Lithium Storage Performance Research Articles

Vertically Aligned MoS2 Nanosheets with Increased Interlayer Spacing on Hollow Polypyrrole Nanotubes for Enhanced Lithium and Sodium Storage Performance

Vertically Aligned MoS₂ Nanosheets with Increased Interlayer Spacing on Hollow Polypyrrole Nanotubes for Enhanced Lithium and Sodium Storage Performance

In situ anchoring of FeNi nanoparticles into three-dimensional nitrogen-doped carbon framework as a self-supporting electrode for high-performance lithium storage

Constructing free-standing electrodes with superior lithium storage capacity and good mechanical performance are fascinating for next-generation lithium-ion batteries (LIBs). Nevertheless, their practical application is hindered by complicated synthesis procedures and high cost. Herein, a highly stable, self-supporting and flexible electrode material for LIBs was constructed by encapsulating spherical FeNi nanoparticles into one-dimensional N-doped carbon fiber film (FeNi/N- CFM) using the electrospinning technique and subsequent heat treatment. The FeNi/N-CFM can be directly used as anode materials for LIBs without conductive additive, current collector and binder. The synergistic effect of uniformly dispersed small FeNi nanoparticles and three-dimensional (3D) conductive network constructed by CF framework effectively improves the utilization rate of active materials, enhances the transport of both electrons and lithium ions, facilitates the electrolyte penetration, and promotes the lithium-ion storage kinetics and stability, thus leading to a greatly enhanced electrochemical performance. Benefiting from the unique architectural feature and flexibility, the FeNi/N-CFM composites employed as binder-free electrodes for LIBs exhibit good lithium storage performance (an initial discharge capacity of 1031.5 mA h g−1 and a reversible capacity of 481.3 mA h g−1 at 100 mA g−1 after 100 cycles), rate capacity (305.1 mA h g−1 at 1000 mA g−1) and outstanding reversibility (coulombic efficiency of around 100 % after 100 cycles). Furthermore, this work also provides a facile and effective pathway to design and fabricate free-standing electrodes.

A K2C2O4/nano-CaCO3 dual-templated method to prepare rich nitrogen-doped hierarchical porous carbon with excellent lithium storage performance

Three-dimensional interconnected porous carbon with diverse guest element doping is considered one of the most promising anode materials in lithium-ion batteries (LIBs) owing to their large lithium storage capacity and the acceleration effects on the electrochemical kinetics. However, the regulation of desirable pore structure and guest element amount and species for high energy density and stable cycling performance is still challenging. Herein, sucrose-based hierarchical N-doped porous carbon (SHC-750) is prepared via a facile one-step carbonization/activation process at 750 °C for 1 h. The K2C2O4 and nano-CaCO3 are employed as the dual activating-agent/template, and the urea is used as an N source. Benefiting from the hierarchical porous structure, abundant defects, and high amount of N/O-containing functional groups with a multi-chemical state, SHC-750 delivers an excellent reversible specific capacity (1051.2 mAh/g at 0.1 A/g and) and great cycling stability. Moreover, SHC-750 exhibits fast lithium ions diffusion kinetics, which is attributed to the special ordered and hierarchical pore structure. This work provides a new pathway for the preparation and application of 3D interconnected porous carbon materials in the field of electrodes.

Three-dimensional porous structure CoP/N-doped carbon nanospheres as anode for enhanced lithium storage performance

Transition metal phosphides (TMPs) with high theoretical capacities and safe operating voltage are recognized as prospective anode materials for lithium-ion batteries (LIBs). While, the huge volume expansion and low conductivity of TMPs still restrict their applications. Engineering nanostructured composites consisting of TMPs and conductive carbon-based materials is of great importance to improve electrochemical performance. Herein, a novel and facile pyrolysis-oxidation-phosphidation approach is designed to fabricate porous nanospheres composing of CoP nanoparticles and N-doped carbon substrate. The abundant pores in CoP/N-C provide ample active sites for lithium storage and facilitate Li+ transport. The introduction of N-doped carbon substrate enhances the electrical conductivity, allowing CoP to maintain its structure during cycling. The CoP/N-C anode achieves remarkable cycle performance, maintaining an extremely stable cycle life over 2000 cycles at 5 A g−1. More importantly, the full cell consisting of CoP/N-C and LiFePO4 also exhibits a prominent cycling durability with a capacity retention of 96.5 % at 0.1 A g−1 after 150 cycles. This work proposes a simple and feasible structural engineering strategy, which can provide a new way for optimizing the electrochemical performance of conversion-type anode materials.

