Superior Lithium Storage Research Articles

Tin-based oxide microsphere reinforced by Al2O3 and CNT with superior lithium storage performance

To improve lithium storage performances of tin-based oxide electrodes, i.e. SnO2 microspheres reinforced by Al2O3 and CNTs (SnO2-Al2O3/CNT) are constructed using a convenient microwave-assisted method. The findings indicate that the SnO2-Al2O3/CNT composite predominantly consisted of the rutile structure phase, with a minor presence of the orthorhombic phase. SnO2-Al2O3/CNT electrodes demonstrate greater capacity, significantly enhanced cyclability and improved rate performance when compared to the electrodes based on SnO2-Al2O3 and SnO2. Specifically, a sable specific capacity of 745.34 mAh/g can be maintained at 1.0 A/g, while a large specific capacity of 617.36 mAh/g can still be demonstrated at a high current density of 4.0 A/g after 100 cycles. The improved Li-storage performances may be attributed to by the significant synergistic effect among SnO2, Al2O3, CNTs, and the morphology as well.

Biomass-derived N–P double-doped porous carbon spheres and their lithium storage mechanism

Biomass-derived carbon materials are widely studied and used in energy storage applications. Unfortunately, the disadvantages such as poor capacity and rate performance limit their development. Heteroatom doping can effectively improve the electrochemical properties of biomass-derived carbon materials. In this work, we designed and prepared environmentally friendly and cost-effective biomass (lotus root)-derived nitrogen-phosphorus (N–P) double-doped porous carbon spheres. When used as an anode material for a lithium-ion battery, the porous carbon spheres exhibited excellent stability performance (a reversible capacity of 739.6 mAh g−1 after 100 cycles at 0.1 A g−1 and 599.16 mAh g−1 after 215 cycles at 0.5 A g−1, respectively) and superior rate performance (a capacity of 187.22 mAh g−1 at 10 A g−1) due to the synergy of the heteroatomic doping and the layered porous spherical structure. The novel biomass-derived material based on N–P double-doped porous carbon spheres can serve as a cost-effective option for anode materials of lithium-ion batteries. Besides, an “adsorption-pore filling/intercalation” hybrid mechanism is proposed to understand the possible principle for superior lithium storage performance based on CV, ex-situ Raman and XRD results.

One pot synthesis of polyoxometalate@polyaniline/MXene/CNTs quaternary composites with a 3D structure as efficient electrode materials for Li-ion batteries applications

Double transition metal carbides (MXenes) are considered promising candidates for a good electrode material because of their enormous specific surface area, metallic conductivity and hydrophilicity. However, their low capacity, easy oxidation and self-restacking restrict their large-scale application. In this paper, we selected Mo2TiC2Tx MXene as the conductive carrier of polyoxometalate (POM), carbon nanotubes (CNTs) as the linker to construct a novel POM@polyaniline (PANI)/Mo2TiC2Tx/CNTs quaternary composites (denoted as PPMC) with a unique 3D structure by using a facile one pot synthesis strategy. The PPMC with unique 3D structure as an anode material for LIBs exhibits superior lithium storage capacity (621 mAh g−1 at 0.1 A g−1) and promising cyclic stability (445 mAh g−1 after 1000 periods at 1.0 A g−1) and good rate capability. The enhanced performance is mainly attributed to the synergistic effect between components. Our work provides an effective strategy to improve the reversibility and cycling stability of electrode materials for LIBs, which will contribute some reference value to the development of high-performance MXene based electrode materials.

Efficient and stable lithium storage of porous carbon fiber composite bimetallic sulfides (FeS-ZnS) anode

To enhance the utilization of lithium-ion battery anodes, it is crucial to improve both the lithium storage stability and kinetics of transition metal sulfides. This optimization is critical for the development of battery technologies that are more efficient, durable, and environmentally sustainable. In this study, a facile electrospinning technique followed by a thermal treatment was used to fabricate a bimetallic sulfide/porous carbon fiber composite (FeS-ZnS/PCFs). Its stability was largely improved due to the buffered ability derived from its porous structure. The presence of FeS-ZnS grain boundaries fosters the generation of extra redox active sites, ultimately boosting the kinetics of lithium storage. The optimized composite material exhibits excellent stability and efficient lithium storage performance. Density functional theory calculations and kinetics analysis further clarify superior lithium storage capabilities of this material.

