A Comprehensive Evaluation of Battery Technologies for High-Energy Aqueous Batteries.

Aqueous batteries have garnered significant attention in recent years as a viable alternative to lithium-ion batteries for energy storage, owing to their inherent safety, cost-effectiveness, and environmental sustainability. This study offers a comprehensive review of recent advancements, persistent challenges, and the prospects of aqueous batteries, with a primary focus on energy density compensation of various battery engineering technologies. Additionally, cutting-edge high-energy aqueous battery designs are emphasized as a reference for future endeavors in the pursuit of high-energy storage solutions. Finally, a dual-compatibility battery configuration perspective aimed at concurrently optimizing cycle stability, redox potential, capacity utilization for both anode and cathode materials, as well as the selection of potential electrode candidates, is proposed with the ultimate goal of achieving cell-level energy densities exceeding 400 Wh kg-1.

Binder-Free MOF-Based and MOF-Derived Nanoarrays for Flexible Electrochemical Energy Storage: Progress and Perspectives.

The fast development of Internet of Things and the rapid advent of next-generation versatile wearable electronics require cost-effective and highly-efficient electroactive materials for flexible electrochemical energy storage devices. Among various electroactive materials, binder-free nanostructured arrays have attracted widespread attention. Featured with growing on a conductive and flexible substrate without using inactive and insulating binders, binder-free 3D nanoarray electrodes facilitate fast electron/ion transportation and rapid reaction kinetics with more exposed active sites, maintain structure integrity of electrodes even under bending or twisted conditions, readily release generated joule heat during charge/discharge cycles and achieve enhanced gravimetric capacity of the whole device. Binder-free metal-organic framework (MOF) nanoarrays and/or MOF-derived nanoarrays with high surface area and unique porous structure have emerged with great potential in energy storage field and been extensively exploited in recent years. In this review, common substrates used for binder-free nanoarrays are compared and discussed. Various MOF-based and MOF-derived nanoarrays, including metal oxides, sulfides, selenides, nitrides, phosphides and nitrogen-doped carbons, are surveyed and their electrochemical performance along with their applications in flexible energy storage are analyzed and overviewed. In addition, key technical issues and outlooks on future development of MOF-based and MOF-derived nanoarrays toward flexible energy storage are also offered.

GenAI for Scientific Discovery in Electrochemical Energy Storage: State-of-the-Art and Perspectives from Nano- and Micro-Scale.

The transition to electric vehicles (EVs) and the increased reliance on renewable energy sources necessitate significant advancements in electrochemical energy storage systems. Fuel cells, lithium-ion batteries, and flow batteries play a key role in enhancing the efficiency and sustainability of energy usage in transportation and storage. Despite their potential, these technologies face limitations such as high costs, material scarcity, and efficiency challenges. This research introduces a novel integration of Generative AI (GenAI) within electrochemical energy storage systems to address these issues. By leveraging advanced GenAI techniques like Generative Adversarial Networks, autoencoders, diffusion and flow-based models, and multimodal large language models, this paper demonstrates significant improvements in material discovery, battery design, performance prediction, and lifecycle management across different types of electrochemical storage systems. The research further emphasizes the importance of nano- and micro-scale interactions, providing detailed insights into optimizing these interactions for improved efficiency and longevity. Additionally, the paper discusses the challenges and future directions for integrating GenAI in energy storage research, highlighting the importance of data quality, model transparency, workflow integration, scalability, and ethical considerations. By addressing these aspects, this research sets a new benchmark for the use of GenAI in battery development, promoting sustainable, efficient, and safer energy solutions.

A Cross-linked n-Type Conjugated Polymer with Polar Side Chains Enables Ultrafast Pseudocapacitive Energy Storage.

