Reversible Lithium Storage Research Articles

Preparation of SnS/reduced graphene oxide@Cu nanocomposite with high reversible lithium storage

SnS/reduced graphene oxide@Cu nanocomposite has been fabricated via a two-step synthetic strategy. In the composite material, most of SnS nanoplates are embedded in reduced graphene oxide. Partial SnS nanoplates exposed on the surface of reduced graphene oxide, have been largely coated with Cu nanoparticles. As a result, the nanocomposite has demonstrated high reversible lithium storage. After 640 cycles at 100 mA g−1, the composite remains a reversible capacity of 710 mAh g−1. The results from the electrochemical impedance spectroscopy suggest that the introduction of Cu can reduce the transfer resistance of the electrode and the enhanced lithium storage properties can be attributed to the synergistic effect of SnS, reduced graphene oxide and Cu.

Sulfur-doped reduced graphene oxide/Sb2S3 composite for superior lithium and sodium storage

Graphene, with excellent electrical conductivity and high theoretical capacity, may be one of the promising anodes for rechargeable batteries. However, several drawbacks, such as low initial coulombic efficiency (ICE) and limited actual reversible capacity, hamper their further development. Herein, a sulfur-doped reduced graphene oxide (rGO)-based composite with low-content Sb2S3 is synthesized through in-situ sulfuration process, which can deliver excellent electrochemical performance (high reversible capacity of 997 mA h g−1 with ICE of 71.6% for lithium storage and 639 mA h g−1 with ICE of 63.9% for sodium storage at 100 mA g−1), much higher than those of sulfur-doped or bare rGO. According to the physical and electrochemical characterizations, the partial substitutions of C–O bonds with C–S in rGO can greatly reduce the irreversible consumption of lithium or sodium, the covalent-bonded sulfur dopants and the doped Sb2S3 nanoparticles are electrochemically active for reversible lithium and sodium storage, and also enhance the structure stability effectively, resulting in superior electrochemical performance.

Hierarchical urchin-like Fe2O3 structures grown directly on Ti foils for binder-free lithium-ion batteries with fast charging/discharging properties

Hierarchical urchin-like Fe2O3 structures were grown on conductive Ti foil with robust adhesion via a facile two-step solvothermal method and subsequent annealing, and directly used as a binder-free lithium-ion battery anode Benefitting by the unique structural features, the resultant Fe2O3 hierarchical structures exhibited excellent electrochemical performance with remarkable specific capacities at a serious of current rates 1–5 A g−1 and good cycling stability for excellently reversible lithium storage. The enhanced electrochemical performance demonstrates their promise for use as integrated binder-free electrodes in lithium-ion batteries. Using this additive/binder-free electrode, a discharge capacity as high as 581.2 mAh g−1 at a current density of 5 A g−1 was achieved after 1000 cycles. Importantly, the facile and effective strategy developed in this study can be extended to other metal oxides for various applications.

Engineering layer structure of MoS2/polyaniline/graphene nanocomposites to achieve fast and reversible lithium storage for high energy density aqueous lithium-ion capacitors

In recent years, many efforts are devoted to enhance the energy density of supercapacitors without sacrificing its intrinsic high power density. To achieve this, high energy density aqueous lithium-ion capacitors (LIC) are demonstrated by employing phosphorus-MoS2/polyaniline/reduced graphene oxide hierarchical nanosheets (P–MoS2/PANI/rGO HNSs) anode electrode via a simple organic/inorganic hybridization method. With the phosphorus and PANI intercalate into the adjacent MoS2 layers and then grow on the rGO nanosheets, the P–MoS2/PANI/rGO HNSs has enlarged and disordered interlayer structure and thus obtain improved Li-ion storage capability. Accordingly, an P–MoS2/PANI/rGO HNSs based LIC delivers an energy density of 56.0 Wh kg−1, when the power density is 0.45 kW kg−1. Moreover, the capacitance retention of the P–MoS2/PANI/rGO based LIC can be up to 93.5% after 30,000 charge/discharge cycles at a current density of 5 A g−1, showing great application potential for future electric vehicle.

Sulfur-terminated tin oxides for durable, highly reversible storage of large-capacity lithium

Sulfur-terminated tin oxides could resist the volume expansion significantly and thus offer highly reversible lithium storage.

