Electrode Electrolyte Research Articles

Solid-state preparation of in-situ grown graphene-embedded bi-metallic NiMnS hybrids for high-performance asymmetric supercapacitor

Endowed with intrinsic redox-rich features and superior electronic conductivities, mixed-metallic sulphides offer high prospects in electrochemical charge storage, especially in supercapacitors. Hence, their rational design and scalable preparation are of great scientific significance. Herein, we report the in-situ growth of nanostructured hybrids of NiMnS directly embedded into graphene sheets by a straightforward, scalable solid-state synthesis method. In this environment-friendly approach, the metal precursors, elemental sulphur, and graphene oxide (GO) are homogeneously mixed under ball-milling, followed by controlled thermal treatment. Incited from their unique synergistic contribution, the resulting NiMnS/G hybrids exhibit impressive electrochemical performance as a battery-type electrode in an aqueous electrolyte. The NiMnS/G hybrid electrode displayed a high specific capacity of 871.7C g−1 at 2 A g−1 with superior rate capability. Moreover, the asymmetric supercapacitor (ASC) device assembled based on the surface-enhanced NiMnS/G nanohybrid as the positive electrode and activated carbon (AC) as the negative electrode achieves an intriguing performance, delivering a maximum energy density of 53.4 Wh kg−1 at a power density of 500 W kg−1. The ASCs were successfully cycled over 10,000 cycles with 87 % capacitance retention and around 99 % Coulombic efficiency. This simple yet scalable strategy holds high promise and may pave the way for preparing other multimetallic sulphide-based hybrid electrode materials for electrochemical energy storage applications.

Automated Robotic Cell Fabrication Technology for Stacked‐Type Lithium‐Oxygen Batteries

AbstractRechargeable lithium‐oxygen batteries (LOBs) are gaining interest as next‐generation energy storage devices due to their superior theoretical energy density. While recent years have seen successful operation of LOBs with high cell‐level energy density, the technology for cell fabrication is still in its infancy. This is because the cell fabrication procedure for LOBs is quite different from that of conventional lithium‐ion batteries. The study presents a fully automated sequential robotic experimental setup for the fabrication of stacked‐type LOB cells. This approach allows for high accuracy and high throughput fabrication of the cells. The developed system enables the fabrication of over 80 cells per day, which is 10 times higher than conventional human‐based experiments. In addition, the high alignment accuracy during the electrode stacking and electrolyte injection process results in improved battery performance and reproducibility. The effectiveness of the developed system was also confirmed by investigating a multi‐component electrolyte to maximize battery performance. We believe the methodology demonstrated in the present study is beneficial for accelerating the research and development of LOBs.

Carbon Dots Enabling High-Performances Sodium-Ion Batteries.

Carbon dots (CDs), known for their quantum size, abundant surface functional groups, excellent biocompatibility, and non-toxicity, have emerged as promising candidates for enhancing various advanced rechargeable batteries. Recent research indicates that electrodes based on or modified with CDs in sodium-ion batteries (SIBs) have shown significant improvements in key performance metrics such as Coulombic efficiency, cycle life, and capacity compared to traditional electrodes. Several key impacts of CDs contribute to these enhancements, including increased conductivity due to their conductive graphitized core, rich absorption sites, and excellent dispersity facilitated by abundant surface functional groups. These features accelerate ion transport through interface edges and ion diffusion paths, inhibit electrode material dissolution, buffer electrode material volume expansion, ensure electrode uniformity and stability, and promote the electrochemical reaction process between the electrode and electrolyte. This review summarizes recent developments, challenges, and opportunities in leveraging CDs as additives in SIBs, focusing on their impact on electrolyte properties, electrode materials, and overall battery performance. It provides a comprehensive understanding of the potential of CDs to significantly advance SIB technology.

