Electrochemical Performance Research Articles

Unlocking dendrite-free zinc metal anodes through anti-corrosive and Zn-ion-regulating interlayer

Aqueous zinc-ion batteries (AZIBs) are a promising solution for large-scale energy storage due to their safety and cost-effectiveness. However, challenges like zinc dendrite growth and electrolyte corrosion hinder their practical use. Surface engineering methods have shown potential in stabilizing the zinc metal anode interface. In this study, we propose a successful approach by combining 2D g-C3N4 nanosheets with 3D ZIF8 nanoparticles to form a g-C3N4@ZIF8 artificial interface. The 3D ZIF8 support on the 2D g-C3N4 enables precise regulation of Zn2+ flux and efficient charge transfer, leading to improved electrochemical performance. Density functional theory confirms ZIF8's superior adsorption energy compared to g-C3N4. Strategically anchoring 3D ZIF8 nanoparticles within 2D g-C3N4 allows robust 3D diffusion of Zn2+, preventing dendrite formation and enabling dendrite-free Zn deposition. This structural design can enhance the performance of symmetric cells with an ultralong cycling lifespan of up to 6200 h at 0.25 mA cm−2/0.25 mA h cm−2 and superior rate capability, even at 40 mA cm−2. When combined with a V2O5 nanopaper cathode, our assembled AZIBs exhibit stable long-term performance. This research paves the way for more efficient and reliable AZIBs for large-scale energy storage.

Unveiling the role of electrolyte to promote enhanced proton storage stability in WO3 for energy storage

In the present work, we systematically investigate the phenomenon of electrochemical proton storage in WO3 and subsequently demonstrate a strategy for enhancing the cycle life for proton storage. It was carried out in three different electrolytes medium based on H3PO4, H2SO4 and HCl. It was found that although H3PO4 can promote better cycling stability and high rate capability than HCl and H2SO4, there still persists an issue in achieving large number of charge/discharge cycles. The typical proton storage capacitance of WO3 in 3.75 M H3PO4 is estimated to be around 288–346 F g−1 at a current rate of 0.5 A g−1 over 30 cycles. The cycling stability could, however, be significantly improved by the utilization of gel electrolyte which is basically a mixture of H3PO4 and polyvinyl alcohol (PVA) of different concentrations. For example, the estimated proton storage capacitance is around 287 F g−1 in 3.75 M H3PO4-PVA gel electrolyte (1:8 wt %) over 100 cycles at a current density of 0.5 A g−1. On the basis of the improved proton storage stability in the gel electrolyte, the electrochemical performance of a proton storage full cell with WO3 and V10O24.12H2O as electrodes is also illustrated. Another important revelation is the drastic reduction of the self-discharge rate of the full cell in the gel electrolyte in comparison to pristine aqueous medium electrolyte.

Thermally Controlled Synthesis of Cr2(NCN)3/CrN Heterostructured Composite Anodes for High‐Performance Li‐Ion Batteries

AbstractCr2(NCN)3 features high specific capacity and fast electrical conductivity, making it a promising anode candidate for Li‐ion batteries. However, inherent chemical and structural metastability severely restrict its capacity output and cycle life, resulting in unsatisfactory battery performance. Here we use its thermal instability characteristic and propose a thermal controlled structural coordination strategy to in‐situ construct a Cr2(NCN)3/CrN heterostructure. Systematic studies reveal the thermodynamic structural evolution of Cr2(NCN)3 under precise temperature regulation, as well as the essential relevancy between electrochemical properties and crystalline structures. An optimal Cr2(NCN)3/CrN heterostructural composite obtained at 690 °C features uniform two‐phase recombination with abundant grain boundaries enables promising electrochemical performance, exhibiting a high reversible discharge capacity (760 mAh g−1) and a good cycle performance (75 % retention after 100 cycles). It is worth noting that the above performance is significantly improved over unmodified pure transition metal carbodiimides or metal nitride anodes. This study provides a simple and universal structural regulation strategy for transition metal carbodiimides that utilizes their thermal sensitivity to synchronously construct synergistic transition metal carbodiimides/transition metal nitrides heterostructures, promoting their potential applications in Li‐ion batteries.

Enhanced Electrochemical Performance in Supercapacitors through KCu-Cy Based Metal-Organic Framework Electrodes.

