Large-scale Energy Storage Devices Research Articles

Bi-Functional Interfacial Modification enables Highly-Exposed Zn(002) Crystal Facet towards Durable Zn Metal Batteries.

Zn-ion batteries (ZIBs) have garnered growing interest in large-scale energy storage devices for the high safety, high theoretical capacity and low electrochemical potential. Nevertheless, their widespread applications are significantly impeded by dendrite formation, hydrogen evolution and corrosion reactions of Zn anodes. Herein, a bi-functional polyacrylic acid (PAA) modified-Zn anode (Zn-PAA) is designed to concurrently inhibit Zn dendrite formation and alleviate side reactions. The bi-functional PAA coating not only selectively acid-etches the active Zn crystal facets to guide the planar deposition along the highly-exposed Zn(002) crystal facet, but also facilitate uniform Zn deposition through coordination between the polymer functional groups and Zn2+. Meanwhile, the electrically-insulated PAA protective layer effectively separates Zn anodes from the electrolyte and modulates the solvation structure of Zn2+.6H2O, significantly suppressing side reactions. Consequently, the assembled Zn-PAA//Zn-PAA symmetrical cell delivers an outstanding cycling stability of 1600 h at 1 mA cm-2 and 1 mAh cm-2. The assembled KVO//Zn-PAA full cell shows exceptional cycling stability over 1500 cycles at 2.0 A g-1 with a high Coulombic efficiency approaching 100%. The facile bi-functional surface modification strategy, which enables to finely tune the crystal facet texture and ion distribution manner, opens up a groundbreaking path towards safe and durable ZIBs.

Regulating interfacial behavior via reintegration the Helmholtz layer structure towards ultra-stable and wide-temperature-range aqueous zinc ion batteries

Aqueous zinc-ion batteries are recognized as a potential candidate in large-scale energy storage devices. However, parasitic reactions on interfaces have severely limited their further development due to sticky de-solvation process of Zn(H2O)62+. Acetylacetone (Hacac) is proposed as a tri-functional additive by altering the solvation structure to address detrimental interface issues. Specifically, the acetyl groups induced by decomposition of Hacac inhibit dendrite growth, by-product aggregation on anode via guiding ordered deposition of zinc ions and suppressing water decomposition in internal Helmholtz plane (IHP). Meanwhile, the acetyl groups remarkably alleviate by-product aggregation and maintain the cathode structure by accelerating zinc ion transfer and inhibiting disintegration of water in IHP. With the addition of 0.5 wt% Hacac, Zn metal maintains a high coulombic efficiency of 99.9 % after 2000 cycles at 10 mA cm−2 and 1 mAh cm−2, with superior longevity of 5200 h at 1 mA cm−2 with 0.5 mAh cm−2 for Zn|Zn cells. As expected, the assembled Zn|NH4V4O10 batteries exhibit an outstanding capacity retention of 90 % up to 22,000 cycles at 10 A/g. As a highly efficient strategy, the reframing of Helmholtz layer structure via electrolyte additive could be broadened to address general interfacial issues in advanced energy storage systems.

High performance rechargeable aluminium ion batteries enabled by full utilization and understanding of polyaniline cathodes

As a renowned conductive polymer, polyaniline (PANI) shows remarkable potential in organic cathode materials for rechargeable aluminium ion batteries (RAIBs). However, existing research has not given sufficient understanding and explanation of the structure and states of PANI but failed to achieve ideal electrochemical performance. In this study, we differentiate and investigate for the first time its primary-doped (PANI-1), re-doped (PANI-Re), secondary-doped (PANI-2), and emeraldine based (PANI-EB) forms, meanwhile attempt to enhance the conductivity of PANI-EB using multi-walled carbon nanotubes (PANI-EB@C). Among them, the high-doped PANI-2 and non-doped PANI-EB exhibit theoretical capacity utilization far superior to lower doped PANI-1 and PANI-Re, with both specific capacities reaching approximately 225 mAh/g (full capacity utilization rate of 76.53 %) at a current density of 1 A/g, while maintaining capacity retention rates of 92.89 % after 2000 cycles and 92.44 % after 5000 cycles, respectively. Furthermore, the high-conductivity PANI-EB@C displays a discharge specific capacity of 284 mAh/g (full capacity utilization rate of 96.59 %), with a capacity retention rate of 91.19 % after 5000 cycles. Electrochemical analysis, Gaussian theoretical calculations, ex-situ characterization collectively indicate that the electrochemical performance of doped PANI is positively correlated with the degree of doping-induced conductivity changes, while the unique internal redox process of PANI-EB enhances the release of performance and could be further optimized by the assistant of conductivity medium. This work advances the classification of the electrochemical performance and structural understanding of PANI cathode materials to an extremely high stage, towards the practical application of a low-cost, high-performance, sustainable, and green cathode material in large-scale energy storage devices.