Effective Water Confinement and Dual Electrolyte–Electrode Interfaces by Zwitterionic Oligomer for High‐Voltage Aqueous Lithium‐Ion Batteries

AbstractAqueous lithium‐ion batteries (ALIBs) have attracted significant interest due to their inherent advantage on safety. However, water itself has a narrow electrochemical stability window (ESW), limiting the energy density of ALIBs. Here, a low‐molecular‐weight zwitterionic oligomer, oligo(propylsulfonate dimethylammonium propylmethacrylamide) (OPDP), as an effective water binding agent for high‐voltage ALIBs is demonstrated. The OPDP can effectively confine water molecules while reducing water activity. The OPDP‐based electrolyte, with an ultra‐high water weight percentage of 25.4%, possesses an outstanding ESW of up to 3.26 V and an ionic conductivity as high as 3.18 mS cm−1. Furthermore, the aqueous Mo6S8//LiMn2O4 full cell with OPDP‐based electrolyte achieves a 99.7% capacity retention after 200 cycles at 0.5C with a high Coulombic efficiency (CE) of 98.7% and a specific energy of 88–101 Wh kg−1. Also, it achieves an 89% capacity retention after 2000 cycles at 10C with a high CE of 99.9%. These postmortem characterizations suggest that robust organic–inorganic hybrid cathode/anode‐electrolyte interfaces have been constructed during the cycling through the heteroatoms of N, S, and O in the zwitterionic oligomer, leading to the inhibited hydrogen/oxygen evolution reactions and high performance of the full cell. This work provides a promising strategy for developing low‐cost and high‐voltage aqueous batteries.

In-situ synthesis nano PtRuW/WC HER catalyst for acid hydrogen evolution by microwave method

Abstract One of the primary challenges in electrocatalysis for the hydrogen evolution reaction (HER) lies in the development of highly efficient catalysts suitable in acidic environments. Tungsten carbide-based materials have long been proposed as potential substitutes for Pt due to their “Pt-like” electronic properties in the HER process. However, tungsten carbide still falls short of the performance exhibited by commercial precious-metal catalysts. Herein, PtRuW/WC was prepared by a microwave heating method and acted as a HER electrocatalyst. The microwave method not only enhances the diffraction peaks of the substrate tungsten carbide, but also facilitates the growth of metal ions at specific sites. The PtRuW/WC catalyst demonstrates outstanding performance in acidic HER, characterized by a minimal overpotential of 40.7 mV at 10 mA/cm2 (η10). Furthermore, it exhibits exceptional stability in acidic solutions, showing no substantial degradation during 20 h at 1000 mA/cm2. The catalyst-assembled PEM electrolytic water electrode further proves that PtRuW/WC has excellent electrolytic water performance and makes some efforts for the development of commercial PEM electrolytic water.

New Redox Chemistries of Halogens in Aqueous Batteries.

Halogen-based redox-active materials represent an important class of materials in aqueous electrochemistry. The existence of versatile halogen species and their rich bonding coordination create great flexibility in designing new redox couples. Novel redox reaction mechanisms and electrochemical reversibility can be unlocked in specifically configurated electrolyte environments and electrodes. In this review, the halogen-based redox couples and their appealing redox chemistries in aqueous batteries, including redox flow batteries and traditional static batteries, that have been studied in recent years are discussed. New aqueous electrochemistry provides hope to outperform the state-of-the-art materials and systems that are facing resources and performance limitation, and to enrich the existing battery chemistries.

Operando Investigation of Al Plating Regimes on HOPG in [EMImCl]:AlCl3 by Electrochemical Reflection Anisotropy Spectroscopy

Rechargeable aluminium batteries show promise as next‐generation systems with a more abundant material base than lithium technology. However, the stable native oxide on top of aluminium metal electrodes leads to poor cell performance. Graphite, on the other hand, is a so far rarely investigated alternative that can be used as both the anode and cathode. Here, metallic aluminium is deposited at the anode, while AlCl4– is intercalated at the cathode. For both cases, understanding the electrode–electrolyte interface is crucial for improving the performance of the battery. In this work, we use reflection anisotropy spectroscopy to study the evolution of the interface under applied potentials. We find that the cathode exhibits an irreversible swelling of the top‐most graphite layer due to AlCl4– intercalation as well as the formation of an SEI during the first voltammetry cycle. On the anode, the electrodeposition of aluminium is initially well‐ordered. However, the evolution of the surface morphology depends on the applied potential, with island‐like growth at less cathodic potentials, and layer‐by‐layer growth at more anodic potentials. With the optical operando spectroscopy, we can follow these qualitatively different plating and stripping regimes in a time‐resolved manner.

