Battery Materials Research Articles

Enhancing the electrochemical characteristics of P2-Na0.7Mn0.6Cu0.3Cr0.1O2 cathode materials through morphological manipulation: assessment of rate capability and coulombic efficiency

Abstract Manganese-based layered oxides are regarded as an excellent cathode material for Na-ion batteries. These materials are susceptible to phase transitions, which result in structural instability and constrain their reversible capacity. Layered self-assembled microsphere-type cathodes Na0.7Mn0.6Cu0.3Cr0.1O2 were developed to modify the efficiency of sodium-ion batteries through a technique focused on controlling morphology. The incorporation of organic compounds such as benzoic acid employs molecular design techniques to modify intermolecular interactions and increase the spacing between layers. The self-assembled layered spherical architecture enhances the interface between the cathode and electrolyte, thereby markedly boosting the transport efficiency of sodium ions. Based on the cathode for batteries, it demonstrates a substantial initial capacity of 200.26 mAh g-1 at a current density of 26 mA g-1 within the voltage amount of 1.5-4.1 V, with a capacity retention of 82.69% after 100 cycles.

Surface structure reconstruction to suppress heterogeneous phase transformation for air-stable single crystalline O3-type sodium oxide

O3-type layered oxide cathode material for sodium-ion batteries (SIBs) has attracted much attention as one of the most viable candidates due to its high specific capacity and mature synthesis process, while the moisture sensitivity and harmful phase transformation lead to poor processing properties and unsatisfactory life-span, hindering its large-scale and commercial application. Herein, single crystallization strategy is adopted to enhance air stability and processing performance, and surface structure reconstruction for single crystalline cathode material O3-NaNi1/3Fe1/3Mn1/3O2 by ammonium tetraborate pretreatment is employed to further remove residual alkali and improve sodium ions diffusion dynamics and suppress heterogeneous phase transformation, achieving superior structure stability. Surface residual alkali is in-situ converted into a protective coating layer of Na2B4O7 and meanwhile partial B atoms enter into the interstitial site of sub-surface or near surface, which accelerates sodium ions transport as well as enhances TM-O bonding and hybridization of surface O (2p)-Fe (3d-t2g) orbital, inhibits TMO6 slabs gliding and strengthens structure on the surface and near surface. Additionally, the formed boron-rich surface exhibits high stability, effectively alleviating structural degradation from surface to bulk and enhancing air stability. Benefiting from the reconstructed surface structure, the modified single crystalline oxides (NFM@B) exhibit distinguished processing performance and electrochemical properties.

Self-limited and reversible surface hydration of Na2Fe(SO4)2 cathodes for long-cycle-life Na-ion batteries

Air stability is a crucial factor in the practical application of a battery material, as it profoundly affects the material's preparation, storage, and electrode fabrication processes. Sodium iron sulfate cathodes, despite their attractive attributes in cost and electrochemical performance, are widely believed to be unstable upon air exposure because of the sulfate group. Here we report remarkable air-stability of the Na2Fe(SO4)2-based (NFS) cathodes (minimal decay in 20 % RH air for 60 days, 91.9 % capacity retention after 3500 cycles in half cells) and their outstanding cycle performance in practically relevant pouch-type full cells (∼100 Wh kg-1 specific energy, >1000 cycle-life). Although the NFS cathodes do react with moisture H2O to produce Na2Fe(SO4)2⋅4H2O but the hydration is spatially confined at the NFS particles’ surface and not propagating into their bulk. Further, the structural changes are reversible when the surface-hydrated NFS particles are heated in the typical electrode vacuum-drying process, avoiding extra treatment and additional cost. This work reveals the promising properties of the NFS cathode materials towards high-performance and sustainable Na-ion batteries.

Improved sodium storage properties NaFePO4/C as cathode material for sodium-ion batteries

Improved sodium storage properties NaFePO4/C as cathode material for sodium-ion batteries

Exploring the potential of MXene nanohybrids as high-performance anode materials for lithium-ion batteries

Lithium-ion batteries (LIBs) are an integral part of modern life, powering diverse applications from transportable devices to electric vehicles. Efficacy of LIBs depends on the performance of their components with anode material playing the pivotal role. Traditional graphite anodes have limitations in capacity and rate capability. This review comprehensively discusses utilization of MXene-based composites as anode materials in LIBs. MXene composites exhibit versatile lithium storage mechanisms, involving intercalation and/or conversion reactions. Pure MXenes offer advantages of high capacity and cycling stability having challenges due to limited conductivity and mechanical fragility, restricting their practical utility, thereby affecting their performance in solid-state polymer electrolytes (SPEs). MXene composites overcome unsystematic dispersal and accumulation issues of pure MXene. MXenes in composite form could increase LIBs performance by overcoming limitations of pure MXenes, enabling breakthroughs in energy storage. The review covers different MXene composites viz., MXene/graphene, MXene/silicon, MXene/tin, MXene/carbon, MXene/metal oxide, and MXene/conducting polymer providing a holistic overview. Their performance, cycling stability, and rate capability are discussed to cover challenges and future prospects.