Fullerenol as a nano-molecular sieve additive enables stable zinc metal anodes

Aqueous zinc batteries (AZBs) with the advantages of safety, low cost, and sustainability are promising candidates for large-scale energy storage devices. However, the issues of interface side reactions and dendrite growth at the zinc metal anode (ZMA) significantly harm the cycling lifespan of AZBs. In this study, we designed a nano-molecular sieve additive, fullerenol (C60(OH)n), which possesses a surface rich in hydroxyl groups that can be uniformly dispersed in the aqueous solution, and captures free water in the electrolyte, thereby suppressing the occurrence of interfacial corrosion. Besides, fullerenol can be further reduced to fullerene (C60) on the surface of ZMA, holding a unique self-smoothing effect that can inhibit the growth of dendritic Zn. With the synergistic action of these two effects, the fullerenol-contained electrolyte (FE) enables dendrite-free ZMAs. The Zn−Ti half-cell using FE exhibits stable cycling over 2500 times at 5 mA cm−2 with an average Coulombic efficiency as high as 99.8 %. Additionally, the Zn−NaV3O8 cell using this electrolyte displays a capacity retention rate of 100 % after 1000 cycles at −20 °C. This work provides important insights into the molecular design of multifunctional electrolyte additives.

Mesoporous copper-doped δ-MnO2 superstructures to enable high-performance aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) are competitive alternatives for large-scale energy-storage devices owing to the abundance of zinc and low cost, high theoretical specific capacity, and high safety of these batteries. High-performance and stable cathode materials in AZIBs are the key to storing Zn2+. Manganese-based cathode materials have attracted considerable attention because of their abundance, low toxicity, low cost, and abundant valence states (Mn2+, Mn3+, Mn4+, and Mn7+). However, as a typical cathode material, birnessite-MnO2 (δ-MnO2) has low conductivity and structural instability. The crystal structure may undergo severe distortion, disorder, and structural damage, leading to severe cyclic instability. In addition, its energy-storage mechanism is still unclear, and most of the reported manganese oxide-based materials do not have excellent electrochemical performance. Herein, we propose a copper-doped Cu0.05K0.11Mn0.84O2·0.54H2O (Cu2-KMO) cathode, which exhibits a large interlayer spacing, a stable structure, and accelerated reaction kinetics. This cathode was prepared using a simple hydrothermal method. The AZIB assembled using Cu2-KMO showed high specific capacity (600 mA h g−1 at 0.1 A g−1 after 75 cycles). The dissolution-deposition energy storage mechanism of Cu-KMO in AZIBs with double electron transfer was revealed using ex situ tests. The good electrochemical performance of the Cu2-KMO cathode fabricated by the doping strategy in this study provides ideas for the subsequent preparation of manganese dioxide using other strategies.

Selective Lattice Doping Enables a Low-Cost, High-Capacity and Long-Lasting Potassium Layered Oxide Cathode for Potassium and Sodium Storage.

Layered transition metal oxides are highly promising host materials for K ions, owing to their high theoretical capacities and appropriate operational potentials. To address the intrinsic issues of KxMnO2 cathodes and optimize their electrochemical properties, a novel P3-type oxide doped with carefully chosen cost-effective, electrochemically active and multi-functional elements is proposed, namely K0.57Cu0.1Fe0.1Mn0.8O2. Compared to the pristine K0.56MnO2, its reversible specific is increased from 104 to 135 mAh g-1. In addition, the Cu and Fe co-doping triples the capacity under high current densities, and contributes to long-term stability over 500 cycles with a capacity retention of 68 %. Such endeavor holds the potential to make potassium-ion batteries particularly competitive for application in sustainable, low-cost, and large-scale energy storage devices. In addition, the cathode is also extended for sodium storage. Facilitated by the interlayer K ions that protect the layered structure from collapsing and expand the diffusion pathway for sodium ions, the cathode shows a high reversible capacity of 144 mAh g-1, fast kinetics and a long lifespan over 1000 cycles. The findings offer a novel pathway for the development of high-performance and cost-effective sodium-ion batteries.

