Engineering or Information and Communications Technology. Shi Xue Dou is professor and director of Institute of Energy Materails Science (IEMS) at the University of Shanghai for Science and Technology. He was the founding director of Institute for Superconducting & Electronic Materials (ISEM) at the University of Wollongong. He received his Ph.D. at Dalhousie University, Canada in 1984, DSc at the University of New South Wales in 1998 and was elected as a Fellow of the Australian Academy of Technological Science and Engineering in 1994. He was awarded the Australian Government's Centenary Medal in 2003, and Medal of Australian Order of Member in 2019, and the ICMC Lifetime Achievement Award in 2021. His research focuses on energy and electronic materials. He has supervised and co-supervised 110 Ph.D. students, and more than 70 postdoctoral and visiting fellows.