Magnesium-ion Batteries Research Articles

Tuning MgCl2 content in BMIMPF6 to optimize mg-ion battery performance

This study aims to explore magnesium chloride salt-ionic liquid as an efficient electrolyte for Magnesium-ion Batteries (MIBs) using graphite as a cathode material. A complete physicochemical and electrochemical characterizations were performed on a number of electrolyte compositions and important properties including ion solvation, specific conductivity, ion transport behaviour, dominant ionic species, and electrochemical stability were tested. Also, the effect of magnesium salt concentration on specific capacity, reversibility, stability, charge retention, and rate capability were examined. Moreover, the effect of graphite electrodes on Solid Electrolyte Interphase (SEI) layer, its practicality, and cyclability of the different electrolyte compositions afforded interesting conclusions by this comprehensive comparison of electrode-electrolyte pairings. This evaluation is further supported by life cycle analysis, which gave an important information on how to keep electrodes structurally intact even after several uses. Though there were differences in the three electrolyte systems with respect to reversibility, stability, cyclicbility, capacity fading, and unexpected failures, the 0.2 M electrolyte showcased a notable feature of a high ionic conductivity (4.6 × 10−3 mS cm−1) at room temperature and strong anodic stability (4.0 V vs. Mg/Mg2+). Thus, endorsing the developed system as promising lead for further exploration. Additionally, magnesium dissolution and deposition on a Pt working electrode in this electrolyte was also thoroughly examined in this study. The process of PF6¯ ion intercalation and de-intercalation into graphite layer structure was examined using Cyclic Voltammetry (CV). Based on the analysis by Field Emission- Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS), a change in the active-material morphology was observed and we hypothesize that this might be the reason for the improved performance.

High cycling stability of MnO2 cathode for aqueous Mg-ion batteries enabled by Fe doping

MnO2 has been widely investigated as a promising cathode material for aqueous magnesium-ion batteries, which, however, suffers from the severe capacity fading during charge/discharge cycling. In present work, we report that the doping of Fe in α-MnO2 enlarges the lattice and alleviates the Jahn–Teller distortions and thus accelerates the Mg2+ diffusion and strengthens the structural stability. Consequently, the capacity retention remarkably increases from 44.3 % to 85.2 % after 1000 cycles by Fe doping. Furthermore, it is found for the first time that Fe doping enables the co-insertion of H+ and Mg2+ in the tunnels of α-MnO2, which improves remarkably the specific capacity from 131.9 to 205.9 mA h g−1 at 0.1 A g−1.

Magnesium-eutectic electrolyte as a winning combination for sustainable battery

Eutectic-Magnesium electrolytes are sparsely used electrolytes in Magnesium ion batteries. In this context, readily available less toxic precursors based eutectic electrolytes are attracting increasing interest owing to the focus of sustainable battery development. The unique benefits of magnesium such as high specific capacity, low reduction potential, and remarkable reversibility without dendrimer formation are highly advantages when compare to lithium based batteries. Developing an optimal electrolyte composition is a key area of study in the field of battery technology. With improved cell performance, stability across cycles, and general safety, we hope to reduce unwanted interfacial reactions. In this study, we examined eutectic combination of trimethylamine hydrochloride and aluminium chloride (TMA: AlCl3 = TMA) along with magnesium perchlorate to understand ion-solvation, complexation, thermal stability, ion transport and conduction, and electrochemical stability, certain physico-chemical and electrochemical parameters were evaluated prior to assessing the cell's performance. The salient features being an ionic conductivity (σ) of 6.25×10−3 mS cm−1 at 30 °C, remarkable performance retention with over 90 cycles of operation with the electrolyte and an impressive capacity of 90 mAh/g. The behaviour of ionic conductivity with temperature followed the Vogel-Tammann-Fulcher (VTF) equation. Moreover, the anodic stability around 2.5 V (Mg/Mg2+) when platinum is used as the working electrode endorses the suitability of the electrolyte for use in Rechargeable Magnesium Batteries (RMBs).The promising results of this first investigation open up new possibilities for investigating complementary pairings with the aim of improving the efficiency of magnesium-ion cells.