Electrochemical kinetic energy harvesting mediated by ion solvation switching in two-immiscible liquid electrolyte

Kinetic energy harvesting has significant potential, but current methods, such as friction and deformation-based systems, require high-frequency inputs and highly durable materials. We report an electrochemical system using a two-phase immiscible liquid electrolyte and Prussian blue analogue electrodes for harvesting low-frequency kinetic energy. This system converts translational kinetic energy from the displacement of electrodes between electrolyte phases into electrical energy, achieving a peak power of 6.4 ± 0.08 μW cm−2, with a peak voltage of 96 mV and peak current density of 183 μA cm−2 using a 300 Ω load. This load is several thousand times smaller than those typically employed in conventional methods. The charge density reaches 2.73 mC cm−2, while the energy density is 116 μJ cm−2 during a harvesting cycle. Also, the system provides a continuous current flow of approximately 5 μA cm−2 at 0.005 Hz for 23 cycles without performance decay. The driving force behind voltage generation is the difference in solvation Gibbs free energy between the two electrolyte phases. Additionally, we demonstrate the system’s functionality in a microfluidic harvester, generating a maximum power density of 200 nW cm−2 by converting the kinetic energy to propel the electrolyte through the microfluidic channel into electricity.

Infiltration-driven performance enhancement of poly-crystalline cathodes in all-solid-state batteries

All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future.

Influence of Electrode Pore Size and Electrolyte on Carbon Aerogel Supercapacitors: Insights from Experimental Studies and Molecular Simulations

Influence of Electrode Pore Size and Electrolyte on Carbon Aerogel Supercapacitors: Insights from Experimental Studies and Molecular Simulations

Enhanced electrocatalytic OER activity following electrochemical pre-cathodic treatment of Mn-substituted nickel ferrite

In this study, the electronic engineering of a high-valent active site for enhanced oxygen evolution reaction (OER) was achieved through the electrochemical pre-cathodic treatment method (EPCTM). This method involves applying a cathodic potential to the drop-cast working electrode of Mn-substituted nickel ferrite (Ni1−xMnxFe2O4; where x = 0.0, 0.2, and 0.4) electrocatalysts. X-ray photoelectron spectroscopy analysis revealed an increase in the ratios of Ni3+/Ni2+ and Mn3+/Mn2+ in Ni1−xMnxFe2O4 after EPCTM followed by OER, leading to an enhancement in electrochemical OER current density at 600 mV overpotential by 3.65 times for x = 0.0, 5.56 times for x = 0.20, and 4.72 times for x = 0.40. This enhancement was further supported by a decrease in the slope of the anodic Tafel equation after EPCTM, indicating improved efficiency of the interaction between the working electrode and electrolyte, as a lower Tafel slope suggests better charge exchange at the electrode–electrolyte interface. The positive slope in the Mott–Schottky (MS) plot for all Ni1−xMnxFe2O4 samples confirmed the p-type nature of the electrocatalysts. Additionally, the significant decrease in the slope of the linear portion of the MS plot indicated an increase in carrier concentration after electrochemical pre-cathodic treatment in all Ni1−xMnxFe2O4 samples. This increase in p-type carrier concentration supports the observed increase in the Ni3+/Ni2+ ratio for OER after EPCTM.

In-situ polymerized solid/quasi-solidpolymerelectrolytefor lithium-metal batteries: recent progress and perspectives.

In pursuit of high energy density, lithium metal batteries (LMBs) are undoubtedly the best choice. However, leakage and inevitable dendrite growth in liquid electrolytes seriously hinder its practical application. Solid/quasi-solid stateelectrolytes have emerged as an answer to solve the above issues. Especially, polymer electrolytes with excellent interface compatibility, high flexibility, and ease of machining have become a research hotspot for LMBs. Nevertheless,the interface contact between polymer electrolyte and inorganic electrode materials and the low ionic conductivity restrict its development. On account of these, in situ polymerized polymer electrolyteis proposed. Polymer solid electrolytes produced through in situ polymerization promote robust interface contact between the electrolyte and electrode while simplifying the preparation steps. Thisreviewsummarized the latest research progress in in situ polymerized solid electrolytes for LMBs. These electrolytes were divided into three parts according to their polymerization methods: thermally induced polymerization, chemical initiator polymerization, ionizing radiation polymerization,and so on. Furthermore, we concluded the major challenges and future trends of in situ polymerized solid electrolytes for LMBs. It's hoped that this review will provide meaningful guidance on designing high-performance polymer solid electrolytes for LMBs.