Enhancing lithium storage rate and durability in sphalerite GeP by engineering configurational entropy

High-entropy sphalerite-structured compounds, derived from cubic GeP, demonstrate remarkable metallic conductivity and superior lithium-storage capabilities when compared to the parent phases of monoclinic layered GeP or SiP.

Novel Ultra-Stable 2D SbBi Alloy Structure with Precise Regulation Ratio Enables Long-Stable Potassium/Lithium-Ion Storage.

The inferior cycling stabilities or low capacities of 2D Sb or Bi limit their applications in high-capacity and long-stability potassium/lithium-ion batteries (PIBs/LIBs). Therefore, integrating the synergy of high-capacity Sb and high-stability Bi to fabricate 2D binary alloys is an intriguing and challenging endeavor. Herein, a series of novel 2D binary SbBi alloys with different atomic ratios are fabricated using a simple one-step co-replacement method. Among these fabricated alloys, the 2D-Sb0.6 Bi0.4 anode exhibits high-capacity and ultra-stable potassium and lithium storage performance. Particularly, the 2D-Sb0.6 Bi0.4 anode has a high-stability capacity of 381.1 mAh g-1 after 500 cycles at 0.2 A g-1 (≈87.8% retention) and an ultra-long-cycling stability of 1000 cycles (0.037% decay per cycle) at 1.0 A g-1 in PIBs. Besides, the superior lithium and potassium storage mechanism is revealed by kinetic analysis, in-situ/ex-situ characterization techniques, and theoretical calculations. This mainly originates from the ultra-stable structure and synergistic interaction within the 2D-binary alloy, which significantly alleviates the volume expansion, enhances K+ adsorption energy, and decreases the K+ diffusion energy barrier compared to individual 2D-Bi or 2D-Sb. This study verifies a new scalable design strategy for creating 2D binary (even ternary) alloys, offering valuable insights into their fundamental mechanisms in rechargeable batteries.

Surface modification of silicon nanowires via drop-casting for high-performance Li-ion battery electrodes: SiNWs decorated with molybdenum oxide nanoparticles

The functionalization of molybdenum oxide (MoO3) nanoparticles is presented as a method to significantly enhance the cycling stability of lithium-ion battery (LIB) anodes based on silicon nanowire (SiNW) arrays. Transition-metal oxides have emerged as promising candidates for advanced anode materials in modern Li-ion batteries. In this study, we explore a novel approach involving the deposition of MoO3 nanoparticles via unique drop-casting technique onto pre-fabricated SiNW arrays, fabricated using a straightforward one-step metal-assisted chemical etching (MACE) process. The primary objective is to assess their potential suitability as anode materials for Li-ion batteries. Our methodology entails the top-down synthesis of binder-free hybrid electrodes, achieved by depositing Mo oxides nanostructures onto SiNW arrays through a combination of drop-casting and thermal annealing processes. The resulting MoO3@SiNWs hybrid structure exhibits distinctive and specialized attributes, including exceptional structural resilience, diminutive particle dimensions, and a porous configuration. These features effectively enhance electron and ion accessibility at the electrode-electrolyte interface.Electrochemical assessments reveal that the MoO3@SiNWs hybrids exhibit superior lithium storage performance compared to bare SiNW electrodes. Particularly under high current densities, MoO3 nanoparticles deposited via drop-casting technique demonstrate improved cycling stability and increased capacity. The enhanced electrochemical characteristics are primarily ascribed to the synergistic effects between the MoO3 nanoparticles and SiNW arrays. The findings of this study strongly suggest that the MoO3@SiNWs hybrid structure holds substantial promise as anode materials for high-performance energy storage devices.