In the realm of electronics and electric energy storage, the convergence of organic and metallic materials has yielded promising outcomes. In this study, we introduce a novel metal-organic polymer synthesized from Cyamelurate and copper (KCu-Cy) and explore its application as an electrode for a supercapacitor. This material was pressed onto a stainless-steel grid as a thin film and synthesized on nickel foam. Comprehensive characterization was carried out to confirm the synthesis, ensure phase purity, and investigate atomic interactions. Single Crystal X-ray Diffraction (SCXRD) and Powder X-ray Diffraction (PXRD) analyses verified the synthesis and phase purity, shedding light on atomic arrangements. Fourier Transform Infrared Spectroscopy (FTIR) analyses provided insights into characteristic peaks within the material. Thermal Gravimetric Analysis (TGA) gauged stability and durability. Electrochemical performance was assessed through cyclic voltammetry. Notably, the nickel-supported electrodes, devoid of binders, exhibited exceptional specific capacity, reaching 1210.89 F/g at a scan rate of 5 mV/s, in contrast to 363.73 F/g for the pressed thin film on the stainless-steel grid, which incorporated a conductive agent and binder. Cu-Cy displayed impressive cyclization resistance, with a capacity retention of 90 % even after 11000 cycles. These findings underline the promise of Cu-Cy as a high-performance electrode material for supercapacitors, particularly in binder-free configurations, and suggest its potential in advanced energy storage applications.

DANOISE; a 3D Printable Battery Cell for Laboratory Operando X‐Ray Diffraction and Absorption Spectroscopy**

AbstractStudying structural and electronic processes in the materials inside a battery as they occur during battery operation is key for developing novel improved materials for future generations of batteries. Such studies often entail X‐ray diffraction and absorption spectroscopy, which have so far primarily been conducted at synchrotron facilities despite the widespread use of laboratory‐based X‐ray diffraction and absorption spectroscopy for day‐to‐day characterisation. With the “Developed in Aarhus: New Operando In‐house Scattering Electrochemical” (DANOISE) cell, these experiments are brought into the laboratories making in‐house operando X‐ray diffraction and absorption spectroscopy on‐demand additions to the existing facilities. The chic and facile design of the DANOISE cell provides high quality scattering and absorption data besides providing reliable electrochemical performance. In this work, we describe the design of the DANOISE cell and demonstrate the capabilities of the cell using different commercial technologies for Li‐ion batteries and from a new Na‐ion battery electrode material.

A Sustainable and Cost-Effective Nitrogen-Doped Three-Dimensional Porous Carbon for High-Performance Lithium-Sulfur Batteries.

Affordable clean energy is one of the major sustainable development goals that can transform our world. At present, researchers are working to develop cheap electrode materials to develop energy storage devices, the Lithium-sulfur (Li-S) battery is considered a promising energy storage device owing to its excellent theoretical specific capacity and energy density. Herein, utilizing the ramie degumming waste liquid as raw materials, after freeze-drying and high-temperature calcination, a sustainable and cost-effective three-dimensional (3D) porous nitrogen-doped ramie carbon (N-RC) was synthesized. The N-RC calcined at 800 °C (N-RC-800) shows a superior high specific surface area of 1491.85 m2 ⋅ g-1 and a notable high pore volume of 0.90 cm3 ⋅ g-1. When employed as a sulfur host, the S@N-RC-800 cathode illustrates excellent initial discharge capacity (1120.6 mAh ⋅ g-1) and maintains a reversible capacity of 625.4 mAh ⋅ g-1 after 500 cycles at 1 C. Simultaneously, the S@N-RC-800 cathode also shows excellent coulombic efficiency and ideal rate performance. Such exceptional electrochemical performance of S@N-RC-800 can be primarily attributable to N-RC's high specific surface area, high porosity, and abundant polar functional groups. This green and low-cost synthesis strategy offers a new avenue for harnessing the potential of waste biomass in the context of clean energy storage.

Correlation Between Li-Fe Anti-Site and Memory Effect of LiFePO4 in Li-Ion Batteries.

In Li-ion batteries, the origin of memory effect in Al-doped Li4Ti5O12 has been revealed as the reversible Al-ion switching between 8a and 16c sites in the spinel structure, but it is still not clear about that for olivine LiFePO4, which is one of the most important cathode materials. In this work, a series of Na-doped and Ti-doped LiFePO4 are prepared in a high-temperature solid-state method, electrochemically investigated in Li-ion batteries and characterized by X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Magic-Angle-Spinning Nuclear Magnetic Resonance (MAS NMR). Compared with non-doped LiFePO4, the Ti doping can simultaneously suppress the memory effect and the Li-Fe anti-site, while they are simultaneously enhanced by the Na doping. Meanwhile, the Ti doping improves the electrochemical performance of LiFePO4, opposite to the Na doping. Accordingly, a schematic diagram of phase transition is proposed to interpret the memory effect of LiFePO4, in which the memory effect is attributed to the defect of Li-Fe anti-site.