Controlled synthesis of N-doped carbon and TiO2 double-shelled nanospheres with encapsulated multi-layered MoO3 nanosheets as an anode for reversible lithium storage.

α-Phase molybdenum trioxide (α-MoO3) is one of the promising anode materials for lithium storage due to its high theoretical capacity and unique intercalation reaction mechanism. Herein, through an efficient step-by-step solvothermal synthesis strategy, multi-layered MoO3 nanosheets are encapsulated by nitrogen-doped carbon (NC) and ultrathin TiO2 double-shells to obtain hierarchical core-shell nanospheres (MoO3@TiO2@NC). The unique nanostructure enables shortening the Li+ diffusion distance, buffer the volume change during the intercalation/deintercalation process, and increase the active sites for the electrochemical reaction. Based on the hierarchical nanostructure and the synergistic effect of each component, the MoO3@TiO2@NC electrode exhibits a high Li+ storage capacity around 979.6 mA h g-1 after 200 cycles at 0.2 A g-1, a stable cycle performance of 800.3 mA h g-1 at 1 A g-1 after 700 cycles and an excellent rate capability of 418.0 mA h g-1 at 5 A g-1. Furthermore, the MoO3@TiO2@NC-based coin-type full cell with a commercial LiNi1/3Mn1/3Co1/3O2 cathode exhibited a good cycling stability at 0.2 A g-1 for 100 cycles (∼190 mA h g-1) and rate capability (134 mA h g-1 at 5 A g-1).

Highly reversible lithium storage in a conversion-type ZnCo2O4anode promoted by NiCl2−xFxhydrate

Highly reversible lithium storage in a conversion-type ZnCo2O4anode is achieved by coating ultrafine NiCl2−xFxhydrate on porous ZnCo2O4microspheres.

Polypyrrole-derived nitrogen-doped carbon coated hierarchical MnO porous microspheres for highly reversible lithium storage

Manganese monoxide (MnO) has emerged as a promising anode material in lithium-ion batteries (LIBs) due to its large lithiation capacity, low voltage hysteresis and environmental friendliness. In this work, we have developed the nitrogen-doped carbon coated MnO porous microspheres (MnO@NC), which consist of small nanocrystals with interparticle mesopores via a self-templated solvothermal synthesis and subsequent in-situ pyrolysis of polypyrrole precursors. By virtue of the conductive outer layer of nitrogen-doped carbon (NC) and the abundant inner mesopores, the hierarchical MnO@NC porous microspheres manifest the superior lithium storage properties as anode for LIBs. In detail, the optimized MnO@NC electrode delivers a high initial discharge capacity of 1037 mAh g−1 at 0.2 A g−1, remains the discharge capacity of 890 mAh g−1 at 1A g−1 after 500 cycles, indicates the outstanding rate capability with a specific capacity of 450 mAh g−1 at 5A g−1.

Preparation of hierarchical hexagonal nanoplates NiO composite with microcrystalline graphite for highly reversible lithium storage

In this work, hierarchical hexagonal nanoplates NiO composite with microcrystalline graphite are successfully synthesized by a hydrothermal process. Carbon nanofibers are disaggregated to the microcrystalline graphite and they are dispersed in NiO hexagonal structure (H–NiO sample). Microcrystalline graphite (1 wt% of the composite) has effect on growth NiO hexagonal nanoplates, improving the sample conductivity and stability. At the first cycle, H–NiO sample presents a high discharge capacity of 1357.2 mAh g−1 and a charge capacity of 1002.6 mAh g−1 with an initial coulombic efficiency of 73.9%. After 45 cycles, H–NiO sample exhibits a high reversible capacity of 1111.6 mAh g−1. The lithium diffusion coefficient of the H–NiO is calculated to be 7.517 × 10−12 cm2 s−1 with faster Li+ diffusion ability than pure NiO sample. The microcrystalline graphite in the composite electrode can effectively decrease the volume change and pulverization of NiO component, meanwhile, it hinders the aggregation in the cycled electrode. The microcrystalline graphite with intrinsic stability has potential application in producing composites with other metal oxides for highly reversible lithium storage capability.