Magnetic field based finite element method for magneto-static problems with discontinuous electric potential distributions

We introduce two finite element formulations to approximate magneto-static problems with discontinuous electric potential based respectively on the electrical scalar potential and the magnetic field. This work is motivated by our interest in Liquid Metal Batteries (LMBs), a promising technology for storing intermittent renewable sources of energy in large scale energy storage devices. LMBs consist of three liquid layers stably stratified and immiscible, with a light liquid metal on top (negative electrode), a molten salt in the middle (electrolyte) and a heavier liquid metal on bottom (positive electrode). Energy is stored in electrical potential differences that can be modeled as jumps at each electrode-electrolyte interface. This paper focuses on introducing new finite element methods for computing current and potential distributions, which account for internal voltage jumps in liquid metal batteries. Two different formulations that use as primary unknowns the electrical potential and magnetic field, respectively, are presented. We validate them using various manufactured test cases, and discuss their applications for simulating the current distribution during the discharge phase in a liquid metal battery.

Principles and Design of Biphasic Self-Stratifying Batteries Toward Next-Generation Energy Storage.

Large-scale energy storage devices play pivotal roles in effectively harvesting and utilizing green renewable energies (such as solar and wind energy) with capricious nature. Biphasic self-stratifying batteries (BSBs) have emerged as a promising alternative for grid energy storage owing to their membraneless architecture and innovative battery design philosophy, which holds promise for enhancing the overall performance of the energy storage system and reducing operation and maintenance costs. This minireview aims to provide a timely review of such emerging energy storage technology, including its fundamental design principles, existing categories, and prototype architectures. The challenges and opportunities of this undergoing research topic will also be systematically highlighted and discussed to provide guidance for the subsequent R&D of superior BSBs while conducive to bridging the gap for their future practical application.

Insights into novel indium catalyst to kW scale low cost, high cycle stability of iron-chromium redox flow battery

Iron-chromium flow batteries (ICRFBs) have emerged as an ideal large-scale energy storage device with broad application prospects in recent years. Enhancement of the Cr3+/Cr2+ redox reaction activity and inhibition of the hydrogen evolution side reaction (HER) are essential for the development of ICRFBs and require a novel catalyst design. However, elucidating the underlying mechanisms for modulating catalyst behaviors remains an unresolved challenge. Here, we show a novel precisely controlled preparation of a novel thermal-treated carbon cloth electrode with a uniform deposit of low-cost indium catalyst particles. The density functional theory analysis reveals the In catalyst has a significant adsorption effect on the reactants and improves the redox reaction activity of Cr3+/Cr2+. Moreover, H+ is more easily absorbed on the surface of the catalyst with a high migration energy barrier, thereby inhibiting the occurrence of HER. The assembled ICRFBs have an average energy efficiency of 83.91% at 140 mA/cm2, and this method minimizes the electrodeposition process and cleans the last obstacle for industry long cycle operation requirements. The ICRFBs exhibit exceptional long-term stability with an energy efficiency decay rate of 0.011% per cycle at 1000 cycles, the lowest ICRFBs reported so far. Therefore, this study provides a promising strategy for developing ICRFBs with low costs and long cycle life.

Methyl-Symmetrically Substituted Poly(3,4-Dimethylthiophene) as Cathode for Aluminum Ion Batteries.

The aggravation of energy problems and the scarcity of lithium resources have forced us to look for new energy storage systems. Aluminum ion batteries, as a promising energy storage system, have the advantages of environmental friendliness and abundant aluminum resources, and have the potential for application in large-scale energy storage and personal portable electronic devices. To solve the stability problem of aluminum ion batteries during cycling for large-scale energy storage needs, we report a polythiophene-based conductive polymer, poly(3,4-dimethylthiophene) (PDMT), as a high performance cathode material for aluminum ion batteries. By introducing two methyl groups on the thiophene ring, we successfully adjust the local charge density of the heterocyclic thiophene, thus changing the electron delocalization characteristics, and improving the electrochemical reaction activity of the polythiophene (PTH) material as a redox electrode material. This also maintains the symmetry and regularity of the polymer structure, giving the material better cycling stability. The discharge specific capacity reaches 110 mAh g-1 at a current density of 200 mA g-1, far exceeding conventional PTH cathodes (~70 mAh g-1), and the capacity retention rate is 92.7 % after 1000 cycles. It also shows excellent rate performance due to the flexible structure of the conductive polymer.