Mechanical and Electrochemical Implications of Drying Temperature on Lithium‐Ion Battery Electrodes

AbstractLithium‐ion battery (LIB) electrodes are typically produced with n‐methyl‐2‐pyrrolidone, a toxic solvent that is a known carcinogen and reproductive hazard. Accordingly, aqueous processing has been an expanding area of research interest in the field of LIB manufacturing. Although aqueous processing has been widely successful in anode processing, serious challenges remain in processing the cathode. In this work, the drying mechanics of cathode processed with both solvents is investigated though implementation of a chemical‐engineering‐based model to better understand the utilization of heat provided by experimentally determining the heat and mass transfer coefficients. Electrochemical performance is also evaluated to determine the impact of drying temperature on cycling performance. Binder distribution is determined via various methods to confirm differences in binder homogeneity as a function of both solvent and drying temperature. Identified is the large difference in the efficiency in which the heat is used as well as an ideal drying temperature for both aqueous and non‐aqueous processed cathodes. Also identified is the increased sensitivity to processing temperature for aqueous processed electrodes compared to non‐aqueous processed counterparts, pointing to the possibility of tuned drying regimes which would capitalize on the potential cost savings of aqueous processing for cathodes.

Boosting Supercapacitor Efficiency with Amorphous Biomass-Derived C@TiO2 Composites.

Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices. This work reports the preparation of amorphous TiO2 nanopowders, which were obtained through the anodization of titanium in ethaline media. The obtained amorphous TiO2 was used to obtain TiO2-decorated carbon (obtained through the carbonization of glycogen precursor from mussel cooking wastewater, under N2 atmosphere) composites through three different methods: electrochemical in-situ attachment of TiO2 nanopowders to the carbon matrix using ultrasounds and sonication in ethaline. Commercial TiO2 was used as the comparison material. Morphology, composition, and structure analysis were performed, followed by the electrochemical analysis in ethaline electrolyte. The in-situ attachment of amorphous TiO2 to the carbon matrix shows the most promising electrochemical performance of 956 F g-1 at 1 A g-1 for the three-electrode cell setup, with 100% and 98% capacitance retention after 1000 and 10000 cycles. On a two-electrode symmetric solid-state electrolyte cell, the gravimetric capacitance is 1251 F g-1, at 1 A g-1, with 90% and 78% capacitance retention after 1000 and 10000 cycles, respectively.

Photocatalytic Drug Degradation and Supercapacitor Applications of FeVO4 and rGO‐FeVO4 Nanocomposite

AbstractConstructing novel multifunctional materials is a promising approach to boost the catalytic activity and electrochemical performance simultaneously. Herein, hydrothermal synthesized FeVO4 nanosized particles dispersed on reduced graphene oxide (rGO) through cost‐effective simple sonochemical assisted route are developed as an efficient material for photocatalysis activity and high‐value‐added supercapacitor applications. The synthesized materials were characterized for structural and morphological purity and found to be in single phase and nanostructured. rGO‐FeVO4 composite shows excellent photodegradation of Levofloxacin (LVO) drug (100 % over 80 min) compared with FeVO4 owing to the bandgap in visible region and larger surface area. Further, the optimized rGO‐FeVO4 composite was employed into supercapacitors and it showed 3 times higher capacitance (211.4 F/g at 0.5 A/g) compared with FeVO4 (70.4 F/g) using half‐cell measurements. Moreover, the developed symmetric supercapacitors (full cell; SSCs) using rGO‐FeVO4 composite device showed 109 F/g capacitance at 0.5 A/g current density having high energy density of 13.6 Wh/kg at the power density of 450 W/kg. The proposed rGO‐FeVO4 composite proved its multifunctional outcomes, which can open new opportunities to develop such materials for numerous future applications.