Exploring role of microbatteries in enhancing sustainability and functionality of implantable biosensors and bioelectronics

Microbatteries are emerging as a sustainable, miniaturized power source, crucial for implantable biomedical devices. Their significance lies in offering high energy density, longevity, and rechargeability, facilitating uninterrupted health monitoring and treatment within the body. The review delves into the development of microbatteries, emphasizing their miniaturization and biocompatibility, crucial for long-term, safe in-vivo use. It examines cutting-edge manufacturing techniques like physical and chemical vapor deposition, and atomic layer deposition, essential for the precision manufacture of the microbatteries. The paper contrasts primary and secondary batteries, highlighting the advantages of zinc-ion and magnesium-ion batteries for enhanced stability and reduced reactivity. It also explores biodegradable batteries, potentially obviating the need for surgical extraction post-use. The integration of microbatteries into diagnostic and therapeutic devices is also discussed, illustrating how they enhance the efficacy and sustainability of implantable biosensors and bioelectronics.

Carbon-coated BiOCl/Bi heterojunction flowerlike microspheres for collaboratively boosting storage magnesium performance

BiOCl is considered a promising anode material for magnesium ion batteries (MIBs), but its further development is limited by the inherent semiconductor properties and the sluggish Mg2+ diffusion kinetics. Herein, carbon-coated BiOCl/Bi heterojunction flowerlike microspheres (BiOCl/Bi@C) were prepared via a simple solvothermal method followed by annealing and used as an anode for MIBs for the first time. In this intricately designed structure, the heterointerface not only provides additional active sites to increase capacity but also creates a built-in electric field to facilitate electron/ion transport, while the carbon-coated flowerlike microsphere not only shortens the ion diffusion path but also relieves volume variation during cycling. As expected, it exhibits impressive specific capacity (134.2 mAh g−1 after 130 cycles) and outstanding rate performance (156.7 mAh g−1 at 500 mA g−1). Importantly, the storage Mg mechanism of BiOCl/Bi@C was investigated, and the results suggest that BiOCl is first converted into Bi and then alloyed to Mg3Bi2 in the discharging process, while Mg3Bi2 is dealloyed to Bi and then turned back to BiOCl in the charging process. The current study provides an effective strategy for constructing heterostructure anodes to enhance the Mg2+ transfer and storage.

Synergistic Cathode Design for High-Performance Dual-Salt Magnesium/Lithium-Ion Batteries Using 2D/2D 1T/2H-MoS2@Ti3C2Tx MXene Nanocomposite.

Magnesium-ion batteries (MIBs) and dual-salt magnesium/lithium-ion batteries (MLIBs) have emerged as promising contenders for next-generation energy storage. In contrast to lithium metal anode in lithium metal batteries, magnesium metal anode in MIBs and MLIBs presents a safer alternative due to the limited dendrite growth and higher volumetric capacity, along with higher natural abundance. This study explores a MLIB configuration with a novel cathode design by employing a 2D/2D nanocomposite of 1T/2H mixed phase MoS2 and delaminated Ti3C2Tx MXene (1T/2H-MoS2@MXene) to address challenges associated with slow kinetics of magnesium ions during cathode interactions. This cathode design takes advantage of the high electrical conductivity of Ti3C2Tx MXene and the expanded interlayer spacing with enhanced conductivity of the 1T metallic phase in 1T/2H mixed phase MoS2. Through a designed synthesis method, the resulting nanocomposite cathode maintains structural integrity, enabling the stable and reversible storage of dual Mg2+ and Li+ ions. The nanocomposite cathode demonstrates superior performance in MLIBs compared to individual components (253 mAh g-1 at 50 mA g-1, and 36% of capacity retention at 1,000 mA g-1), showcasing short ion transport paths and fast ion storage kinetics. This work represents a significant advancement in cathode material design for cost-effective and safeMLIBs.