Three-dimensionally architectured tungsten trioxide/tungsten trioxide hydrate/carbon cloth composite as a binder-free anode for lithium-ion batteries

The exploration of suitable host structures as anodes is essential for lithium-ion batteries. In this work, a three-dimensionally architectured tungsten trioxide/tungsten trioxide hydrate/carbon cloth composite was synthesized by a simple and cost-effective hydrothermal process. The obtained tungsten trioxide/tungsten trioxide hydrate/carbon cloth composite was directly used as the binder-free electrode and evaluated as an anode for lithium-ion batteries by cyclic voltammetry, galvanostatic discharge-charge measurements, and electrochemical impedance spectroscopy. The binder-free electrode exhibits a high reversible lithium storage capacity of 825 mA h g−1 after 100 cycles at a current density of 0.1 A g−1. When cycled at a current density of 2 A g−1, a capacity of 309 mA h g−1 remained. The excellent electrochemical performance may be due to the unique self-assembled tungsten trioxide/tungsten trioxide hydrate nanorods on the carbon cloth conductive substrate with a three-dimensional architecture.

Reversible lithium storage capacity on carbon nitride by electric field

Abstract Graphitic carbon nitride (g-C3N4) has attracted enormous interest because of its prominent photocatalytic performance. Due to the planar π conjugation structure which should provide good binding energy for adsorption of metal atoms including lithium (Li) and sodium (Na), g-C3N4 also possesses great application potential in ion batteries. Here, first-principles calculations are performed to investigate its application in lithium ion batteries (LIBs), focusing on the electric field effect on the Li storage. Our results revealed that Li adsorbed C3N4 (Li–C3N4) exhibits good modulation of its Li binding energy by applying external vertical electric field. The Bader charge analysis and charge density difference calculations provide a deep insight into the tunable Li adsorption to C3N4 sheets. Our theoretical results suggest that C3N4 is a suitable anode material for LIBs.

Identification of reversible insertion-type lithium storage reaction of manganese oxide with long cycle lifespan

Abstract Recently, MnO2 has gained attention as an electrode material because of its very high theoretical capacity and abundant availability. However, the very high volumetric change caused by its conversion-type reaction results in bad reversibility of charge-discharge. In this study, δ-MnO2 of thickness 8 nm anchored on the surface of carbon nanotubes (CNT) by Mn-O-C chemical bonding is synthesized via a facile hydrothermal method. Numerous ex-situ characterizations of the lithium storage process were performed. Furthermore, density functional theory (DFT) calculations indicated that δ-MnO2 (0 1 2) thermodynamically prefers bonding with CNTs. Moreover, the interfacial interaction reinforces the connection of Mn-O and reduces the bond strength of Li-O in lithiated MnO2, which could facilitate an intercalation-type lithium storage reaction. Consequently, the as-synthesized δ-MnO2 retains an excellent reversible capacity of 577.5 mAh g − 1 in 1000 cycles at a high rate of 2 A g − 1 between 0.1 V and 3.0 V. The results of this study demonstrate the possibility of employing the cost-effective transition metal oxides as intercalation lithium storage dominant electrodes for advanced rechargeable batteries.

Facile synthesis of heteroatom doped and undoped graphene quantum dots as active materials for reversible lithium and sodium ions storage

Zero-dimensional graphene quantum dots have attractive properties but the synthesis of graphene quantum dots in a simple and scalable technique is tedious, which limits its utilization in different energy storage application. In this study, we present a simple and scalable approach to produce graphene quantum dots and heteroatom doped graphene quantum dots using chemical vapor deposition technique. Graphene quantum dots are prepared using alloy-based catalyst and methane as a carbon source. Boron-doped and nitrogen-doped graphene quantum dots are prepared at low temperature using graphite oxide without the use of dialysis bag. Here, the electrochemical lithium and sodium ion storage properties of doped and undoped graphene quantum dots are studied without being used as a supporting material for the performance enhancement as reported in previous reports. Boron doped GQD (B-GQD) exhibits a high specific capacity of 1097 mAh g−1 and 310 mAh g−1 at a specific current of 50 mA g−1 for lithium and sodium ion batteries respectively. B-GQD exhibits high volumetric energy density of 537 Ah L−1 and 214 Ah L−1 with an average voltage of 0.43 V and 0.57 respectively for lithium ion and sodium ion batteries. Also, the cells observe a satisfactory cyclic performance for 500 cycles with good capacity retention. Detailed investigations show that the edge defects present in GQD and doped GQDs help to enhance the electrochemical storage performance of lithium and sodium ions.