Construction of FeSbO4-Sb2O4 hetero-nanocrystals anchored on reduced graphene oxide sheets for superior lithium and sodium storage

Antimony-based oxides with conversion-alloying/dealloying mechanism have attracted great attentions as alternative anode materials for lithium/sodium-ion batteries due to their high theoretical capacities. However, slow reaction kinetics, inherent poor conductivity and large volume change severely inhibit their practical application. Herein, a novel composite with FeSbO4-Sb2O4 hetero-nanocrystals anchored on reduced graphene oxide (rGO) sheets is designed and successfully constructed by a facile solvothermal method. The intense interaction between Fe3+ and Sb5+ oxidized from Sb3+ by graphene oxide (GO) boosts priority formation of rutile FeSbO4 nanoparticles. And the excess Sb3+ and Sb5+ subsequently generate nano-sized cervantite Sb2O4 to form FeSbO4-Sb2O4 hetero-interface. Such unique structure not only can enhance electrical conductivity and structural stability of electrode, but also shorten diffusion distance of lithium/sodium ions during discharge/charge processes. Moreover, the in-situ generated Fe during electrochemical reaction can boost lithium/sodium release from Li2O/Na2O. Attributed to the unique structure, the as-obtained FeSbO4-Sb2O4/rGO-200 electrode delivers greatly improved electrochemical performance for both lithium and sodium storage, including large reversible capacities, high rate capability, and superior long-term cycling stability. This work provides an efficient route to rationally design and synthesize hetero-structural composites boosting lithium-/sodium-storage properties.

W-based MOF derived ZnWO4/ZnO@C hierarchical nanoflakes with superior lithium storage performance

Tungstate-based materials as lithium-ion battery anodes have drawn multitudinous attention owing to their great theoretical capacity and typical multielectron transfer process. Nevertheless, their slow electrochemical reaction kinetics and big volume variation often trigger poor lithium storage properties. Herein, novel ZnWO4/ZnO@C hierarchical nanoflakes are engineered via a facile W-based metal-organic framework (W-MOF) template method. The ZnWO4/ZnO@C nanoflakes with a rectangular shape and high porosity are constructed by carbon-coated nanocrystal subunits. The unique composition and microstructure of ZnWO4/ZnO@C can shorten the pathway for Li+/electron transport, expand the contact with the electrolyte, improve the electrical conductivity, and fortify structural stability. Consequently, the ZnWO4/ZnO@C material as LIBs anodes delivers a high reversible capacity of 734 mAh g-1 after 150 cycles at 200 mA g-1, decent rate capability (426 mAh g-1 at 1000 mA g-1), and outstanding cyclic stability (93.8 % capacity retention over 350 cycles at 500 mA g-1). The in-situ XRD combined with ex-situ XPS and FT-IR was performed to elucidate the lithium storage mechanism of ZnWO4/ZnO@C. This work presents a simple and efficient approach for the synthesis of novel tungstate-based anodes for lithium-ion battery applications.

A three-dimensional fibrous tungsten-oxide/carbon composite derived from natural cellulose substance as an anodic material for lithium-ion batteries

To meet the ever-growing demands over electrochemical energy storage, tungsten trioxide (WO3) has aroused substantial attention as a promising anodic material for lithium-ion batteries due to its high theoretical capacity, abundant earth storage, and eco-friendliness. However, developing high-performance WO3-based electrodes is hampered by its restrictive conductivity and tremendous structural as well as the volumetric changes during the charge/discharge processes. Herein, a novel bio-inspired nanofibrous WO3/carbon composite was synthesized via a facile hydrothermal method employing pre-carbonized cellulose substrate (e.g., ordinary filter paper) as both the structural scaffold and the carbon source. The urchin-like WO3 microspheres with diameters of 3–6 μm assembled by nanorods were uniformly anchored on the surfaces of the cellulose-derived carbon fibers. The three-dimensional network structure of the composite was beneficial in alleviating the volume expansion of WO3 nanorods and enhanced the charge-transport kinetics of the electroactive materials. The composite with an optimized content of WO3 (26.36 wt%) exhibited superior lithium storage properties with an initial discharge capacity of 1470 mAh g−1 and an extraordinary long-term cycling performance of 682 mAh g−1 capacity retention after 300 cycles at 100 mA g−1. Furthermore, cyclic voltammetry, ex-situ XRD, and SEM measurements for mechanism studies were carried out to yield deeper insights into the synergism in the WO3/carbon electrodes, revealing the predominance of reversible pseudocapacitive intercalation of lithium-ions during the electrochemical reaction inside the WO3/carbon anode.