Hollow Carbon and MXene Dual-Reinforced MoS2 with Enlarged Interlayers for High-Rate and High-Capacity Sodium Storage Systems.

Sodium-ion batteries (SIBs) and sodium-ion capacitors (SICs) are promising candidates for cost-effective and large-scale energy storage devices. However, sluggish kinetics and low capacity of traditional anode materials inhibit their practical applications. Herein, a novel design featuring a layer-expanded MoS2 is presented that dual-reinforced by hollow N, P-codoped carbon as the inner supporter and surface groups abundant MXene as the outer supporter, resulting in a cross-linked robust composite (NPC@MoS2/MXene). The hollow N, P-codoped carbon effectively prevents agglomeration of MoS2 layers and facilitates shorter distances between the electrolyte and electrode. The conductive MXene outer surface envelops the NPC@MoS2 units inside, creating interconnected channels that enable efficient charge transfer and diffusion, ensuring rapid kinetics and enhanced electrode utilization. It exhibits a high reversible capacity of 453 mAh g-1, remarkable cycling stability, and exceptional rate capability with 54% capacity retention when the current density increases from 100 to 5000mA g-1 toward SIBs. The kinetic mechanism studies reveal that the NPC@MoS2/MXene demonstrates a pseudocapacitance dominated hybrid sodiation/desodiation process. Coupled with active carbon (AC), the NPC@MoS2/MXene//AC SICs achieve both high energy density of 136Wh kg-1 at 254W kg-1 and high-power density of 5940W kg-1 at 27Wh g-1, maintaining excellent stability.

Self-assembled high polypyrrole loading flexible paper-based electrodes for high-performance supercapacitors

Despite the intriguing features of freestanding flexible electronic devices, such as their binder-free nature and cost-effectiveness, the limited loading capacity of active material poses a challenge to achieving practical high-performance flexible electrodes. We propose a novel approach that integrates multiple self-assembly and in-situ polymerization techniques to fabricate a high-loading paper-based flexible electrode (MXene/Polypyrrole/Paper) with exceptional areal capacitance. The approach enables polypyrrole to form a porous conductive network structure on the surface of paper fiber through MXene grafting via hydrogen bonding and electrostatic interaction, resulting in an exceptionally high polypyrrole loading of 10.0 mg/cm2 and a conductivity of 2.03 S/cm. Moreover, MXene-modified polypyrrole paper exhibits a more homogeneous pore size distribution ranging from 5 to 50 μm and an increased specific surface area of 3.11 m2/g. Additionally, we have optimized in-situ polymerization cycles for paper-based supercapacitors, resulting in a remarkable areal capacitance of 2316 mF/cm2 (at 2 mA/cm2). The capacitance retention rate and conductivity rate maintain over 90 % after undergoing 100 bends.The maximum energy density and cycling stability are characterized to be 83.6 μWh/cm2 and up to 96 % retention after 10,000 cycles. These results significantly outperform those previously reported for paper-based counterparts. Overall, our work presents a facile and versatile strategy for assembling high-loading, paper-based flexible supercapacitors network architecture that can be employed in developing large-scale energy storage devices.

Stable organic polymer anode for high rate and fast charge sodium based dual-ion battery.

Considering the extensive resources, flexible structural designability, and abundant active sites, organic electrodes have been considered as the ideal sodium storage materials. However, organic materials generally face the limitations of unstable and dissolved characteristic, leading to a poor cyclic stability. In this work, we proposed a carbon nanotube (CNT) modified polyimide as the anode for sodium-based dual-ion battery (SDIB). The polyimide remains well the structure and morphology of monomer with a stable conjugated structure and high degree of crystallinity, effectively enhancing the electrochemical performance of the SDIBs. Also, the cooperation with CNT particularly improves the ion conductivity of the anode and advances the rate performance. Combined with an ionic liquid electrolyte, the constructed dual-ion battery exhibits excellent rate capability, high specific discharge capacity and stable cycling performance. It delivers a specific discharge capacity of 119.3 mA h g-1 at 0.2 C (1 C=100 mA g-1) and still has a specific discharge capacity of 82.3 mA h g-1 even after 1000 cycles at 10 C. Besides, the system displays a low self-discharge rate and stable fast charging performance, which is expected to be applied in the large-scale electrochemical energy storage devices and inspire the future development of SDIBs.