Pseudocapacitive behavior of amorphous Nb 2 O 5 at low potentials

Supercapacitor has been demonstrated as one of the most attractive electrochemical energy storage devices for practical applications, especially for electric transportation systems, because of high power density, long cycle life, impressive conversion efficiency and desirable usage safety. However, energy densities of supercapacitors are typically low comparing with lithium-ion batteries, which impedes their broad applications. The development of advanced supercapacitors mainly concerns with increasing their energy densities. Being different from conventional double layer supercapacitors, pseudocapacitive materials can deliver much higher capacitances and energy densities. For example, some metal oxides can be used as electrode materials for stable charge and discharge at high rates on the basis on of reversible surface redox reactions, resulting in desired energy densities comparable to that of lithium-ion batteries. In this work, we study an amorphous α-Nb2O5, which is prepared using a facile hydrothermal method followed by a low temperature post-annealing process. The α-Nb2O5 is evaluated as a pseudocapacitive electrode material in the LiPF6-based organic electrolyte for lithium storage performance. The α-Nb2O5 demonstrates reversible Li+ intercalation/deintercalation behavior in a voltage range of 0.1–2.5 V (vs. Li/Li+), resulting in an impressive reversible lithium storage capacity higher than 250 mAh/g at 0.2 C (1 C = 400 mA/g), together with excellent cycling stability and rate capability up to 10 C for 10000 cycles. In addition, the cyclic voltammetry (CV) profiles obtained at a low scanning rate of 0.1 mV/s show unexpected square patterns in multiple cycles even at low potentials between 1.0 and 0.1 V (vs. Li/Li+), which is distinctly different from that of crystalline orthorhombic Nb2O5 electrode material. The CV analysis also indicates apparent intercalation capacity contribution of such α-Nb2O5 electrode material during lithium ion storage. All electrochemical experiments verify typical pseudocapacitive behavior for the amorphous α-Nb2O5 material in a wide voltage range of 0.1–2.5 V (vs. Li/Li+). The special pseudocapacitive property at low potentials enables the α-Nb2O5 to be used as an attractive anode in a hybrid supercapacitor coupled with the active carbon (AC) material as cathode with a wide voltage window. As a result, the assembled α-Nb2O5//AC hybrid supercapacitor full cell can be charged to a high voltage up to 4.5 V. According to the calculated energy density of the supercapacitor based on E =1/2 CV 2, the high working voltage results in an impressive energy density of 178.5 Wh/kg for this hybrid supercapacitor cell on the basis of the mass of two active electrode materials. In addition, the full cell also shows outstanding high-rate performance, and our ongoing work will optimize associated structure to improve its cycling stability at harsh work conditions. This work offers a promising Nb2O5 material that is amorphous and showing pseudocapacitive behaviors for lithium ion storage at low potentials. Improved capacity and energy density have been achieved, together with desired cycling stability for prolonged cycles. Such an electrode material can be served as a feasible anode material for high-voltage and high-energy hybrid supercapacitor full cell when it is coupled with high-rate cathode materials.

Imine-Rich Poly( o -phenylenediamine) as High-Capacity Trifunctional Organic Electrode for Alkali-Ion Batteries

Alkali-ion batteries, including potassium-ion batteries, lithium-ion batteries, and sodium-ion batteries are important energy storage devices; however, with the cation size increased, there exists ...

Highly Reversible Lithium Storage of Nitrogen‐Doped Carbon@MnO Hierarchical Hollow Spheres as Advanced Anode Materials

AbstractThe practical implementation of MnO‐based anode materials is still obstructed because of their short cyclic life and unsatisfactory rate performance, attributable to low conductivity, large volume variation and self‐aggregation of MnO during intense cycles. To overcome these obstacles, we successfully fabricated nitrogen‐doped carbon@MnO hierarchical hollow spheres through a novel approach. As anode nanomaterials for Li‐ion batteries, the nanocomposite possesses a highly reversible capacity of 1302 mAh g−1 after the 200th cycle at 0.1 Ag−1 and 964 mAh g−1 after the 500th cycle at 0.5 Ag−1, respectively. The prominent electrochemical performances of the nanocomposite may result from synthetic effects of nitrogen‐doped carbon hollow structures, nanosized MnO and the gradual generation of high‐oxide‐state manganese oxide on nitrogen‐doped carbon hollow spheres during intensive cycles. The aforementioned results also demonstrate that MnO nanocrystals can be well utilized by attaching to nitrogen‐doped carbon hollow spheres, which is a valid way to achieve excellent lithium storage properties for transition metal oxides.