Pristine Metal‐Organic Frameworks for Sodium‐Ion Batteries: Past, Present, and Future

AbstractOwing to their adjustable redox‐active sites, designable structures high porosity, and fully activated organic ligands, pristine metal‐organic frameworks (MOFs) have been widely utilized as advanced electrode materials (i. e., both anodes and cathodes) for sodium‐ion batteries (SIBs) to satisfied the insertion/extraction larger size and mass of Na+ cations, achieving significant progresses with excellent electrochemical performance in electrochemical energy storage devices. Here, the recent advances on pristine MOFs as anodes and cathodes for SIBs are summarized. A thorough investigation delves into the detailed characteristics, energy storage mechanisms, and electrochemical performance of diverse pristine MOFs for SIBs are also clarified. Furthermore, the outlooks on pristine MOF electrodes in SIBs are also provided.

Preparation and properties of two-dimensional Ti2CT x MXene based on electroetching method

The continuous advancements in wearable electronics have drawn significant attention toward 2D MXenes materials for energy storage owing to their abundant availability, adaptability, and distinctive physicochemical properties. Two unresolved concerns currently revolve around environmental pollution by F-containing etching and finite kinetics caused because of re-stacking of nanosheets. In this study, Al was electrochemically etched from porous Ti2AlC electrodes without the use of fluorine, through a selective electrochemical etching process in dilute hydrochloric acid. Subsequently, Ti2CT x MXene was vertically grown on carbon fiber (CF) substrates. The resulting Ti2CT x @CF electrodes are lightweight, thin, and flexible, exhibiting a surface capacitance of 330 mF cm−2 at a constant current density of 1 mA cm−2 after 2000 cycles. They display a surface capacitance retention of 96.16% and a high energy density of 45.3 μWh cm−2 at a power density of 0.497 mW cm−2. These metrics underscore the Ti2CT x @CF electrode’s commendable multifunctionality, electrochemical performance, ion transport efficiency, and charge storage capacity. Moreover, a flexible energy storage electrode material with a high area capacity was developed by combining Ti2CT x MXene nanosheets, possessing a large specific surface area, with a flexible carbon fabric substrate.

Enhanced low-temperature resistance of lithium-ion batteries based on methyl propionate-fluorinated ethylene carbonate electrolyte

Low temperature has been a major challenge for lithium-ion batteries to maintain satisfied electrochemical performance, as it leads to poor rechargeability and low capacity retention. Traditional carbonate solvents, vinyl carbonate and dimethyl carbonate are indispensable components of commercial electrolytes. However, the higher melting point of these carbonate solvents causes their electrical conductivity to be easily reduced when temperatures drop below zero, limiting their ability to facilitate lithium ion transport. In this work, we demonstrate that the use of methyl propionate (MP) carboxylate and fluorocarbonate vinyl (FEC) electrolytes can overcome the limitations of low temperature cycling. Compared with carbonate electrolyte, MP has the characteristics of low melting point, low viscosity and low binding energy with Li+, which is crucial to improve the low temperature performance of the battery, while FEC is an effective component to inhibit the side reaction between MP and lithium metal. The carefully formulated MP-based electrolyte can generate a solid electrolyte interface with low resistance and rich in inorganic substances, which is conducive to the smooth diffusion of Li+, allowing the battery to successfully cycle at a high rate of 0.5 C at −20 °C, and giving it a reversible capacity retention rate of 65.3% at −40 oC. This work designs a promising advanced electrolyte and holds the potential to overcome limitations of lithium-ion batteries in harsh conditions.

Metal Doped Unconventional Phase IrNi Nanobranches: Tunable Electrochemical Nitrate Reduction Performance and Pollutants Upcycling.

Electrochemical nitrate reduction (NO3RR) provides a new option to abate nitrate contamination with a low carbon footprint. Restricted by competitive hydrogen evolution, achieving satisfied nitrate reduction performance in neutral media is still a challenge, especially for the regulation of this multielectron multiproton reaction. Herein, facile element doping is adopted to tune the catalytic behavior of IrNi alloy nanobranches with an unconventional hexagonal close-packed (hcp) phase toward NO3RR. In particular, the obtained hcp IrNiCu nanobranches favor the ammonia production and suppress byproduct formation in a neutral electrolyte indicated by in situ differential electrochemical mass spectrometry, with a high Faradaic efficiency (FE) of 85.6% and a large yield rate of 1253 μg cm-2 h-1 at -0.4 and -0.6 V (vs reversible hydrogen electrode (RHE)), respectively. In contrast, the resultant hcp IrNiCo nanobranches promote the formation of nitrite, with a peak FE of 33.1% at -0.1 V (vs RHE). Furthermore, a hybrid electrolysis cell consisting of NO3RR and formaldehyde oxidation is constructed, which are both catalyzed by hcp IrNiCu nanobranches. This electrolyzer exhibits lower overpotential and holds the potential to treat polluted air and wastewater simultaneously, shedding light on green chemical production based on contaminate degradation.