Pseudocapacitors bridge the performance gap between batteries and electric double-layer capacitors by storing energy via a combination of fast surface/near-surface Faradaic redox processes and electrical double-layer capacitance. Organic semiconductors are an emerging class of pseudocapacitive materials that benefit from facile synthetic tunability and mixed ionic-electronic conduction. Reported examples are mostly limited to p-type (electron-donating) conjugated polymers, while n-type (electron-accepting) examples remain comparatively underexplored. This work introduces a new cross-linked n-type conjugated polymer, spiro-NDI-N, strategically designed with polar tertiary amine side chains. This molecular design aims to synergistically increase the electroactive surface area and boost ion transport for efficient ionic-electronic coupling. Spiro-NDI-N demonstrates excellent pseudocapacitive energy storage performance in pH-neutral aqueous electrolytes, with specific capacitance values of up to 532 F g-1 at 5 A g-1 and stable cycling over 5000 cycles. Moreover, it maintains a rate capability of 307 F g-1 at 350 A g-1. The superior pseudocapacitive performance of spiro-NDI-N, compared to strategically designed structural analogues lacking either the cross-linked backbone or polar side chains, validates the essential role of its molecular design elements. More broadly, the design and performance of spiro-NDI-N provide a novel strategy for developing high-performance organic pseudocapacitors.

Electrochemically Dealloying Engineering toward Integrated Monolithic Electrodes with Superior Electrochemical Li-Storage Properties.

Integrated monolithic electrodes (IMEs) free of inactive components demonstrate great potential in boosting energy-power densities and cycling life of lithium-ion batteries. However, their practical applications are significantly limited by low active substance loading (< 4.0 mg cm-2 and 1.0 g cm-3), complicated manufacturing process, and high fabrication cost. Herein, employing industrial Cu-Mn alloy foil as a precursor, a simple neutral salt solution-mediated electrochemical dealloying strategy is proposed to address such problems. The resultant Cu-Mn IMEs achieve not only a significantly larger active material loading due to the in situ generated Cu2O and MnOx (ca. 16.0 mg cm-2 and 1.78 g cm-3), simultaneously fast transport of ions and electrons due to the well-formed nanoporous structure and built-in Cu current collector, but also high structural stability due to the interconnected ligaments and suitable free space to relieve the volume expansion upon lithiation. As a result, they demonstrate remarkable performances including large specific capacities (> 5.7 mAh cm-2), remarkable pseudocapacitive effect despite the battery-type constitutes, long cycling life, and good working condition in a lithium-ion full cell. This study sheds new light on the further development of IMEs, enriches the existing dealloying techniques, and builds a bridge between the two.

Plasma Technology for Advanced Electrochemical Energy Storage.

"Carbon Peak and Carbon Neutrality" is an important strategic goal for the sustainable development of human society. Typically, a key means to achieve these goals is through electrochemical energy storage technologies and materials. In this context, the rational synthesis and modification of battery materials through new technologies play critical roles. Plasma technology, based on the principles of free radical chemistry, is considered a promising alternative for the construction of advanced battery materials due to its inherent advantages such as superior versatility, high reactivity, excellent conformal properties, low consumption and environmental friendliness. In this perspective paper, we discuss the working principle of plasma and its applied research on battery materials based on plasma conversion, deposition, etching, doping, etc. Furthermore, the new application directions of multiphase plasma associated with solid, liquid and gas sources are proposed and their application examples for batteries (e. g. lithium-ion batteries, lithium-sulfur batteries, zinc-air batteries) are given. Finally, the current challenges and future development trends of plasma technology are briefly summarized to provide guidance for the next generation of energy technologies.

Recent advances in scanning electrochemical microscopy for energy applications.

Scanning electrochemical microscopy (SECM) is a scanning probe technique capable of imaging substrate topography and measuring the local electrochemical reactivity of interfaces. Since introduced by Allen J. Bard and co-workers in 1989, it has expanded into a wide variety of fields, such as nanomaterial characterization, energy, kinetics, electrocatalysis, metal anti-corrosion, biology and instrumental development. SECM uses an ultra-microelectrode as the probe to record redox current during probe scanning across sample surfaces to obtain local topography and electrochemical reactivity of samples. Specifically, three main topics are reviewed and discussed: (1) the working principles and operating modes of SECM; (2) the recent developments in the application of SECM in energy science, including solar cell, rechargeable batteries, fuel cells and supercapacitors, with an emphasis on the last five years (2019-2023); (3) the perspectives and outlook of SECM in various energy devices. We anticipate that a wider adoption of SECM by the energy community will allow for the operando characterization of many types of reactions, and hold the potential to provide new insights into the structure/activity and composition/activity relationships.