Chemical Roadmap toward Stable Electrolyte–Electrode Interfaces in All-Solid-State Batteries

Chemical Roadmap toward Stable Electrolyte–Electrode Interfaces in All-Solid-State Batteries

N, O and P co-doped hierarchically porous carbon fiber for high performance Zinc-ion hybrid capacitors

Multi-heteroatoms co-doped hierarchically porous carbon-based electrode is an effective strategy to solve the low energy density and poor cycle stability of Zn-ion hybrid capacitors (ZHCs). Herein, N/O/P co-doped porous carbon nanofiber (N-P-PCF) was prepared, which displays fibrous network hierarchically porous structure to fast electron/ Zn2+ transport and enhance Zn2+ adsorption sites. Meanwhile, rich N (9.47 at.%), O (11.29 at.%) and P (1.29 at.%) co-doping can be beneficial for the infiltration of electrode–electrolyte interface and provide an additional pseudocapacitance. The N-P-PCF based ZHCs can yield a large specific capacitance (205 mAh g−1 at 1 A g−1), high energy density (173 Wh kg−1 at 823 W kg−1) and excenllent cycle stability for 10,000 cycles (98.6 % capacity retention), which provides a reliable multi-heteroatoms co-doped porous carbon fiber for high-performance ZHCs.

Self‐Encapsulated Ni Nanoparticles on Delignified Wood Carbon for Efficient Urea‐Assisted Hydrogen Production

AbstractDeveloping efficient, low‐cost electrocatalysts for industrial‐level hydrogen production remains a significant challenge. Here lattice‐distorted Ni nanoparticles (NPs) encapsulated within a nitrogen‐doped carbon shell on delignified wood carbon (Ni‐NC@DWC) are constructed through a chitosan‐induced assembly and the pyrolysis process. Experimental and theoretical results indicate that the lattice distortion due to strong metal‐support interactions, boosts electron transfer and reaction intermediate adsorption/desorption, enhancing both the urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Interestingly, the active center Ni3+‐O is dynamically cyclically generated during the UOR. When utilized as a self‐standing electrode in an alkaline electrolyte, the Ni‐NC@DWC exhibits low potentials of 24 mV and 1.244 V at 100 mA cm−2 for HER and UOR, respectively. Moreover, the Ni‐NC@DWC achieves an ultrasmall cell voltage of 1.13 V at 100 mA cm−2 for urea‐assisted water splitting and can operate stably over 1000 h. Furthermore, when it is self‐assembled as an anion exchange membrane (AEM) electrolyzer, it requires only 1.62 V at 2000 mA cm−2 for industrial urea‐assisted water splitting and operates stably for 150 h without degradation, confirming that it is highly attractive for economical, sustainable, and scalable hydrogen production.

Sodium-Ion Battery at Low Temperature: Challenges and Strategies.

Sodium-ion batteries (SIBs) have garnered significant interest due to their potential as viable alternatives to conventional lithium-ion batteries (LIBs), particularly in environments where low-temperature (LT) performance is crucial. This paper provides a comprehensive review of current research on LT SIBs, focusing on electrode materials, electrolytes, and operational challenges specific to sub-zero conditions. Recent advancements in electrode materials, such as carbon-based materials and titanium-based materials, are discussed for their ability to enhance ion diffusion kinetics and overall battery performance at colder temperatures. The critical role of electrolyte formulation in maintaining battery efficiency and stability under extreme cold is highlighted, alongside strategies to mitigate capacity loss and cycle degradation. Future research directions underscore the need for further improvements in energy density and durability and scalable manufacturing processes to facilitate commercial adoption. Overall, LT SIBs represent a promising frontier in energy storage technology, with ongoing efforts aimed at overcoming technical barriers to enable widespread deployment in cold-climate applications and beyond.