Enhanced reversible lithium storage property of Sn0.1V2O5 in the voltage window of 1.5–4.0 V

Sn4+ doped V2O5 (Sn0.1V2O5) sample was synthesized by a sol-gel method and post annealing at 400 °C for 1 h in air. The microstructure of the as-prepared the Sn0.1V2O5 was analyzed by XRD, XPS, and SEM. The lithium storage performance of the Sn0.1V2O5 was characterized by CV, EIS, and charge/discharge tests in the voltage window of 1.5–4.0 V (vs. Li/Li+). The results demonstrated that Sn doping can refine the grain size of V2O5, increase V4+ concentration in Sn0.1V2O5, and favor the formation of two-dimensional sheet-like morphology. Compared to undoped V2O5, the Sn0.1V2O5 exhibited significantly enhanced lithium storage performance in the voltage window of 1.5–4.0 V (vs. Li/Li+). For example, after 100 cycles at 200 mA g−1, the Sn0.1V2O5 retained a specific discharge capacity of 135 mAh g−1, much higher than that (91 mAh g−1) of the pure V2O5. In addition, Sn0.1V2O5 exhibited a higher initial coulombic efficiency (98.16%) than the undoped V2O5 (91.05%). The improved lithium storage performance can be attributed to the increased lithium ion diffusion coefficient, enhanced electrochemical reaction reversibility, and decreased electrochemical reaction resistance upon Sn4+ doping.

One-pot hydrothermal synthesis of ZnS/C microsphere as an electrode for reversible lithium-storage

A one-pot hydrothermal followed by annealing route has been developed to prepare ZnS/C microspheres which are comprised of ZnS nanoparticles incorporated with in-situ gluconate-derived carbon. The robust hybrid structure greatly enhances the stability and conductivity of composites. As a result, the great enhancement in electrochemical Li-storage of ZnS/C can be achieved due to the desirable structural features as well as capacitive contribution.

Three-dimensional hierarchical porous MnCo2O4@MnO2 network towards highly reversible lithium storage by unique structure

In this paper, a three-dimensional hierarchical porous MnCo2O4@MnO2 network was prepared via a facile route and used as anode material for lithium-ion batteries. The prepared material possesses three-dimensional interconnect structure and abundant pore structure, which is favorable for alleviating volume expansion and constructing electron/ion transport channels. In addition, the synergistic and protective effects produced by core-shell structure further enhance the electrochemical performance of material. Merited by this unique structure, MnCo2O4@MnO2 delivers superior cycle stability with a capacity retention of 96% after 200 cycles at a current density of 100 mA g−1 and large capacitive contribution. Besides, the strategy holds potential for mass production, since the method is simple and most of chemicals is recyclable.

Rational design of NiCo2O4/g-C3N4 composite as practical anode of lithium-ion batteries with outstanding electrochemical performance from multiple aspects

The spinel oxide NiCo2O4 is regarded as a desirable electrode material in lithium-ion batteries with high performance due to its better electrochemical activity and higher capacity compared to traditional simple oxides. However, lithium-ion batteries with this conversion reaction anode still suffer from low initial Coulombic efficiency accompanied by the generation of solid electrolyte interface layer. Herein, a facile strategy is proposed to couple nanoparticulate NiCo2O4 with g-C3N4, which effectively reduces solid electrolyte interface formation and leads to a high initial Coulombic efficiency. Various characterization techniques confirm that NiCo2O4 nanoparticles grow homogeneously on g-C3N4 nanosheets. This NiCo2O4/g-C3N4 hybrid, as an anode material for lithium-ion batteries, can reach an initial Coulombic efficiency of 84.5%, which is attributed to low interfacial surface area and high discharge potential of electrodes. Owing to the synergistic effect in the NiCo2O4/g-C3N4 hybrid, excellent reversible capacities of 1252 and 476 mAh g−1 are maintained at respective current densities of 100 and 500 mA g−1 after 100 cycles. The highly reversible lithium storage is a result of high NiCo2O4 electrode performance, unique layered structure, and excellent g-C3N4 properties.