Electrochemical Kinetics of LiFePO4 Cathode Material in Non-flammable Inorganic Liquid Electrolyte.

We unveil the fundamental insights of electrochemical kinetics of LFP cathode material and the passivation layer formation in the SO2-based non-flammable inorganic liquid electrolyte (IE). The influence of temperature and electrochemical potential cutoff in the electrochemical activity of LFP cathode and IE is disclosed. Furthermore, the materials compatibility, structural and chemical stability of LFP in IE is demonstrated using very slow galvanostatic cycling in combination with LiFePO4||Li0.1FePO4 symmetric cells. The lithium storage performance of LFP half-cell using inorganic electrolyte is presented with the optimum voltage window. LFP half-cells exhibit discharge capacities of 147, 111, and 75 mAh/g at 1, 4, 8 C rates, respectively, with coulombic efficiencies of ~99.98 %. The electrochemical behavior and mechanism of LFP||Graphite cell in IE is investigated while concurrently tracking the electrochemical potentials of LFP and Graphite half-cell.

Unveiling the Influences of In Situ Carbon Content on the Structure and Electrochemical Properties of MoS2/C Composites.

In this work, a MoS2/C heterostructure was designed and prepared through an in situ composite method. The introduction of carbon during the synthesis process altered the morphology and size of MoS2, resulting in a reduction in the size of the flower-like structures. Further, by varying the carbon content, a series of characterization methods were employed to study the structure and electrochemical lithium storage performance of the composites, revealing the effect of carbon content on the morphology, structure characteristics, and electrochemical performance of MoS2/C composites. The experimental setup included three sample groups: MCS, MCM, and MCL, with glucose additions of 0.24 g, 0.48 g, and 0.96 g, respectively. With increasing carbon content, the size of MoS2 initially decreases, then increases. Among these, the MCM sample exhibits the optimal structure, characterized by smaller MoS2 dimensions with less variation. The electrochemical results showed that MCM exhibited excellent electrochemical lithium storage performance, with reversible specific capacities of 956.8, 767.4, 646.1, and 561.4 mAh/g after 10 cycles at 100, 200, 500, and 1000 mA/g, respectively.

Nitrogen plasma-induced phase engineering and titanium carbide/carbon nanotubes dual conductive skeletons endow molybdenum disulfide with significantly improved lithium storage performance

MoS2/Ti3C2 MXene composite has emerged as a promising anode material for lithium storage due to the synergistic combination of high specific capacity offered by MoS2 and conductive skeleton provided by Ti3C2 MXene. However, its two-dimensional/two-dimensional (2D/2D) structure is susceptible to collapse after long cycles, while the inherent low conductivity of MoS2 limits its rate performance. In this study, we developed a novel approach combining plasma-induced phase engineering with dual skeleton structure design to fabricate a unique P-MoS2/Ti3C2/CNTs anode material featuring highly conductive 1T phase MoS2 and a stable one-dimensional/two-dimensional (1D/2D) architecture. Within this architecture, growth of MoS2 nanosheets on the surface of Ti3C2 cross-linked by carbon nanotubes (CNTs) was achieved. The resulting Ti3C2/CNTs dual skeleton not only provides robust mechanical support to prevent structural collapse during long cycles but also offers increased specific surface area and additional Li+ storage space, thereby enhancing the lithium storage capacity of the composite. Subsequent N2 plasma treatment induced a phase transition in MoS2 from 2H to 1T configuration. Density functional theory (DFT) calculations confirmed that the induced 1T-MoS2 exhibits higher conductivity and lower Li+ diffusion barrier compared to 2H-MoS2. Benefiting from these synergistic effects, our P-MoS2/Ti3C2/CNTs anode demonstrated remarkable electrochemical performance including a high reversible specific capacity of 1120 mAh g−1 at 0.1 A g−1, excellent cycling stability with a specific capacity retention of 670 mAh g−1 after 600 cycles at 1 A/g, and superior rate performance with a specific capacity of 614 mAh g−1 at 2 A g−1. This combined modification strategy will serve as guidance for designing other energy storage materials.