Polyacrylonitrile and aluminum metal dual functionalization interconnected network for superior lithium storage in silicon anode

Currently, silicon-based anode is one of the most promising anode materials that can be applied in next-generation lithium-ion batteries. However, the high activity of the electrode–electrolyte interface and low electronic conductivity of Si anode during the cycling process greatly limits its large-scale application. Aluminum (Al) is the metallic current collector known to promote electronic conductivity and lithium-ion transfer at low cost. However, to our knowledge, scalable interface engineering incorporating Al with carbonized polymer has not been reported. Herein, a polyacrylonitrile (PAN) and aluminum metal dual functionalization interconnected network is achieved via a simple sol-gel method followed by high-temperature calcination to obtain a stable solid electrolyte interphase (SEI) while allowing fast Li+ transmission. The calculated diffusion energy barrier for lithium ions in Al is 0.2198 eV, significantly lower than that in Cu and Fe. Benefiting from the enhanced interfacial protection and kinetics of Si with polyacrylonitrile/Al, the prepared Si@Al@CPAN anode exhibits high lithium storage capacity (2034.90 mAh/g after 150 cycles at 0.84 A/g). At the same time, the prepared Si@Al@CPAN anode outperforms the pure Si anode in rate performance at 12.6 A/g (1116.75 mAh/g vs. 2.84 mAh/g). The present work delivers new design ideas for high-performance Si anode with a multi-functionalization interface.

An Overview of Different Water Electrolyzer Types for Hydrogen Production

While fossil fuels continue to be used and to increase air pollution across the world, hydrogen gas has been proposed as an alternative energy source and a carrier for the future by scientists. Water electrolysis is a renewable and sustainable chemical energy production method among other hydrogen production methods. Hydrogen production via water electrolysis is a popular and expensive method that meets the high energy requirements of most industrial electrolyzers. Scientists are investigating how to reduce the price of water electrolytes with different methods and materials. The electrolysis structure, equations and thermodynamics are first explored in this paper. Water electrolysis systems are mainly classified as high- and low-temperature electrolysis systems. Alkaline, PEM-type and solid oxide electrolyzers are well known today. These electrolyzer materials for electrode types, electrolyte solutions and membrane systems are investigated in this research. This research aims to shed light on the water electrolysis process and materials developments.

Exploring Electrolyte Adsorption on the Different Types of Layered Cathode Surfaces in Lithium-Ion Batteries via a Universal Neural Network Potential Method.

LiNi x Mn y Co z O2 (NCM) is a promising cathode material for lithium-ion batteries. Their long-term stability and impedance growth as cycles are strongly influenced by the properties of the cathode electrolyte interface (CEI), formed by the reaction between the electrolyte and electrode surface. Understanding of these interactions at the atomic level of the NCM electrode surface and electrolyte will provide a new strategic approach for the design of a highly functional CEI layer. In this study, we explored the influence of Ni content in transition metal layers on surface energies under different synthetic conditions and terminations using a density functional theory (DFT) validated universal neural network potential (UNNP) method. Furthermore, we investigated the adsorption of ethylene carbonate (EC) and dimethyl carbonate (DMC) on the most favorable NCM surfaces. EC and DMC displayed similar adsorption energy trends; however, differences were observed in the preferred configurations, which can affect the formation of the CEI.

Curved surface coupled structural battery composites manufactured by resin transfer molding process: Microstructure and multifunctional performance

To bridge industrial production and lab-scale research, this work demonstrates a technology to manufacture curved surface structural battery composites (CSBCs) that can simultaneously achieve electrochemical energy storage and load-bearing. The curved-surface carbon fiber structural anode and cathode are fabricated by coating the active materials on carbon fiber fabric with a vacuum-bag-assisted technique. The resin transfer molding (RTM) process is conducted to manufacture the coupled CSBCs by infusing bi-continuous phase epoxy resin electrolyte and curing at high temperatures. The microstructure of structural electrodes and CSBCs is characterized by scanning electron microscopy (SEM). Due to good interfacial compatibility between high mechanical strength carbon fiber structural electrode and high ionic conductivity solid polymer electrolyte bulk for load support, the fabricated CSBCs demonstrate a high density of 294 mWh kg−1 based on the whole mass of devices, a tensile strength of 257.4 MPa with Young's modulus of 12.9 GPa and a flexural strength of 194.1 MPa with flexural modulus of 11.1 GPa. In situ electrochemical-mechanical tests further confirm the durability of CSBCs under mechanical loads with a multifunctional efficiency of 1.07, suggesting the effectiveness of the introduced manufacturing techniques for coupled structural battery composites.