Effect of porous layer and initial salt gradient on improving SGSP stability: Transient numerical simulation and theoretical analysis

The salt gradient solar pond (SGSP) is a low-cost and large-scale solar energy capture and storage device. The stability of the non-convective zone (NCZ) is critical for the well-functioning and efficiency of SGSP. To understand when and how SGSP lost its effectiveness, the turbulent double-diffusive convection in solar ponds was first solved numerically with a Large Eddy Simulations (LES) model. The simulations show that attaching a porous layer or increasing the initial salt concentration effectively delays the destruction of NCZ. By increasing the initial salt concentration from 5.2% to 20.8%, the destruction time increases from 7 to 22 h. By attaching a porous layer, the overturn time can increase by about 8 h, resulting in a temperature rise from 46 °C to 73 °C in the storage layer. The flow field analysis shows that both interface erosion and turbulent mixing in NCZ cause the destruction of NCZ. The stability analysis shows that the turbulent mixing decreases the salinity gradient in NCZ, making it more susceptible to erosion. By inhibiting the turbulent mixing, the porous layer at the bottom can effectively delay the arrival of NCZ destruction. Thus, the heat storage capacity and stability of solar ponds are enhanced.

Rationally designed carbon-encapsulated manganese selenide composites from metal–organic frameworks for stable aqueous Zn–Mn batteries

Electrochemical kinetics unveiled enhanced surface pseudocapacitance in C@MnSe@GO-2, while ex situ XRD exposed the transformation mechanism during activation.

Ni0.5Co0.5S nano-chains: a high-performing intercalating pseudocapacitive electrode in asymmetric supercapacitor (ASC) mode for the development of large-scale energy storage devices.

Grid-scale energy storage solutions are necessary for using renewable energy sources efficiently. A supercapattery (supercapacitor + battery) has recently been introduced as a new variety of hybrid devices that engage both capacitive and faradaic charge storage processes. Nano-chain architectures of Ni0.5Co0.5S electrode materials consisting of interconnected nano-spheres are rationally constructed by tailoring the surface structure. Nano-chains of the bimetallic sulfide Ni0.5Co0.5S are presented to have a superior charge storage capacity. The Ni0.5Co0.5S nano-chain electrode presents a capacitance of 2001.6 F g-1 at 1 mV s-1, with a specific capacity of 267 mA h g-1 (1920 F g-1) at 1 A g-1 in 4 M KOH aqueous electrolyte through the galvanostatic charge-discharge (GCD) method. The reason behind the high charge storage capacity of the materials is the predominant redox-mediated diffusion-controlled pseudocapacitive mechanism coupled with surface capacitance (electrosorption), as the surface (outer) and intercalative (inner) charges stored by the Ni0.5Co0.5S electrodes are close to 46.0% and 54.0%, respectively. Additionally, a Ni0.5Co0.5S//AC two electrode full cell operating in asymmetric supercapacitor cell (ASCs) mode in 4 M KOH electrolyte exhibits an impressive energy density equivalent to 257 W h kg-1 and a power density of 0.73 kW kg-1 at a current rate of 1 A g-1.

Use of Mixed Methanesulfonic Acid/Sulfuric Acid as Positive Supporting Electrolyte and the Study of Ion Crossover in Zn-Ce Redox Flow Battery