Supercapatteries as Hybrid Electrochemical Energy Storage Devices: Current Status and Future Prospects.

Among electrochemical energy storage (EES) technologies, rechargeable batteries (RBs) and supercapacitors (SCs) are the two most desired candidates for powering a range of electrical and electronic devices. The RB operates on Faradaic processes, whereas the underlying mechanisms of SCs vary, as non-Faradaic in electrical double-layer capacitors (EDLCs), Faradaic at the surface of the electrodes in pseudo-capacitors (PCs), and a combination of both non-Faradaic and Faradaic in hybrid supercapacitors (HSCs). EDLCs offer high power density but low energy density. HSCs take advantage of the Faradaic process without compromising their capacitive nature. Unlike batteries, supercapacitors provide high power density and numerous charge-discharge cycles; however, their energy density lags that of batteries. Supercapatteries, a generic term that refers to hybrid EES devices that combine the merits of EDLCs and RBs, have emerged, bridging the gap between SCs and RBs. There are numerous articles and reviews on EES, and many of those articles have emphasized various aspects of HSCs and supercapatteries. However, there are no recent reviews that dealt with supercapatteries in general. Here, we review recently published critically selected articles on supercapatteries. The review discusses different EES devices and how supercapatteries are different from others. Also discussed are properties, design strategies, and future perspectives on supercapatteries.

Transforming Waste into Wealth: Advanced Carbon-Based Electrodes Derived from Refinery and Coal By-Products for Next-Generation Energy Storage.

This comprehensive review addresses the need for sustainable and efficient energy storage technologies against escalating global energy demand and environmental concerns. It explores the innovative utilization of waste materials from oil refineries and coal processing industries as precursors for carbon-based electrodes in next-generation energy storage systems, including batteries and supercapacitors. These waste-derived carbon materials, such as semi-coke, coal gasification fine ash, coal tar pitch, petroleum coke, and petroleum vacuum residue, offer a promising alternative to conventional electrode materials. They present an optimal balance of high carbon content and enhanced electrochemical properties while promoting environmental sustainability through effectively repurposing waste materials from coal and hydrocarbon industries. This review systematically examines recent advancements in fabricating and applying waste-derived carbon-based electrodes. It delves into the methodologies for converting industrial by-products into high-quality carbon electrodes, with a particular emphasis on carbonization and activation processes tailored to enhance the electrochemical performance of the derived materials. Key findings indicate that while higher carbonization temperatures may impede the development of a porous structure, using KOH as an activating agent has proven effective in developing mesoporous structures conducive to ion transport and storage. Moreover, incorporating heteroatom doping (with elements such as sulfur, potassium, and nitrogen) has shown promise in enhancing surface interactions and facilitating the diffusion process through increased availability of active sites, thereby demonstrating the potential for improved storage capabilities. The electrochemical performance of these waste-derived carbon materials is evaluated across various configurations and electrolytes. Challenges and future directions are identified, highlighting the need for a deeper understanding of the microstructural characteristics that influence electrochemical performance and advocating for interdisciplinary research to achieve precise control over material properties. This review contributes to advancing electrode material technology and promotes environmental sustainability by repurposing industrial waste into valuable resources for energy storage. It underscores the potential of waste-derived carbon materials in sustainably meeting global energy storage demands.

Electrochemical Doping and Structural Modulation of Conductive Metal-Organic Frameworks.