Stress-relieved hollow porous carbon nanoring structures anchored with ZnCo2O4 nanoparticles towards super stable lithium storage

Stress-induced structural mechanical instability is a common occurrence in the electrode material during electrochemical cycling, especially for composite material systems. The structural mechanics engineering of nanocomposites comprising electrochemical active materials and carbon with novel structures holds great promise in addressing this issue. However, conventional carbonaceous materials often encounter challenges in long-term durability and high specific capacity stemming from their intrinsic uneven stress distribution and few active sites. Herein, finite element analysis reveals that the ring-like structure effectively mitigates stress concentration from expansion and possesses high packing density, outperforming traditional nanosphere and nanocube architectures. Accordingly, nanocomposites consisting of hollow porous nanostructured N-doped carbon nanorings (N-CNRs) anchored with bimetallic ZnCo2O4 nanoparticles are designed, which exhibit an extraordinary cycling performance for lithium storage with 96.4 % capacity retention following 1000 cycles and an impressively low storage degradation rate of 0.00357 % per cycle, as well as displaying an excellent specific capacity (1218 mA h/g at 0.1 A g−1) and outstanding rate performance (565 mA h/g at 5.0 A g−1). The well-engineered design nanocomposite features the synergistic effect of electrochemically active ZnCo2O4 nanoparticles integrated with structurally stable carbon nanorings for enhanced electrochemical performance.

Synthesis of porous Mg2MnO4 spinel microspheres and enhanced lithium storage properties

Porous Mg2MnO4 spinel microspheres were synthesized by a facile solvothermal method. Various techniques such as X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, were used to characterize the phase composition, morphology and electronic structure of materials. The results show that Mg2MnO4 spinel material was obtained at the temperature of 600–800 °C and has a microsphere structure. The microspheres were assembled by nanoparticles, and the particle size increases with the increase of annealing temperature. Analyses of XPS spectra reveal that Mn exists in multiple valence states (+2, +3, +4) in Mg2MnO4 materials, and all the materials are mixed spinel with Mg2+ and Mn2+/3+/4+ ions occupy both tetrahedral and octahedral sites of spinel structure, and the degree of inversion decreases with increasing annealing temperature. Mg2MnO4 microspheres exhibit excellent lithium storage performance, the first discharge specific capacity of M2MO-8 is 835.3 mAh g−1 under a voltage window of 0–3 V and with a current density of 100 mA g−1, and after 100 cycles the discharge capacity of the material is as high as 406.5 mAh g−1. In addition, this material shows high cyclic reversibility. The enhanced lithium storage properties of the material can be attributed to its porous structure, which promote the transport of lithium ions and reduce the damage to the structure caused by the volume change during the charge and discharge process.

Constructing stress-release layer on Si nanoparticles for high-performance lithium storage

Tailing structures of silicon anode to alleviate the mechanical stress has an important significance in the development of lithium-ion batteries (LIBs). Herein, the stress-released layer of N-doped cubic carbon on the surface of Si nanoparticles (Si@NCC) is explored to stabilize the electrode. Endowed with the unique superiority, the Si@NCC electrode delivers an impressive lithium storage performance with high specific capacity of 630 mAh/g at 0.1 A/g, excellent cycling stability (72.0 % capacity retention after 100 cycles at 0.1 A/g) and good rate capability (375 mAh/g at 2 A/g). It has been demonstrated that the N-doped cubic carbon shell with high conductivity can effectively limit the expansion and agglomeration of Si nanoparticles. Besides, the COMSOL simulations of the stress distributions in materials confirm that the N-doped cubic carbon layer could remarkably decrease the stress originated from the volume expansion of Si nanoparticles during the lithiation. Therefore, this work provides ideas for the mechanical effect of Si-based anodes for lithium storage and sheds lights on the designing advanced materials toward high-performance energy storage devices.