The development of a highly efficient and inexpensive energy storage technology is central to the operation of a sustainable smart grid and widespread utilization of intermittent renewable energy sources. An emerging and promising grid-scale technology for electrochemical energy storage is the redox flow battery (RFB). A unique and particularly valuable aspect of the design of RFBs is that their energy and power capacities can be scaled independently. Some of their other advantages include short response time, long life-cycles and no detrimental effects associated with being fully charged or discharged [1]. The Zn-Ce RFB, first developed by Plurion Inc (UK) in 2005 [2], has an open-circuit voltage as high as 2.4 V which is one of the highest among the various RBFs.To further improve the efficiency of Zn-Ce RBFs, the effect of different positive supporting electrolytes on the performance of a bench-scale Zn-Ce RFB has been studied. The effectiveness of mixed methanesulfonic/sulfuric acid, mixed methanesulfonic/nitric acid and pure methanesulfonic acid has been assessed and compared on the basis of the cyclic voltammetry response for the Ce(III)/Ce(IV) redox couple and galvanic charge-discharge of a bench-scale Zn-Ce RFB. We have observed the Ce(III)/Ce(IV) reaction to exhibit faster kinetics and the battery to attain higher coulombic efficiency and long-term performance over ~40 charge-discharge cycles in the mixed 2 mol/L MSA–0.5 mol/L H2SO4 electrolyte compared to that achieved in the commonly used 4 mol/L pure MSA electrolyte due to lower H+ crossover and the prevention of CeO2 precipitation. The coulombic efficiency fade rate in the mixed MSA-H2SO4 electrolyte is 0.55% per cycle over 40 charge-discharge cycles, while the fade rate is 1.26% in the case of 4 mol/L MSA. Furthermore, the positive electrode reaction is no longer the limiting half-cell reaction even at the end of long-term battery charge-discharge operation [3]. Our results show that a mixed MSA–H2SO4 acid electrolyte may be a better option for the positive side of a Zn-Ce RFB as a large-scale energy storage device.At the same time, undesired ion crossover is a practical issue that cannot be neglected since it decreases the concentrations of electroactive species in both negative and positive electrolytes and can cause battery self-discharge and thereby lower battery efficiency and longevity. The concentrations of electroactive species in both the positive and negative electrolytes after each charge-discharge cycle have been monitored as a function of cycle number. We have found that as much as 48.6% of the Zn(II) ions are transported through the Nafion 117 membrane from the negative to the positive electrolyte and 11.1% of Ce(III) ions are transported from the positive to the negative electrolyte by the end of 30 cycles (~55 hours of battery operation). A simple and efficient method to mitigate this problem is to add a certain amount of Zn(II) to the positive electrolyte and Ce(III) to the negative electrolyte at the outset of operation in order to reduce the concentration gradients between the two sides. From our cyclic voltammetry results, the addition of Zn(II) ions into the positive electrolyte has no deleterious effect on the Ce(III)/Ce(IV) redox couple and in fact appears to slightly reduce the separation between the reduction and oxidation peaks, suggesting better reversibility of the positive electrode reaction. In addition, experiments involving 30 cycles of battery charge-discharge have been conducted using Zn(II)-containing pure MSA positive electrolyte as well as Zn(II)-containing MSA-H2SO4 mixed acid electrolytes to analyze battery efficiency. Our results show that both the coulombic and voltage efficiencies are increased compared to that attained using the original electrolytes without Zn(II) initially added to the positive electrolytes. The energy efficiency increases by 19.7% in the case of the Zn(II)-containing pure MSA electrolyte and 6.1% for the Zn(II)-containing H2SO4-MSA mixed acid electrolyte (see Figure 1). Another benefit of adding Zn(II) ions to the MSA pure positive electrolyte is that it prevents the precipitation of CeO2 routinely observed to occur in MSA-only electrolytes after 10 – 15 charge-discharge cycles, which further enhances the energy density of the Zn-Ce RFB.References Nguyen, T. and R.F. Savinell, Flow Batteries. Electrochemical Society Interface, 2010. 19(3), 54.Clarke, R., B. Dougherty, S. Harrison, P. Millington, and S. Mohanta, US Patent 2004/0202925 A1. Cerium Batteries, 2004.Yu, H., M. Pritzker, and J. Gostick, Use of Mixed Methanesulfonic Acid/Sulfuric Acid as Positive Supporting Electrolyte in Zn-Ce Redox Flow Battery. J. Electrochemical Society, 2023. 170(2), 020536. Figure 1