Highly cycle-stable VOPO4-based cathodes for magnesium ion batteries: Insight into the role of interlayer engineering in batteries performance

Highly cycle-stable VOPO4-based cathodes for magnesium ion batteries: Insight into the role of interlayer engineering in batteries performance

Tin–containing Silicon Oxycarbonitride Ceramic Nanocomposites as Stable Anode for Magnesium Ion Batteries

AbstractThe development of magnesium ion batteries as a viable alternative to lithium–ion batteries is impeded by the lack of efficient and stable electrode materials. Here, we present the synthesis of nanocomposites of tin–containing silicon oxycarbonitride (Sn/SiOCN) as anode materials for magnesium ion batteries (MIBs). The elemental and phase composition, morphology, and surface area of the nanocomposites are assessed by several characterization techniques. The galvanostatic cycling tests indicate a substantial initial discharging capacity for the anode with 42.2 wt . % of tin. Specifically, the first discharging capacities are 489.9 mA/g, 172.9 mA/g, and 136.6 mA/g at current densities of 0.5 mA/g, 50 mA/g, and 500 mA/g, respectively. After 100 cycles at a current density of 500 mA/g, the anode containing 33.8 wt % of tin exhibits a reversible capacity of 101.8 mAh/g and a remarkable rate performance efficiency of 76.5 %. Increasing tin content in the electrode materials increases the battery performance by decreasing electrode impedance and thus facilitating Mg2+ diffusion, as revealed by electrochemical impedance spectroscopy (EIS). Ex situ XRD and X‐ray photoelectron spectroscopy (XPS) characterizations following the magnesiation–demagnesiation process confirm the storage of reversible storage of Mg2+ ions in Sn/SiOCN electrode through incorporation in the SiOCN network and alloying/dealloying process involving Mg−Mg2Sn−Mg.

High-performance magnesium/sodium hybrid ion battery based on sodium vanadate oxide for reversible storage of Na+ and Mg2+

Magnesium ion batteries (MIBs) are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation. Magnesium-sodium hybrid ion batteries (MSHBs) are an effective way to address these problems. Here, we report a new type of MSHBs that use layered sodium vanadate ((Na, Mn)V8O20·5H2O, Mn-NVO) cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) anode in Mg2+/Na+ hybrid electrolytes. During electrochemical cycling, Mg2+ and Na+ co-participate in the cathode reactions, and the introduction of Na+ promotes the structural stability of the Mn-NVO cathode, as cleared by several ex-situ characterizations. Consequently, the Mn-NVO cathode presents great specific capacity (249.9 mA h g−1 at 300 mA g−1) and cycling (1500 cycles at 1500 mA g−1) in the Mg2+/Na+ hybrid electrolytes. Besides, full battery displays long lifespan with 10,000 cycles at 1000 mA g−1. The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method, and the mechanism for these improvements is discussed.

Heterojunction structure of cobalt sulfide cathodes for high-performance magnesium-ion batteries

Heterojunction structure of cobalt sulfide cathodes for high-performance magnesium-ion batteries

A DFT-based design of B/N/P-co-doped oxo-triarylmethyl as a robust anode material for magnesium-ion batteries