Solid-Liquid-Solid Growth of Doped Silicon Nanowires for High-Performance Lithium-Ion Battery Anode

Silicon nanowires (SiNWs) have great potential in electronic devices, sensors, energy storage, and conversion devices. Despite various ways to synthesize SiNWs, however, the growth of SiNWs directly from stable, abundant, sustainable silica sources has yet to be achieved. Herein, we report a modified alumino-reduction process of the silica to produce tin (Sn)-doped SiNWs that can be initiated at low temperature (250 °C) based on a solid-liquid-solid growth mechanism in analogy to the well-known vapor-liquid-solid (VLS). In this growth process, the reduced silicon atoms migrate freely in the molten salt and alloy with pre-reduced Sn. The supersaturation of silicon in the Sn-Si alloy leads to the precipitation of single-crystal SiNWs. The prepared SiNWs are of excellent crystallinity and doped with high non-equilibrium concentration (~3.0at.%) of Sn. This process with the solid-liquid-solid mechanism can also be extended to produce other group IV elements-based nanowires such as germanium. In addition, the prepared Sn-doped SiNWs as the anode material in lithium-ion batteries exhibit excellent performance with a high initial Coulombic efficiency of 85.4%, and a substantial reversible capacity of 1133 mAh g-1 even after 500 cycles at 4Ag-1. By utilizing the solid-liquid-solid mechanism, this modified alumino-reduction process offers a novel route for synthesizing doped SiNWs, holding promise for diverse applications.

Preparation of Fe2O3 nanoparticles with ultrathin carbon covered as lithium storage anodes

This study focuses on the development of ultrathin carbon (UTC) treated with Fe2O3 nanoparticles as anode materials for lithium-ion batteries (LIBs). Here, a simple hydrothermal method has been adopted to prepare Fe2O3@C nanocomposite, followed by annealing. The obtained Fe2O3@C demonstrates Fe2O3 nanoparticles (NPs) with uniform carbon, which effectively mitigates volume expansion and enhances electrochemical performance. Encouraging, the first principal calculations ensure that carbon doping in Fe2O3 can notably reduce the band gap from 2.12 to 1.10 eV and enhance electronic conductivity.

Enhanced lithium-sulfur battery eilectrochemistry via Se-doped MoS2/rGO ultrathin sheets as sulfur hosts

In the pursuit of advancing lithium-sulfur (Li-S) battery technology, the intrinsic challenges of sulfur conductivity and the shuttle effect during charge-discharge cycles have posed significant barriers. Despite many efforts made through physical and chemical methodologies, the development of host materials with more active sites and good catalytic activities might still remain a challenging problem in Li-S batteries. This study presents a novel selenium-doped molybdenum disulfide (Se-MoS2) nanosheet, synthesized on reduced graphene oxide (rGO), which would address these issues. The Se-MoS2/rGO composite enhances conductivity and catalytic activity through the creation of anionic vacancies, facilitating lithium polysulfide adsorption. As a sulfur host, this material delivers an impressive initial capacity of 1008.1 mAh g−1 at 1C, maintaining 620.7 mAh g−1 after 500 cycles with a minimal capacity fade of 0.077 % per cycle, demonstrating superior coulombic efficiency and stability. The findings underscore the impact of heteroatom doping on the electrochemical performance of graphene-based materials for Li-S batteries.