Ultra-Efficient Synthesis of Nb4 C3 Tx MXene via H2 O-Assisted Supercritical Etching for Li-Ion Battery.

Nb4 C3 Tx MXene has shown extraordinary promise for various applications owing to its unique physicochemical properties. However, it can only be synthesized by the traditional HF-based etching method, which uses large amounts of hazardous HF and requires a long etching time (> 96h), thus limiting its practical application. Here, an ultra-efficient and environmental-friendly H2 O-assisted supercritical etching method is proposed for the preparation of Nb4 C3 Tx MXene. Benefiting from the synergetic effect between supercritical CO2 (SPC-CO2 ) and subcritical H2 O （SBC-H2 O）, the etching time for Nb4 C3 Tx MXene can be dramatically shortened to 1h. The as-synthesized Nb4 C3 Tx MXene possesses uniform accordion-like morphology and large interlayer spacing. When used as anode for Li-ion battery, the Nb4 C3 Tx MXene delivers a high reversible specific capacity of 430mAhg-1 at 0.1Ag-1 , which is among the highest values achieved in pure-MXene-based anodes. The superior lithium storage performance of the Nb4 C3 Tx MXene can be ascribed to its high conductivity, fast Li+ diffusion kinetics and good structural stability.

Rational design of p-ZnS@CN with 3D interconnected hierarchical pore structure through pyrolysis of an organic hybrid zinc thiocyanide for electrochemical lithium storage

3D interconnected porous carbon-coupled metal-sulfide composites have been demonstrated as promising lithium storage materials owing to their large surface areas as well as the acceleration effect to electrochemical kinetics. However, constructing these materials with ordered hierarchical pore structure is still a challenge. To address this issue, we found that the crystals of an organic hybrid zinc thiocyanide [Zn(NCS)2(phen)2] (phen = 1,10-phenanthroline) could become a fluid at 400 °C, and during the melting process, the phen ligand was simulatneously carbonized to form nitrogen-doped carbon materials, while the Zn(NCS)2 species were converted into ZnS quantum dots. This property could allow us to employ a hard template strategy for preparation of a porous p-ZnS@CN composite featuring 3D interconnected hierarchical structure, namely employing SiO2 nanospheres as sacrificial template and [Zn(NCS)2(phen)2] as precursor and thermal treatment this mixture at 400 °C. The as-obtained p-ZnS@CN (p = porous structure, CN = nitrogen-doped carbon) composite possesses ordered macro- and mesoporous nitrogen-doped carbon structures, where the ZnS quantum dots are embedded in. Due to their structural features, p-ZnS@CN showed a superior lithium storage performance in comparison with ZnS nanoparticles. The well-defined 3D interconnected hierarchical pore structure not only enhances the efficiency of lithium-ion diffusion, but also offers ample void space to buffer the volume expansion during lithiation. Given the diversity of crystalline organic hybrid metal thiocyanates, this work opens a new avenue of preparing 3D interconnected porous carbons-coupled metal-sulfide composites.

Synergistic effect of defects and heterostructures endowing bronze titanium dioxide with superior lithium storage performances

Bronze titanium dioxide (TiO2(B)) as anode materials in lithium-ion batteries (LIBs) have attracted widespread attentions, due to their especial channels and high specific capacity. However, poor electrical/ionic conductivity and limited electrochemical kinetics hinder the practical applications of TiO2(B). Here, we use a simple strategy to construct TiO2(B)-carbon nanosheets heterostructures that combine the merits of highly conductive carbon nanosheets with defect-rich TiO2(B), and thus achieving superior cycling performances with high specific capacities of 205 mAh/g at 2.0C and 162 mAh/g at 5.0C over 800cycles, and superior rate capability.