Magnesium-ion batteries (MIBs) are emerging as a promising alternative to lithium-ion batteries (LIBs) due to their superior safety features and cost-effectiveness. In this work, heteroatoms-co-doped oxo-triarylmethyl (B/N/P@oxTAM) as a favorable anode material for MIBs was investigated using density functional theory calculations. The B/N/P@oxTAM is a highly porous structure and has a better affinity for Mg-ions to attach to vacancy site. Partial density of states, open-circuit voltage, theoretical specific capacity, and diffusion energy barrier were calculated and discussed. A significant decrease in the HOMO-LUMO gap with no structural deformation occurred, suggesting the high cycling performance of B/N/P@oxTAM for MIBs. Moreover, the designed anode material demonstrated full loading with six Mg-ions at different active sites, indicating a high theoretical specific capacity of 513.75 mAh g−1 and a low open-circuit voltage of 0.07 V. The presence of a heterocyclic ring (borabenzene) with a diffusion energy barrier of 0.039 eV increased the diffusion of Mg-ions. Therefore, B/N/P@oxTAM can be used as a viable anode material for MIBs with extended life cycle and quick charge-discharge rates due to its low open-circuit voltage and diffusion energy barrier, as well as its high theoretical specific capacity value.

Theoretical investigation of Mo2C and Mo2CO2 as anodes for sodium/magnesium-ion batteries

Due to the rapid evolution of the global electronic product industry, the limited availability of lithium resources has prompted extensive research into alternative metal ion batteries that can substitute for lithium batteries. The exceptional potentiality for MXenes as electrode materials in energy storage batteries is demonstrated by excellent conductivity, expansive surface area, and mechanical strength. The performance of Na and Mg on Mo2C and Mo2CO2 monolayers have been investigated employing first-principles calculations, including geometry configurations, electronic structures, ion diffusion properties, open-circuit voltages, and theoretical specific capacities. The conductivity of stable anodes is superior both before and after ion adsorption. Additionally, the formation energies of Na/Mg on the monolayer are negative, indicating a strong binding between metal atoms and the substrate. The migration energy barriers of Na and Mg on Mo2C are estimated to be 0.017 eV and 0.070 eV, respectively, suggesting a significant level of mobility and reversibility for Mo2C. The predicted range of average open-circuit voltages for Na/Mg-ion battery anodes is approximately 0.05–1.00 V in the case of Mo2C and Mo2CO2. The highest concentrations of Na and Mg atoms on Mo2C and Mo2CO2 are achieved through multilayer adsorption up to Mo2CNa3.3, Mo2CMg2, Mo2CO2Na3.3, and Mo2CO2Mg1.8, resulting in corresponding theoretical capacities of 438, 526, 379 and 411 mA·h/g, respectively. In conclusion, the outstanding electrochemical performance of Mo2C and Mo2CO2 anode materials in sodium-ion batteries (SIBs) and magnesium-ion batteries (MIBs) has prompted the exploration of other MXenes electrodes with advantageous characteristics for ion battery applications, contributing to the advancement of renewable energy technology.

Inducing Rigidity in Layered Structures for Improved Anodic Performance in Magnesium-Ion Battery: A Computational Design

Inducing Rigidity in Layered Structures for Improved Anodic Performance in Magnesium-Ion Battery: A Computational Design

Hollow Porous Cu2S Nano-Spheres as High-Rate Magnesium Battery Cathode

The magnesium ion batteries are gaining huge attention in the field of battery energy due to high energy density, low cost potential and high safety performance. So far, the research of magnesium ion batteries has been slow. The surface and structural properties of cathode electrode materials greatly limiting the discharge performance of magnesium ion battery. Herein, a facile synthesis of Cu2S nano-hollow spheres for high performance magnesium ion battery cathode electrode materials was reported. This nano-hollow spheres have a large specific surface area (12.84 m2 g−1) which can reduce the volume expansion caused by magnesium ions during embedding and detachment, and facilitate ion diffusion during the discharge-charging process. Consequently, the nano-hollow porous Cu2S deliver a 152 mAh g−1 after 850 cycles at 560 mA g−1 hold a long-term cycling stability as cathode materials for magnesium ion battery. This work not only demonstrates the great potential of NHP-Cu2S materials, for application in magnesium ion batteries, but also sheds a new light on the application of metal sulfides in magnesium ion batteries.