In this study, we introduce an electrochemical doping strategy aimed at manipulating the structure and composition of electrically conductive metal-organic frameworks (c-MOFs). Our methodology is exemplified through a representative c-MOF, Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene), synthesized into porous thin films supported by nanocellulose. While the c-MOF exhibits characteristic capacitive behavior in neutral electrolyte; it manifests redox behaviors in both acidic and alkaline electrolytes. Evidence indicates that the organic ligands within c-MOF undergo oxidation (p-doping) and reduction (n-doping) when exposed to specific electrochemical potentials in acidic and alkaline electrolyte, respectively. Interestingly, the p-doping process proves reversible, with the c-MOF structure remaining stable across cyclic p-doping/de-doping. In contrast, the n-doping is irreversible, leading to the gradual decomposition of the framework into inorganic species over a few cycles. Drawing on these findings, we showcase the versatile electrochemical applications of c-MOFs and their derived composites, encompassing electrochemical energy storage, electrocatalysis, and ultrafast actuation. This study provides profound insights into the doping of c-MOFs, offering a new avenue for modulating their chemical and electronic structure, thereby broadening their potential for diverse electrochemical applications.

MXene Triggered Free Radical Polymerization in Minutes toward All-Printed Zn-Ion Hybrid Capacitors and Beyond.

Additive manufacturing of (quasi-) solid-state (QSS) electrochemical energy storage devices (EES) highlights the significance of gel polymer electrolytes (GPEs) design. Creating well-bonded electrode-GPEs interfaces in the electrode percolative network via printing leads to large-scale production of customized EES with boosted electrochemical performance but has proven to be quite challenging. Herein, we report on a versatile, universal and scalable approach to engineer a controllable, seamless electrode-GPEs interface via free radical polymerization (FRP) triggered by MXene at room temperature. Importantly, MXene reduces the dissociation enthalpy of persulfate initiators and significantly shortens the induction period accelerated by SO- 4·, enabling the completion of FRP within minutes. The as-formed well-bonded electrode-GPEs interface homogenizes the electrical and concentration fields (i.e., Zn2+), therefore suppressing the dendrites formation, which translates to long-term cycling (50,000 times), high energy density (105.5 Wh kg-1) and power density (9231 W kg-1) coupled with excellent stability upon deformation in the zinc-ion hybrid capacitors (ZHCs). Moreover, the critical switch of the rheological behaviours of the polymer electrolyte (as aqueous inks in still state and become solids once triggered by MXene) perfectly ensures the direct all-printing of electrodes and GPEs with well-bonded interface in between, opening vast possibilities for all-printed QSS EES beyond ZHCs.

Local Degradation of PEDOT:PSS on Silicon Nanostructures Using Scanning Electrochemical Microscopy.

Conducting polymers show attractive characteristics as electrode materials for micro-electrochemical energy storage (MEES). However, there is a lack of characterization techniques to study conjugated/conducting polymer-based nanostructured electrodes. Here, scanning electrochemical microscopy (SECM) is introduced as a new technique for in situ characterization and acceleration of degradation processes of conducting polymers. Electrodes of PEDOT:PSS on flat silicon, silicon nanowires (SiNWs) and silicon nanotrees (SiNTrs) are analyzed by SECM in feedback mode with approach curves and chronoamperometry. The innovative degradation method using SECM reduces the time required to locally degrade polymer samples to a few thousand seconds, which is significantly shorter than the time usually required for such studies. The degradation rate is modeled using Comsol Multiphysics. The model provides an understanding of the phenomena that occur during degradation of the polymer electrode and describes them using a mathematical constant A0 and a time constant τ.

Single-Particle Measurements: A Powerful Method for Investigating Electrochemical Reactions.

The relationship between interface structure (e. g., the facet of the solid phase and the configuration of solvation) and the reactivity of the corresponding electrode is a critical issue in electrochemistry. Compared to macroscopic electrode measurements, electrochemical methods established on the single-particle scale have advantages in establishing the structure-property relationship. In recent years, great achievements have been made in electrochemical energy storage and electrocatalysis that allow the evolution and kinetics of electrodes to be understood by employing single-particle measurements. This concept aims to provide an overview of the update of single-particle measurements in related electrochemical processes. Furthermore, the challenges and prospects for the development and application of single-particle measurements are also discussed.

Enhanced Active Sites and Stability in Nano-MOFs for Electrochemical Energy Storage through Dual Regulation by Tannic Acid.