Fabrication of honeycomb-like amorphous carbon-encapsulated Si nanoparticles/graphene composite for superior lithium storage

Silicon (Si) anodes have great potential for high-energy lithium-ion batteries (LIBs). However, poor electrical conductivity, high cost and huge volume change during the (de)lithiation processes of silicon anodes hinder the practical application. Herein, we demonstrate a facile and scalable approach to fabricate a porous honeycomb-like amorphous carbon-encapsulated Si nanoparticles/graphene composite via a sol-gel & CO2-introduced magnesiothermic reduction method. The greenhouse gas CO2 is efficiently transformed into carbon layers. Interconnected carbon network consisting of graphene sheets and amorphous carbon layers not only significantly improves the electrical conductivity and mechanical properties of the Si-based composites, but also provides the strong interaction between Si and carbon materials. Besides, both unique honeycomb-like porous structure and interconnected carbon network can butter large volume effects of Si nanoparticles. The as-prepared amorphous carbon-encapsulated Si/graphene anode with the carbon content of 8 wt% has excellent rate performance and outstanding cycling stability, delivering a high discharge capacity of 908 mAh g−1 with 65.9 % of capacity retention at 0.5 A g−1 after 200 cycles. Thus, such honeycomb-like amorphous carbon-encapsulated Si nanoparticles/graphene composite anode is highly promising for practical next-generation LIBs.

Facile construction of ZnWO4/ZnO porous nanoplates on reduced graphene oxide for superior lithium storage

Zinc tungstate (ZnWO4) shows great promise as an anode material for lithium-ion batteries (LIBs) owing to its reversible multi-electron redox reactions and high theoretical capacity. Nevertheless, the low conductivity and big strain during cycling can lead to the inferior electrochemical properties of the ZnWO4 anode, hindering its practical application. Herein, we report a novel composite with ZnWO4/ZnO porous nanoplates in-situ constructed on reduced graphene oxide (rGO) by a metal–organic framework template strategy. The nanoplates with good porosity are composed of nanoparticles and nanorods, providing a short Li+-diffusion distance and plentiful Li+ storage active sites. The introduction of rGO can accelerate charge transfer and reinforce structural stability. As a result of these advantages, the ZnWO4/ZnO/rGO composite as LIBs anode delivers a high reversible capacity of 811 mAh g after 100 cycles at 200 mA g−1, excellent rate capability (437 mAh g at 5000 mA g−1), and good long cycling stability (485 mAh g after 500 cycles at 2000 mA g−1). Notably, the rate capability of the composite far precedes the previously reported ZnWO4-based anodes. This work provides an efficient approach for designing and fabricating advanced metal tungstate-based anodes for high-performance LIBs.

Nanostructured Porous Polymer with Low Volume Expansion, Structural Distortion, and Gradual Activation for High and Durable Lithium Storage.

Organic compounds exhibit great potential as sustainable, tailorable, and environmentally friendly electrode materials for rechargeable batteries. However, the intrinsic defects of organic electrodes, including solubility, low ionic conductivity, and restricted electroactivity sites, will inevitably decrease the cycling life and capacity. We herein designed and prepared nanostructured porous polymers (NPP) with a simple one-pot method to overcome the above defects. Theoretical calculations and experimental results demonstrate that the as-synthesized NPP exhibited low volume expansion, molecular-structural distortion, and a gradual function activation process during cycling, thus exhibiting superior, high, and durable lithium storage. The gradual molecular distortion during the lithium storage processes provides more redox-active sites for Li storage, increasing the Li-storage capacity. Ex situ spectrum studies reveal the redox reaction mechanism of Li storage and demonstrate a gradual activation process during the repeated charging/discharging until the full storage of 18 Li ions is achieved. Additionally, a real-time observation on the NPP anode by in situ transmission electron microscope reveals a slight volume expansion during the repeating lithiation and delithiation processes, ensuring its structural integrity during cycling. This quantitative work for high-durability lithium storage could be of immediate benefit for designing organic electrode materials.

C-Doped LiVO3 Honeycombs Derived from the Biomass Template Strategy for Superior Lithium Storage.

LiVO3 as a prospective anode for lithium-ion batteries has drawn considerable focus based on its superior ion transfer capability and relatively elevated specific capacity. Nevertheless, the inherent low electrical conductivity and sluggish reaction kinetics hindered its commercial application. Herein, C-doped LiVO3 honeycombs (C-doped LiVO3 HCs) are designed via introducing low-cost and scalable biomass carbon as a template, and the influence of the structure on the lithium storage property is systematically studied. The prepared C-doped LiVO3 HC electrode delivers a high reversible capacity of 743.7 mA h g-1 at 0.5 A g-1 after 400 cycles and superior high-rate performance with an average discharge capacity of 420.8 mA h g-1 even at 5.0 A g-1. The remarkable comprehensive electrochemical performance is attributed to the high electrical conductivity caused by carbon doping and rapid ion transport triggered by the honeycomb structure. This work may offer a rational design on both the hierarchical structure and doping engineering of future battery electrodes.