Fatal Impurity for Electrochemical Mg Deposition/Dissolution

Rechargeable magnesium batteries (RMBs) are promising large-scale stationary energy storage devices. A manufacturing system similar to that used for lithium-ion batteries should be adoptable to the fabrication of RMBs. However, the compatibility of RMB components with atmospheric components other than moisture has not been studied yet. This might be due to the uncertain preconception and misunderstanding of the passivation characteristics of magnesium. In this study, we investigated the effects of atmospheric conditions on the electrochemical dissolution–deposition behavior of magnesium in non-aqueous electrolytes.1 The compatibility of magnesium metal and electrolytes incorporating air-stable weakly-coordinated anions [B(HFIP)4]− or [Al(HFIP)4]− (HFIP: hexafluoro-iso-propoxyl) with dry air was investigated. The results of a simple cyclic voltammetry (CV) clearly demonstrate the far excessive care of magnesium metals against atmospheric O2, because reversible magnesium deposition/dissolution is possible using magnesium metals polished under dry air. However, cells assembled under a dry-air atmosphere show no features of electrochemical magnesium deposition/dissolution. To identify which component of a dry air has a significant detrimental effect on the electrochemical characteristics, systematic CV and open-circuit potential (OCP) measurements were conducted under certain atmospheric conditions with Ar, N2, and O2 and an air-tight voltammetry cell equipped with gas-inlet lines. The platinum and magnesium working electrodes show characteristic responses dependent on the inlet gases, and O2 gas is found to be detrimental for the electrochemical activities of magnesium (Figure 1). The time-profile of OCP and that of O2 content in the electrolyte under steady flow of O2 gas are correlated well, suggesting passivation of magnesium metal upon uptake of O2 in the electrolyte. The electrochemical impedance spectra of symmetric magnesium metal cells using oxygenated and deoxygenated electrolytes and X-ray photoelectron spectra further corroborate inactivation of magnesium by even miniscule amount, ca., 10 ppm, of O2 impurity. Acknowledgement This work was financially supported by the Advanced Low-Carbon Technology-Specially Promoted Research for Innovative Next Generation Batteries Program (ALCA-SPRING, Grant Number JPMJAL1301), NEXT Center of Innovation Program (COI-NEXT, Grant Number JPMJPF2016) of the Japan Science and Technology Agency, and KAKENHI (Grant No. 21K05263) of the Japan Society for the Promotion of Science. Reference T. Mandai and M. Watanabe, under revision. Figure 1

Performance analysis and gradient-porosity electrode design of vanadium redox flow batteries based on CFD simulations under open-source environment

As a promising large-scale energy storage device, the vanadium redox flow battery (VRFB) has attracted attention due to its excellent safety, the independence between energy capacity and power capacity, the suitable polarization potential, and the ability to avoid cross-contamination. In this work, a 3D model of VRFB is developed based on the open-source computational fluid dynamics (CFD) platform OpenFOAM, which is well-validated. Then, the effect of operating conditions is studied, which shows that a higher electrolyte concentration can reduce the overpotential and increase the discharge voltage. Reducing the current density can increase the deepness of charge and discharge, reduce the electrolyte concentration gradient, the mass transfer loss and the activation loss. In addition, the effect of electrode porosity is studied that the overpotential decreases near the membrane and increases near the current collector with increasing porosity. Finally, the effect of porosity changes in different directions is studied, and an attempt is made to utilize this overpotential distribution by introducing the gradient-porosity electrode to reduce the non-uniformity of overpotential. The gradient-porosity electrode design using higher porosity near the membrane and lower porosity near the current collector can effectively improve the distribution of overpotential and increase battery performance by 1.67 mV.

Promoting reversibility of layered potassium cathode through interstitial doping

With the increasing needs for large-scale and low-cost energy storage devices, Mn-based layered oxide cathodes have achieved considerable researching interests for potassium-ion batteries owing to their high energy density, abundant resource and low toxicity. However, their developments are challenged by the absence of suitable cathode materials to tolerate large-sized K-ion insertion/extraction and the presence of Jahn-Teller distortion of Mn3+. To address this issue, we present a strategy of embedding boron into interstitial tetrahedral sites to obtain a P3-K0.5Mn0.8Co0.2B0.1O2 cathode. Strong B-O covalent bonds facilitate the construction of robust orthorhombic framework and alleviate the undesired elongation of Mn-O bonds, contributing to excellent electrochemical performance. In addition, boron ions are verified to promote the formation of a homogeneous cathode electrolyte interphase layer, improving interfacial stability and realizing highly reversible cycling in a wide voltage range (1.4–4.3 V). This strategy provides a new pathway towards the development of high-performance cathode materials for potassium-ion batteries.