The limited active sites and poor acid-alkaline solution stability of metal-organic frameworks (MOFs), significantly limit their wider application. In this study, the acid property of tannic acid (TA) was used as an etchant to etch the surface-active sites. Subsequently, the further chelation of the protonated TA with the exposed metal active site can effectively protect the metal ions. Meanwhile, the TA provided a large amount of phenolic hydroxyl groups, which can greatly improve the stability of imidazolate-coordinated MOFs. The electrochemical test results indicated that the MOFs composite materials synthesized using this scheme had high specific capacitance and stability. And the mechanism of its electrochemical reaction process was explored through in situ X-ray diffraction (XRD) and theoretical calculations. In addition, the same treatment was carried out through a series of carboxyl-coordinated MOFs, which further confirmed the principle of this scheme to obtain a higher active site and stability. This paper explains the mechanism of functionalization of nano-MOFs by polyphenolic compounds, providing new ideas for the research of nano-MOFs.

Coupled Solar Battery with 6.9 % Efficiency.

Solar-to-electrochemical energy storage in solar batteries is an important solar utilization technology comparable to solar-to-electricity (solar cells) and solar-to-fuel (photocatalytic cells) conversion. Unlike the indirect approach of integrated solar flow batteries combining photoelectrodes with redox-electrodes, coupled solar batteries enable direct solar energy storage, but are hampered by low efficiency due to rapid charge recombination of materials and misaligned energy levels between electrodes. Herein, we propose a design for a coupled solar battery that intercouples two photo-coupled ion transfer (PCIT) reactions through electron-ion transfer upon co-photo-pumping of photoelectrochemical storage cathode and anode. We used a representative covalent organic framework (COF) to achieve efficient charge separation and directional charge transfer between two band-matched photoelectrochemical storage electrodes, with a photovoltage sufficient for COF dual-redox reactions. By pumping these electrodes, the coupled solar battery stores solar energy via two synergistic PCIT reactions of electron-proton-relayed COF oxidation and reduction, and the stored solar energy is released as electrochemical energy during COF regeneration in discharge while interlocking the loops. A breakthrough in efficiency (6.9 %) was achieved, adaptive to a large-area (56 cm2 ) tandem device. The presented photo-intercoupled electron-ion transfer (PIEIT) mechanism provides expandable paths toward practical solar-to-electrochemical energy storage.

Highly Reversible Sodium Metal Battery Anodes via Alloying Heterointerfaces.

As a promising pathway toward low-cost, long-duration energy storage, rechargeable sodium batteries are of increasing interest. Batteries that incorporate metallic sodium as anode promise a high theoretical specific capacity of 1166 mAh g-1 , and low reduction potential of -2.71 V. The high reactivity and poor electrochemical reversibility of sodium anodes render sodium metal anode (SMA) cells among the most challenging for practical implementation. Here, the failure mechanisms of Na anodes are investigated and the authors report that loss of morphological control is not the fundamental cause of failure. Rather, it is the inherently poor anchoring/root structure of electrodeposited Na to the electrode substrate that leads to poor reversibility and cell failure. Poorly anchored Na deposits are prone to break away from the current collector, producing orphaning and poor anode utilization. Thin metallic coatings in a range of chemistries are proposed and evaluated as SMA substrates. Based on thermodynamic and ion transport considerations, such substrates undergo reversible alloying reactions with Na and are hypothesized to promote good root growth-regardless of the morphology. Among the various options, Au stands out for its ability to support long Na anode lifetime and high reversibility (Coulombic Efficiency > 98%), for coating thicknesses in the range of 10-1000 nm. As a first step toward evaluating practical utility of the anodes, their performance in Na||SPAN cells with N:P ratio close to 1:1 is evaluated.

Graphdiyne Electrochemistry: Progress and Perspectives.

Graphdiyne, a carbon allotrope, was synthesized in 2010 for the first time. It consists of two acetylene bonds between adjacent benzene rings. Graphdiyne and its composites thus exhibit ultrahigh intrinsic electrochemical activities. As "star" electrode materials, they have been utilized for various electrochemical applications. With the aim of giving a full screen of graphdiyne electrochemistry, this review starts from the history of graphdiyne materials, followed by their structural and electrochemical features. Recent progress and achievements in the synthesis of graphdiyne materials and their composites are overviewed. Subsequently, various electrochemical applications of graphdiyne materials and their composites are summarized, covering those in the fields of electrochemical energy conversion, electrochemical energy storage, and electrochemical sensing. The perspectives of graphdiyne electrochemistry are also discussed and outlined.