Solid-State Construction of CuO-Cu2O@C with Synergistic Effects of Pseudocapacity and Carbon Coating for Enhanced Electrochemical Lithium Storage.

The pseudocapacitive effect can improve the electrochemical lithium storage capacity at high-rate current density. However, the cycle stability is still unsatisfactory. To overcome this issue, a multivalent oxide with a carbon coating represents a plausible technique. In this work, a CuO-Cu2O@C composite has been constructed by a one-step bilayer salt-baking process and utilized as anode material for lithium-ion batteries. At a current density of 2.0 A g-1, the as-prepared composite delivered a stable discharge capacity of 431.8 mA h g-1 even after 600 cycles. The synergistic effects of the multivalence, the pseudocapacitive contribution from copper, and the carbon coating contribute to the enhanced electrochemical lithium storage performance. Specifically, the existence of cuprous suboxide improves the electrochemical conductivity, the pseudocapacitive effect enhances the lithium storage capacity, and the presence of carbon ensures cycle stability. The testing results show that CuO-Cu2O@C composite has broad application prospects in portable energy storage devices. The present work provides an instructive precedent for the preparation of transition metal oxides with controllable electronic states and excellent electrochemical performance.

Hollow core-shell Si-PEI@ZIF-67 with cross-linking effect for high-performance Li-ion batteries

Owing to its extremely high theoretical capacity (4200 mAh g−1), silicon (Si) has emerged as a promising candidate for lithium-ion batteries (LIBs) anodes. However, challenges such as a volumetric expansion of up to 300 % and poor electrical conductivity have impeded its application. Here, hollow core-shell Si-PEI@ZIF-67 synthesized via a simple one-pot method utilizing the unique properties of ZIF-67, including its porous nature, high surface area, and well-ordered structure, ZIF-67 coating effectively mitigates the volume expansion of nano-Si during cycles. Hollow core-shell structure can accelerate ion transfer and alleviate volume expansion. Moreover, Co2+ enrichment in the coating promotes the formation of a strong cross-linking network with the binder sodium alginate. This interaction not only enhances the adhesion between active material and current collector but also accelerates ion transport. Si-PEI@ZIF-67 composites demonstrate outstanding lithium storage performance in LIBs, achieving a stable capacity of 1134.4 mAh g−1 after 500 cycles at 1000 mA g−1. In addition, the discharge capacity of 828.7 mAh g−1 is maintained after 200 cycles at the high current density of 5000 mA g−1. The innovative synthesis method, utilizing ZIF-67 as a coating for nano-Si and establishing an interconnected network with the binder, offers a novel approach for other anodes.

Facile preparation of MnO/Mn3O4 anode from commercial manganese(II) oxalate dihydrate and its advanced lithium storage performance

Manganese oxides are considered a highly promising anode material in lithium ion batteries (LIBs) because of their high theoretical capacity, abundant sources, relatively low voltage hysteresis, nontoxic and cost-effectiveness. Nevertheless, the practical application of these materials faces many challenges such as poor lifespan and serious volume variation during operation. Herein, MnO/Mn3O4–600 composite was obtained based on a single-step pyrolysis procedure from commercial manganese(II) oxalate dihydrate (MOD, C2H4MnO6). The MnO/Mn3O4–600 anode exhibits an exceptionally high reversible capacity of 1041.8 mAh g−1 at the current density of 200 mA g−1, and a remarkable lifespan at 1000 mA g−1. The outstanding performance benefits from the formation of porous structures on nanoparticles, which not only mitigate volume changes and prevent the aggregation of internal MnO/Mn3O4 nanoparticles, but also enhance the ion diffusion. The in-depth insights into the (de)lithiated mechanism of the electrode are investigated by in situ X-ray diffraction (XRD) technique. Moreover, when applied in a full cell, the MnO/Mn3O4–600 anode demonstrates exceptional electrochemical property.