Optimizing Interface Chemistry with Novel Covalent Molecule for Highly Sustainable and Kinetics-Enhanced Sodium Metal Batteries

Metallic sodium has attracted increasing attention as an ideal anode material for next-generation high energy density and low-cost secondary batteries. However, it is highly desired yet remains challenging to improve their cycling stability and safety due to unstable solid electrolyte interphase and dendrite growth. Herein, a hybrid interface layer composed of Na2Se and Na3P is constructed on the surface of Na (Na@NPS) via in situ spontaneous reaction. The hybrid interface layer with merits of high sodiophilicity and high Na-ion conductivity can effectively induce homogeneous Na-ion flux distribution, accelerate the reaction kinetics and suppress decomposition of electrolyte components. Benefitting from the above advantages, the Na@NPS symmetric cell delivers a long cycle life (1000 h at 1 mA cm–2 and 1 mAh cm–2). Furthermore, the full cell coupling with Na3V2(PO4)3-based cathode provides an exceptionally long lifespan (1500 cycles) at 20 C with a capacity retention of 98.2% and high energy density (226 Wh kg–1). Therefore, the enhanced electrochemical performance illustrates the feasibility of the covalent molecule derived hybrid multifunctional interfaces in solving the irregular deposition of Na-ion and expediting reaction kinetics in Na metal batteries.

NiCo2S4 nanoparticles encapsulated within hollow mesoporous carbon spheres enabling rapid and stable sodium storage

Poor rate capability and cycling performance significantly impair the utilization of NiCo2S4 as an anode material in sodium-ion batteries. Herein, hollow mesoporous carbon spheres (HMCSs) are synthesized using a hard-template method. NiCo2S4 nanoparticles with sizes ranging from 15 to 43 nm are grown in-situ within HMCSs (NiCo2S4@HMCS) by melt adsorption, solution impregnation, and gas-phase sulfurization. Specifically, NiCo2S4 nanoparticles are uniformly distributed on the inner walls of HMCSs and within the mesoporous channels of spherical shells. In half-cells, NiCo2S4@HMCS exhibits reversible capacities of 482 mAh g−1 after 340 cycles at 1.0 A g−1, 340 mAh g−1 after 600 cycles at 5.0 A g−1, and 271 mAh g−1 after 700 cycles at 10.0 A g−1. In NiCo2S4@HMCS//Na3V2(PO4)3 full-cells, NiCo2S4@HMCS maintain reversible capacities of 203 mAh g−1 after 1200 cycles at 1.0 A g−1 and 122 mAh g−1 after 2000 cycles at 5.0 A g−1. The unique nano-encapsulated structure prevents the detachment of NiCo2S4 from HMCSs, maintaining electrochemical activity and stability of NiCo2S4. Additionally, the nano-encapsulated structure also facilitates electrolyte penetration and enhances the electronic conductivity of NiCo2S4. These effects synergistically result in rapid and stable sodium storage performance.

Pomegranate-like cobalt Phosphides@P-Doped carbon Nanostructures with controlled phase as anode materials for Lithium-Ion batteries

Transition metal phosphides (TMPs) have recently emerged as prominent energy conversion and storage materials owing to their unique physicochemical property. Nevertheless, it’s still a difficult task to obtain phase-control of TMPs owing to multiple energetically favorable stoichiometries. Herein, a phase-controllable cobalt phosphide@C with the pomegranate core–shell structure are successfully realized by employing Co-glycerate as precursors and phytic acid (PA) as P sources, etching and coordination agents. With the presence of six phosphoryl groups and the strong coordination ability, PA allows the self-phosphating of Co atoms and the P-doped carbon shell, as well as the confinement of the obtained nanoparticles Additionally, as an organic acid, PA can etch the Co-glycerate precursors with the formation of hollow structures. With different etching time, metal-rich phosphides Co2P@C and monophosphides CoP@C are successfully achieved. When applied as anode materials, CoP@C demonstrates superior lithium storage performance by delivering a prominent reversible capacity up to 1187 mAh/g at 0.1 A/g and shows no capacity loss at 1 A/g after 500 cycles. This work presents a simple protocol to obtain TMPs with tunable metal/phosphorus ratios, phase selectivity and interface engineering, which could be applied in the field of energy storage and electrocatalysis.

Impact of tetracyanoethylene plasticizer on PEO based solid polymer electrolytes for improved ionic conductivity and solid-state lithium-ion battery performance