Green and Scalable Template-Free Strategy to Fabricate Honeycomb-Like Interconnected Porous Micro-Sized Layered Sb for High-Performance Potassium Storage.

The tremendous volume change and severe pulverization of micro-sized Sb anode generate no stable capacity in potassium-ion batteries (PIBs). The honeycomb-like porous structure provides free spaces to accommodate its volume expansion and offers efficient ion transport, yet complex synthesis and low yield limits its large-scale application. Here, a green, scalable template-free method for designing a 3D honeycomb-like interconnected porous micro-sized Sb (porous-Sb) is proposed. Its honeycomb-like porous formation mechanism is also verified. Under hydrothermal conditions, Sb reacts with water and dissolved oxygen in water, undergoing non-homogeneous and continuous corrosion at grain boundaries, and producing soluble H2 Sb2 O6 (H2 O), which regulates the porous structure of Sb by controlling reaction time. Benefiting from its porous structure and micron size, porous-Sb anode displays large gravimetric and volumetric capacities with 655.5 mAh g-1 and 2,001.9 mAh cm-3 at 0.05 A g-1 and superior rate performance of 441.9 mAh g-1 at 2.0 A g-1 in PIBs. Furthermore, ex situ characterization and kinetic analysis uncover the small volume expansion and fast K+ reaction kinetics of porous Sb during potassiation/depotassiation, originating from its large electrolyte contact area and internal expansion mechanism. It verifies a green, scalable template-free strategy to construct honeycomb-like porous metals for energy storage and conversion.

Exploring 2D Energy Storage Materials: Advances in Structure, Synthesis, Optimization Strategies, and Applications for Monovalent and Multivalent Metal-Ion Hybrid Capacitors.

The design and development of advanced energy storage devices with good energy/power densities and remarkable cycle life has long been a research hotspot. Metal-ion hybrid capacitors (MHCs) are considered as emerging and highly prospective candidates deriving from the integrated merits of metal-ion batteries with high energy density and supercapacitors with excellent power output and cycling stability. The realization of high-performance MHCs needs to conquer the inevitable imbalance in reaction kinetics between anode and cathode with different energy storage mechanisms. Featured by large specific surface area, short ion diffusion distance, ameliorated in-plane charge transport kinetics, and tunable surface and/or interlayer structures, 2D nanomaterials provide a promising platform for manufacturing battery-type electrodes with improved rate capability and capacitor-type electrodes with high capacity. In this article, the fundamental science of 2D nanomaterials and MHCs is first presented in detail, and then the performance optimization strategies from electrodes and electrolytes of MHCs are summarized. Next, the most recent progress in the application of 2D nanomaterials in monovalent and multivalent MHCs is dealt with. Furthermore, the energy storage mechanism of 2D electrode materials is deeply explored by advanced characterization techniques. Finally, the opportunities and challenges of 2D nanomaterials-based MHCs are prospected.

A Review of MnO2 Composites Incorporated with Conductive Materials for Energy Storage.

Manganese dioxide (MnO2 ) has been widely used in the field of energy storage due to its high specific capacitance, low cost, natural abundance, and being environmentally friendly. However, suffering from poor electrical conductivity and high dissolvability, the performance of MnO2 can no longer meet the needs of rapidly growing technological development, especially for the application as electrode material in metal-ion batteries and supercapacitors. In this review, recent studies on the development of binary or multiple MnO2 -based composites with conductive components for energy storage are summarized. Firstly, general preparing methods for MnO2 -based composites are introduced. Subsequently, the binary and multiple MnO2 -based composites with carbon, conducting polymer, and other conductive materials are discussed respectively. The improvement in their performance is summarized as well. Finally, perspectives on the practical applications of MnO2 -based composites are presented.