Formation of hollow stepped FePBA@rGO anode for high-performance lithium-ion batteries

Prussian blue and its analogues (PBAs) have been considered promising anode materials for lithium-ion batteries (LIBs) owing to their high theoretical capacity and cost-effectiveness. However, they often encounter challenges such as poor electronic conductivity and structural instability. Herein, we introduce a hollow stepped FePBA framework structure coated with reduced graphene oxide (FePBA@rGO). This sophisticated design significantly improves electronic conductivity and optimizes the diffusion pathways for lithium ions, leading to exceptional cycling stability and rate performance. The FePBA@rGO-15 anode developed in this study shows a notable rate capability of 294 mAh g−1 at a current density of 2 A g−1. More significantly, it demonstrates exceptional lithium storage performance, maintaining a capacity of 1245 mAh g−1 after 600 cycles at a current density of 1 A g−1. Density functional theory simulations further support our findings by illustrating that the robust interface between FePBA and rGO significantly accelerates the reactions kinetics of Li+ within the FePBA framework. This study represents a significant advancement towards improving the capacity and cycling stability of PBA-based anode materials, offering promising prospects for future battery applications.

Lithium modulated spinel high entropy oxide anode of LIBs through microwave solvothermal method

Spinel structured high entropy oxides (HEO) with three-dimensional Li+ transport channel and two different Wyckoff sites show high theoretical capacities due to multiple hypervalent ions and abundant oxygen vacancies. However, the intrinsic poor electrical conductivity of oxides and the lack of low-energy-consumption synthesis methods remain problems. Herein, Li+ with low-electronegativity is introduced into (FeCoNiCrMn)3O4 through high-efficiency microwave-assisted solvothermal method. The nano-scale high entropy oxide particles with homogeneous distribution of elements are successfully obtained in a short time. The addition of Li+ in HEO not only increases the valence states of transition metal cations to increase the number of electron transfers, but also induces more oxygen vacancies, which facilitates Li ion storage and increases ionic conductivity. The Li induced lattice distortion together with the entropy stabilization mechanism alleviate the lattice stress, featuring the anode superior electrochemical stability. The anode HEO-15 with the optimal Li content shows the specific capacity of 452.8 mAh g-1 at a current density of 500 mA g-1 after 300 cycles for LIBs, much higher than that of HEO-0 (248.9 mAh g-1). This research provides an effective method to improve the lithium storage performance of HEO.

Carbon Nanotubes Connecting and Encapsulating MoS2-Doped SnO2 Nanoparticles as an Excellent Lithium Storage Performance Anode Material.

Doping and carbon encapsulation modifications have been proven to be effective methods for enhancing the lithium storage performance of batteries. The hydrothermal method and ball milling are commonly used methods for material synthesis. In this study, a composite anode material rich in carbon nanotubes (CNTs) conductive tubular network connection and encapsulation of SnO2-MoS2@CNTs (SMC) was synthesized by combining these two methods. In this highly conductive network, nano-SnO2 particles are uniformly dispersed and embedded in MoS2 with a layered structure, and the obtained SnO2-MoS2 composite material is tightly connected and encapsulated by the tubular network of CNTs. It is worth noting that the incorporation of layered MoS2 not only effectively anchors the SnO2 nanoparticles, but also provides a broader space for lithium-ion movement due to the larger interlayer spacing. The conductive network of CNTs shortens the diffusion path of electrons and Li+ and provides more diffusion channels. The reversible capacity of the SnO2-MoS2@CNTs nanocomposite material remains at 1069.3 mA h g-1 after 320 cycles at 0.2 A g-1, and it exhibits excellent long-term cycling stability, maintaining 904.5 mA h g-1 after 1000 cycles at 1.0 A g-1. The composite material demonstrates excellent pseudocapacitive contribution rate performance, with a contribution rate of 87% at 2.0 mV s-1. The results indicate that SnO2-MoS2@CNTs has excellent electrochemical lithium storage performance and is a promising anode material for lithium-ion batteries.