Poly(ethylene oxide) is a promising material for solid-state lithium batteries due to its safety, ease of processing, and compatibility with lithium. However, conventional linear PEO falls short of practical requirements due to its limited ionic conductivity, a consequence of the high crystallinity of its ethylene oxide chains. This crystallinity hinders the movement of lithium ions, limiting its performance in solid-state battery applications. In this study, we successfully prepared the plasticized solid polymer electrolytes (PSPEs) based on poly(ethylene oxide) (PEO)/tetracyanoethylene (TCE) complexed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and studied the effect of TCE on structural, mechanical, electrical and electrochemical properties of PSPEs. The addition of tetracyanoethylene effectively disrupts the crystallinity of the PEO matrix, as confirmed by X-ray diffraction analysis. The addition of TCE also enhanced the elongation-at-break of the PEO12-LiTFSI system, indicating improved flexibility. Consequently, the ionic conductivity of the SPEs increases with increasing tetracyanoethylene content, reaching a maximum of 1.14 × 10−4 S/cm at 25 °C for the electrolyte containing 30 wt% of tetracyanoethylene. Furthermore, the plasticized SPEs exhibit a wide electrochemical stability window, as determined by linear sweep voltammetry. Solid-state battery tests demonstrate a high initial discharge capacity of 143.5 mAhg−1 at 0.1C along with good cycling performance.

Synthesis of high-entropy perovskite metal fluoride anode materials for lithium-ion batteries via a one-pot solution method

Synthesis of high-entropy perovskite metal fluoride anode materials for lithium-ion batteries via a one-pot solution method

Six element high-entropy Prussian blue analogue cathode enabling high cycle stability for sodium-ion batteries

Prussian blue analogues (PBA) are promising cathode materials for sodium-ion batteries. However, the cycle life of PBA is limited due to its structure instability during cycling. Here, we successfully introduce six transition metals into N coordination site to increase the configurational entropy, significantly improving the structure stability and cycle life of PBA cathode materials. Electrochemical characterization methods are used to compare the behavior of hexa-, penta-, quadr-, and tri-metal PBA, exhibiting the characteristic of performance increasing with entropy. Time-resolved in situ X-ray diffraction confirms the “quasi-zero-strain” structure of H-PBA during desodiation/sodiation process. X-ray absorption spectroscopy and density functional theory calculations reveal that Mn, Fe, Co and Cu contribute the high capacity of H-PBA, while Ni and Zn stabilize the structure. The strategy will inspire new ideas in designing long life cathode materials with high capacity for sodium-ion batteries.

Pre-lithiation synergized with magnesiothermic reduction to enhance the performance of SiO anode for Advanced lithium-ion batteries

Due to its high theoretical specific capacity, micron-sized silicon monoxide (SiO) is regarded as one of the most competitive anode materials for lithium-ion batteries with high specific energy density. However, originating from the low initial Coulombic efficiency (ICE) and large volume expansion, its large-scale application is seriously hindered. Herein, an easy-to-implement solid-state pre-lithiation method synergized with the magnesiothermic reduction process was performed to enhance the ICE of SiO and a common bimetallic hydride was used as a prelithiation reagent. Moreover, the effects of different pre-lithiation reagent amounts on the physical and electrochemical properties of SiOx are investigated. Notably, the SiOx-LA@C composite anchored by in-situ generated LiAl(SiO3)2 shows a more stable microstructure and excellent electrochemical properties, which delivers an ultrahigh ICE of 89.4 % and an excellent initial capacity of 1864.4 mAh g−1. Furthermore, the full cells were successfully assembled by using the prepared anodes, which exhibit relatively stable cycle performance over 150 cycles. This work suggests a safe and feasible route to enhance the ICE of SiOx for the applicable SiO-based anode materials.

Effect of carbon coating on the structure and electrochemical properties of β-LiVOPO4 cathode material for lithium-ion batteries

Effect of carbon coating on the structure and electrochemical properties of β-LiVOPO4 cathode material for lithium-ion batteries

Fast kinetics for lithium storage rendered by Li3VO4 nanoparticles/porous N-doped carbon nanofibers

Li3VO4 (LVO) has been recognized as an alternative anode material for lithium-ion batteries (LIBs) because of its appropriate lithium storage potential and capacity merits. However, its practical application is seriously hindered by slow reaction kinetics stemming from poor electronic conductivity. Herein, Li3VO4/porous N-doped carbon nanofibers (LVO/PNC NFs) are firstly designed and fabricated via an electrospinning method, utilizing the thermal decomposition characteristics of polylactic acid (PLA). The porous N-doped carbon nanofibers provide efficient electrolyte diffusion paths and facilitate ion transport. In addition, LVO nanoparticles are uniformly dispersed along the nanofibers to effectively inhibit particle aggregation. The obtained LVO/PNC NFs are evaluated as anodes for LIBs and deliver high reversible capacity of 768 mAh g−1 after 300 cycles at 0.2 A g−1, along with excellent rate capability (average capacity of 355 mAh g−1 at 8 A g−1 after 6 periodic rate testing) and long cycling life (286 mAh g−1 after 2000 cycles at 4 A g−1). The special porous nanofiber represents an effective strategy for improving the electronic conductivity, inhibiting particle aggregation, and ensuring rapid ion/charge transport towards advanced energy storage technologies.