Pyrazinoquinoxaline graphdiyne: A novel high-capacity anode material for metal-ion batteries

The rapid expansion of the electronics industry and the growing need for advanced energy storage solutions have driven the quest for rechargeable batteries with improved capacity and prolonged lifetimes. In this context, significant attention has been directed towards the exploration of two-dimensional (2D) materials, particularly carbon nanosheets such as Graphdiyne, owing to their compelling electrical, optical, mechanical, and chemical properties. The recent achievement in producing pyrazinoquinoxaline graphdiyne (PQ-GDY) nanosheets, distinguished by their remarkable stability and exceptional physical properties, has ignited our research curiosity, prompting an exploration of their potential suitability as anode materials for lithium (Li), sodium (Na), calcium (Ca), and magnesium (Mg) ion batteries. This investigation is conducted using first-principle electronic structure simulations. Drawing from our rigorous theoretical analysis, pyrazinoquinoxaline graphdiyne (PQ-GDY) has demonstrated favorable electrode properties, positioning it as a promising candidate for potential utilization in Li, Na, and Ca ion batteries. Notably, the pyrazinoquinoxaline graphdiyne rectangular (PQ-GDY-Rec) material demonstrates remarkable storage capacities for Li, Na, and Ca ions, reaching values of 1938 mAh/g, 1716 mAh/g, and 830.60 mAh/g, respectively. These findings position PQ-GDY-Rec as a highly promising material for application in metal-ion batteries, suggesting new avenues for the advancement of rechargeable batteries with significantly enhanced storage capabilities.

High-rate aqueous magnesium ion battery enabled by Li/Mg hybrid superconcentrated electrolyte

Rechargeable aqueous magnesium ion batteries (AMIBs) are considered a promising energy storage system due to the relatively high energy density, excellent rate performance and reversibility, and absence of dendrite formation during cycling. However, the high surface charge density of Mg2+ ions results in slow diffusion kinetics, and high voltage leads to excessive electrolyte decomposition at the electrode/aqueous electrolyte interface, thereby limiting the development of high-energy–density MIBs. In this work, we extend the electrochemical stability window of the aqueous electrolyte to 2.1 V by using a hybrid ion superconcentrated electrolyte at concentrations not achievable with Mg2+ electrolytes alone. The AMIB with a water-in-salt (WIS) electrolyte delivers discharge capacities of up to 200.6 and 84.4 mAh g−1, and energy densities of 170.1 and 68.1 Wh Kg−1 at 0.5 and 20 A g−1, respectively, representing excellent rate performance, while retaining 85 % of the specific capacity after 2000 cycles. Additionally, we explore the corresponding electrochemical reaction mechanism, revealing the synergistic effect of Mg2+ and Li+ ions in the charge/discharge process, which supports the excellent electrochemical performance of AMIB.

A novel two-dimensional monolayer MB4(M = Cr, Mo, W) MBenes as a high-performance anode material for Mg-ion batteries

Rechargeable magnesium-ion batteries have garnered with great interest because abundant resources of magnesium and their potential for achieving high energy density. However, the realization of MIBs is hindered by the lack of appropriate electrode materials. In this study, the potential of 2D monolayers of CrB4, MoB4, and WB4 as anode materials for MIBs has been thoroughly studied using DFT calculations. Our preliminary investigations indicate that these monolayers demonstrate structural, mechanical, and thermodynamic stability. The significantly negative adsorption energy plays a vital role in stabilizing the surface adsorption of Mg ions, preventing clustering, and ensuring the stability of MIBs. The maximum TSC values are 3377 mA h g−1,2311 mA h g−1 and 1416 mA h g−1; and relatively low average OCV of 0.27 V,0.28 V and 0.19 V for CrB4, MoB4 and WB4 respectively, which is favoring to attaining high energy-density. The electronic properties revealed that as the Mg ion concentration increased, the electrical conductivity of the materials improved while maintaining their metallic nature, even after adsorption. However, the energy barriers were slightly higher and consistent with those of many common materials used as 2D anodes. Anticipated light shading of CrB4, MoB4, and WB4 was predicted to identify novel anode materials for MIBs.