Fluorine-Doped Li7La3Zr2O12 Fiber-Based Composite Electrolyte for Solid-State Lithium Batteries with Enhanced Electrochemical Performance.

Garnet-based electrolytes with high ionic conductivity and excellent stability against lithium metal anodes are promising for commercial applications in solid-state lithium batteries (SSLBs). However, the further development of SSLBs is inhibited by issues such as low ionic conductivity and uncontrolled lithium dendrite growth. Herein, we report the synthesis of fluorine-doped Li7La3Zr2O12 (LLZO-F0.2) fibers by electrospinning and the subsequent calcination at high temperatures. The solid composite electrolyte with LLZO-F0.2 exhibits an ionic conductivity of 5.37 × 10-4 S cm-1 and a high lithium-ion transference number of 0.61 at room temperature. Meanwhile, it exhibits lower resistance and more uniform lithium metal stripping and deposition in symmetric cells. The full cell with LiFePO4 cathode exhibits excellent rate capability and cycling stability for 800 cycles at 0.5 C with a discharge specific capacity retention of 97.7%. This fluorine-doped fibrous garnet-type electrolyte provides a viable option for preparing high-performance SSLBs.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Deciphering Sodium-Ion Storage: 2D-Sulfide versus Oxide Through Experimental and Computational Analyses.

Transition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium-ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS2 micro-flower is synthesized by thermal sulfurization of WO3. Comprising interconnected thin nanosheets, this structure offers increased surface area, facilitating extensive internal surfaces for electrochemical redox reactions. The WS2 micro-flower demonstrates a specific capacity of ≈334mAhg-1 at 15mAg-1, nearly three times higher than its oxide counterpart. Further, it shows very stable performance as a high-temperature (65°C) anode with ≈180mAhg-1 reversible capacity at 100mAg-1 current rate. Post-cycling analysis confirms unchanged morphology, highlighting the structural stability and robustness of WS2. DFT calculations show that the electronic bandgap in both WS2 and WO3 increases when going from the bulk to monolayers. Na adsorption calculations show that Na atoms bind strongly in WO3 with a higher energy diffusion barrier when compared to WS2, corroborating the experimental findings. This study presents a significant insight into electrode material selection for sodium-ion storage applications.

Production and New Green Activation of Conductive 3D-Printed Cu/PLA Electrode: Its Performance in Hydrogen Evolution Reactions in Alkaline Media

In this study, Cu-polylactic acid (PLA) composite filaments were produced with an extruder and three-dimensional (3D) Cu/PLA electrodes were 3D printed with Fused Deposition Modelling (FDM) method. To improve the electrochemical performance of the 3D-Cu/PLA electrode, a novel electrochemical activation method, which differentiates from complex activation methods in the literature, was applied in 1 M KOH solution without using any solvent. Field emission scanning electron microscopy (FE-SEM), Energy-Dispersive X-ray Spectroscopy (EDX), Fourier Transform Infrared Spectroscopy (FT-IR), and RAMAN techniques were used to characterize the 3D-Cu/PLA electrode before and after activation. The results showed that Cu particles were released after the degradation of PLA after activation. In addition, the thermal stability of the 3D electrode was demonstrated by the TGA technique. The performance of the 3D Cu/PLA electrode before and after activation in the hydrogen evolution reaction (HER) in 1M solution was measured using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cathodic polarization curves methods. The EIS results showed that the charge transfers resistance values of the 3D-Cu/PLA electrode in 1 M KOH decreased significantly after activation. Post-activation hydrogen content measurements of the 3D-Cu/PLA electrode after electrolysis at different potentials and energy efficiency tests at different current densities were also carried out. The results indicate that the electrocatalytic properties of 3D-Cu electrodes were improved for HER through the activation process.

PolyanionNaNi1 − xCuxPO4 glass and glass-ceramic cathode network: Structure with improved electrochemical performance

PolyanionNaNi1 − xCuxPO4 glass and glass-ceramic cathode network: Structure with improved electrochemical performance

Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnyFe1-yF3@CFx was generated by the all-fluoride strategy, converting most of the carbon in MnyFe1-yF3@C into electrochemical active CFx through a controllable NF3 gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of MnyFe1-yF3@CFx composite was up to 765 mAh g-1 (pure FeF3 is 712 mAh g-1) and 728 mAh g-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF3@CFx).