Facile synthesis of Co3O4 nanocrystals with superior lithium storage properties from bis (8–hydroxyquinoline) cobalt complex as anode materials for lithium–ion batteries

A simple and facile approach to synthesis Co3O4 nanocrystals by a two–step pyrolysis process of bis (8–hydroxyquinoline) cobalt complex under Ar and air atmospheres successively. The structures and physical properties of the complex, Co@C intermediate and the Co3O4 nanocrystals are characterized by the following techniques: FTIR, XRD, TGA–DTG, Raman, FESEM, HRTEM, N2 adsorption/desorption measurement and XPS. As anode materials in lithium ion batteries, the Co3O4 nanocrystals exhibit high charge/discharge specific capacity, excellent rate performance and remarkable cycle stability. The superior electrochemical properties of the Co3O4 nanocrystals could be attributed to the nanoscaled particle size, high crystallinity and high specific surface area, which is helpful to increase the number of active sites, shorten the diffusion path of lithium ions and electrons, alleviate the volume expansion effect as well as improve the dynamic characteristics during cycling.

Rational engineering of a carbon skeleton supported tin dioxide nanocomposite from MOF on graphene precursor for superior lithium and sodium ion storage

Tin dioxide (SnO2) is being investigated as a promising anode material for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Effectively dispersing small sized SnO2 crystals in well-designed carbonaceous matrices using eco-friendly materials and simplified methods is an urgent task. Herein, gallic acid (GA) molecules, abundant in plant kingdom, are firstly selected to react with few-layered graphene oxide (GO) in mild hydrothermal condition, and the GA modulated reduced graphene oxide (GA@RGO) supporting skeleton can be obtained. Then Sn-GA metal–organic framework (MOF) domains can be directly engineered on the surface of the GA@RGO sheets with controlled size and improved dispersion. Finally, the well-designed Sn-GA@RGO precursor is converted to the SnO2/C/RGO nanocomposite with significantly optimized microstructure. The SnO2/C/RGO sample delivers an excellent specific capacity of 823.6 mAh·g−1 after 700 cycles at 1000 mA·g−1 in half-cells and 741.3 mAh·g−1 after 50 cycles at 200 mA·g−1 in full-cells for LIBs, a specific capacity of 370.3 mAh·g−1 after 600 cycles at 200 mA·g−1 in half-cells for SIBs. The sample preparation strategy is rationally established by comprehensively understanding the interactions between GO sheets, Sn2+ ions and GA molecules, and the engineered SnO2/C/RGO nanocomposite has good prospects in wider fields.

Nitrogen-Doped Porous Carbon Derived from Coal for High-Performance Dual-Carbon Lithium-Ion Capacitors.

Lithium-ion capacitors (LICs) are emerging as one of the most advanced hybrid energy storage devices, however, their development is limited by the imbalance of the dynamics and capacity between the anode and cathode electrodes. Herein, anthracite was proposed as the raw material to prepare coal-based, nitrogen-doped porous carbon materials (CNPCs), together with being employed as a cathode and anode used for dual-carbon lithium-ion capacitors (DC-LICs). The prepared CNPCs exhibited a folded carbon nanosheet structure and the pores could be well regulated by changing the additional amount of g-C3N4, showing a high conductivity, abundant heteroatoms, and a large specific surface area. As expected, the optimized CNPCs (CTK-1.0) delivered a superior lithium storage capacity, which exhibited a high specific capacity of 750 mAh g-1 and maintained an excellent capacity retention rate of 97% after 800 cycles. Furthermore, DC-LICs (CTK-1.0//CTK-1.0) were assembled using the CTK-1.0 as both cathode and anode electrodes to match well in terms of internal kinetics and capacity simultaneously, which displayed a maximum energy density of 137.6 Wh kg-1 and a protracted lifetime of 3000 cycles. This work demonstrates the great potential of coal-based carbon materials for electrochemical energy storage devices and also provides a new way for the high value-added utilization of coal materials.