A metallic lithium anode for solid-state batteries with low volume change by utilizing a modified porous carbon host

Lithium metal is a promising negative electrode material for solid-state batteries (SSBs). However, uncontrolled lithium deposition and stripping cause several issues during cycling. Herein, the microporous carbon YP-50F and its modifications obtained by thermal ethene-based chemical vapor deposition (CVD) are investigated as 3D host to accommodate and control the deposition of metallic lithium. In half-cells vs. lithium, the CVD-YP composite electrode with Li6PS5Cl electrolyte shows significantly higher initial coulombic efficiency (79.5 %) than the pristine carbon (55.3 %) due to the reduction of side reactions. The metallic character of the deposited lithium is evidenced by 7Li Nuclear Magnetic Resonance spectroscopy. However, full cells with nickel-rich NCM (LiNi0.9Co0.05Mn0.05O2) positive electrode and CVD-YP composite negative electrode show reasonable performance over 50 cycles without occurrence of (micro-) short-circuits (in contrast to 2D reference electrodes). In addition, small prototype pouch cells are investigated and the thickness change during (dis)charging is less than one third compared to a bare lithium metal electrode. This demonstrates low breathing behavior of the CVD-YP electrode and confirms the reversible storage of metallic lithium within the 3D carbon-based composite electrode.

Structural regulation of 1T-MoS2/Graphene composite materials for high-performance lithium-ion capacitors

Heterogeneous composite structures are considered an effective strategy by utilizing the advantages of heterogeneous components. However, the relationship between structural modifications and electrochemical performance remains inadequately understood. In this study, we leveraged DFT calculations to elucidate the key advantages of the 1T-MoS2/Gr heterostructure, including its exceptional electrical conductivity, enhanced Li+ adsorption capabilities, and improved Li+ diffusion kinetics. To synthesize the 1T-MoS2/Gr composite, we developed a facile, one-step hydrothermal method using glucose as a reducing agent, achieving an optimal heterostructure that maximized the synergistic properties of the components. By comparing different levels of graphene content, the relationship between structural regulation and electrochemical performance has been studied, and a remarkably significant heterostructure composite material (1T-MoS2/Gr-0.8) was identified. As the anode material for lithium-ion batteries (LIBs), 1T-MoS2/Gr-0.8 presents excellent cycle performance with 467 mAh g−1 under the condition (0.5 A g−1, 600 cycles). Simultaneously, when assembling the lithium-ion capacitor (LIC) device with an activated carbon (AC) cathode, even at a high power density of 11.7 kW kg−1, the energy density of the 1T-MoS2/Gr-0.8//AC LIC is as high as 137.0 Wh kg−1. Moreover, the capacity retention rate remains at 89.9 % even after 2000 cycles at 2 A g−1, demonstrating its candidacy as a high-performance anode material for LICs.

Breaking boundaries in O3-type NaNi1/3Fe1/3Mn1/3O2 cathode materials for sodium-ion batteries: An industrially scalable reheating strategy for superior electrochemical performance

To address the challenges of air stability and slurry processability in layered transition metal oxide O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) for sodium-ion batteries (SIBs), we have designed an innovative 500 °C reheating strategy. This method improves the surface properties of NFM without the need for additional coating layers, making it more efficient and suitable for large-scale applications. Pristine NFM (NFM-P) was first synthesized through a high-temperature solid-state method and then modified using this reheating approach (NFM-HT). This strategy significantly enhances air stability and electrochemical performance, yielding an initial discharge specific capacity of 151.46 mAh/g at 0.1 C, with a remarkable capacity retention of 95.04% after 100 cycles at 0.5 C. Additionally, a 1.7 Ah NFM||HC (hard carbon) pouch cell demonstrates excellent long-term cycling stability (94.64% retention after 500 cycles at 1 C), superior rate capability (86.48% retention at 9 C), and strong low-temperature performance (77% retention at −25 °C, continuing power supply at −40 °C). Notably, even when overcharged to 8.29 V, the pouch cell remained safe without combustion or explosion. This reheating strategy, which eliminates the need for a coating layer, offers a simpler, more scalable solution for industrial production while maintaining outstanding electrochemical performance. These results pave the way for broader commercial adoption of NFM materials.