Uncovering the interactions and potentials of magnesium and boron nitride nanostructures for magnesium-ion batteries

In present research paper, relationships between a magnesium atom and a magnesium ion (Mg2+) were examined with four different nanostructures: a boron nitride nanotube and a boron nitride nanocone. Our goal was to determine cell voltage (V) values for Mg-ion batteries (MIBs). We conducted calculations employing ωB97XD level of theory and 6-31G(d) basis set to analyze total energy, optimize the geometry, and examine the frontier molecular orbitals. The DFT calculations provided clarification regarding the energy adsorption changes (Ead) between the Mg2+ ion and nanostructures, indicating that the order of Ead is BN tube > BN cone. However, the nanocone exhibits the highest Vcell value, and alterations in Vcell for Mg-ion batteries follow order of BN cone > BN tube. Present research provides theoretical insights into the potential of magnesium as an anode material in batteries, highlighting its favorable Vcell.

Anisotropy of V3O7 nanobelts enables ultralong cycling life of magnesium ion battery

Magnesium ion batteries (MIBs) are a promising alternative to lithium-ion batteries, which suffer from the short cycling life and sluggish Mg2+ diffusion kinetics of cathodes. Nano morphologies are used to shorten Mg2+ diffusion path for diffusion kinetics acceleration, but the cycling life is still unsatisfactory. Herein, the anisotropy of layered V3O7⋅1.9H2O nanobelts is utilized to stabilize their structure during discharging/charging. The V3O7⋅1.9H2O nanobelts grow along the preponderant migration direction of Mg2+, and the resulted axial migration of Mg2+ enables the stress caused by Mg2+ insertion to be decentralized in large zone, thus improving the cycling stability of V3O7⋅1.9H2O nanobelts. The inserted Mg2+ cations bond with O atoms in adjacent V3O8 layers of V3O7⋅1.9H2O, further stablizing the layered structure. Meanwhile, the axial migration of Mg2+ significantly reduces the charge transfer resistance at electrode/electrolyte interface, which accelerates the Mg2+ diffusion kinetics. Thus, the symmetric RMB assembled from V3O7⋅1.9H2O nanobelts exhibits an ultralong cycling life of 11,000 cycles at 4 A g−1, alongside a high specific capacity of 137 mAh g−1 at 0.05 A g−1. According to our knowledge, this ultralong cycling life surpasses those of reported full RMBs. This strategy provides insight into the design of cathode materials with improved cycling lives.

Catalyzing Desolvation at Cathode-Electrolyte Interface Enabling High-Performance Magnesium-Ion Batteries.

Magnesium ion batteries (MIBs) are expected to be the promising candidates in the post-lithium-ion era with high safety, low cost and almost dendrite-free nature. However, the sluggish diffusion kinetics and strong solvation capability of the strongly polarized Mg2+ are seriously limiting the specific capacity and lifespan of MIBs. In this work, catalytic desolvation is introduced into MIBs for the first time by modifying vanadium pentoxide (V2O5) with molybdenum disulfide quantum dots (MQDs), and it is demonstrated via density function theory (DFT) calculations that MQDs can effectively lower the desolvation energy barrier of Mg2+, and therefore catalyze the dissociation of Mg2+-1,2-Dimethoxyethane (Mg2+-DME)bonds and release free electrolyte cations, finally contributing to a fast diffusion kinetics within the cathode. Meanwhile, the local interlayer expansion can also increase the layer spacing of V2O5 and speed up the magnesiation/demagnesiation kinetics. Benefiting from the structural configuration, MIBs exhibit superb reversible capacity (≈300mAhg-1 at 50mAg-1) and unparalleled cycling stability (15 000 cycles at 2Ag-1 with a capacity of ≈70mAhg-1). This approach based on catalytic reactions to regulate the desolvation behavior of the whole interface provides a new idea and reference for the development of high-performance MIBs.