Modification of Li3PO4 layer effectively boosting lithium storage and thermal safety performance for LiCoO2 batteries

To meet the demand for high-performance LiCoO2 batteries, it is necessary to overcome challenges such as interface degradation and rapid capacity degradation caused by changes in bulk structure, especially under deep delithiation and high temperature conditions. The ion conductive coating layer of Li3PO4 has been directly modified on the surface of LiCoO2 particles using magnetron sputtering method, significantly improving the lithium storage performance of LiCoO2@Li3PO4 composites. Compared to pure LiCoO2, the modified LiCoO2 sample exhibits obviously better cycle life and high-temperature performance. Especially, under the conditions of 2 and 1 C, the LiCoO2@Li3PO4 electrode delivers excellent cycling performance at high voltage of 4.5 V, with capacity retention rates of 89.7% and 75.7% at room temperature and high temperature of 45 °C, being far greater than those of 12.3% and 29.1% for bare LiCoO2 electrodes. It is discovered that the Li3PO4 coating layer not only effectively enhances interface compatibility and suppresses the irreversible phase transition of LiCoO2, but also further improves the Li+ transport kinetics and significantly reduces battery polarization, ultimately enabling the modified LiCoO2 electrode to exhibit excellent lithium storage performance and thermal safety characteristics under high voltage conditions. Thus, such effective modified strategy can undoubtedly provide an important academic inspiration for LiCoO2 implication.

Study on the synthesis mechanism of new α-FeOOH@3DGF material and its lithium storage performance

A new self-supporting material contained nanorods α-FeOOH and three-dimensional skeleton graphene foam (3D Graphene Foam, 3DGF) was prepared by hydrothermal method. The growth mechanism and phase change rules of nanorods α-FeOOH@3DGF were studied to obtain the electrochemical lithium storage performance. The results showed that growth mechanism of nanorods α-FeOOH was accompanied by the consumption of nanoparticles β-FeOOH. If the hydrothermal time reached to 12 h, the nanoparticle β-FeOOH phase completely disappeared with only rod-shaped α-FeOOH@3DGF single phase obtained. Rod-shaped α-FeOOH@3DGF was used as anode material of lithium-ion batteries and the reversible specific capacity remained at about 305 mAh·g−1 after charging and discharging 250 times at 500 mA·g−1, with significantly cycling stability compared with that of the monomaterial α-FeOOH.

Empowering lithium-ion storage: unveiling the superior performance of niobium-based oxide/perovskite heterojunction with built-in electric field

The increasing demand for high-performance electrode materials in lithium-ion batteries has driven significant attention towards Nb2O5 due to its high working voltage, large theoretical capacity, environmental friendliness, and cost-effectiveness. However, inherent drawbacks such as poor electrical conductivity and sluggish electrochemical reaction kinetics have hindered its lithium storage performance. In this study, we introduced KCa2Nb3O10 into Nb2O5 to form a heterojunction, creating a built-in electric field to enhance the migration and diffusion of Li+, effectively promoting electrochemical reaction kinetics. Under the regulation of the built-in electric field, the charge transfer resistance of the KCa2Nb3O10/Nb2O5 anode decreased by 3.4 times compared to pure Nb2O5, and the Li+ diffusion coefficient improved by two orders of magnitude. Specifically, the KCa2Nb3O10/Nb2O5 anode exhibited a high capacity of 276 mAh g−1 under 1 C, retaining a capacity of 128 mAh g−1 even at 100 C. After 3000 cycles at 25 C, the capacity degradation was only 0.012% per cycle. Through combined theoretical calculations and experimental validation, it was found that the built-in electric field induced by the heterojunction interface contributed to an asymmetric charge distribution, thereby improving the rates of charge and ion migration within the electrode, ultimately enhancing the electrochemical performance of the electrode material. This study provides an effective approach for the rational design of high-performance electrode materials.

Robust nitrogen-doped porous carbon encapsulated NiCo2S4 nanodecahedrons for enhanced lithium storage

Transition metal sulfides (TMSs) are attractive anode materials for lithium-ion batteries (LIBs) due to their cost effectiveness, impressive redox properties, and high specific capacity. Among them, NiCo2S4 stands out with a substantial theoretical capacity of 703 mAh g−1 and a high electronic conductivity of 1.25 × 106 S m−1, making it a strong candidate for LIBs. However, NiCo2S4 experiences volume changes and mechanical stress during long-term cycling, leading to structural degradation and rapid capacity decay, which hinders its application. To address these issues, we have developed dodecahedral NiCo2S4 embedded within a nitrogen-doped porous carbon structure (NiCo2S4/NC). The optimal NiCo2S4/NC-300 material exhibits minimum charge transfer resistance, maximum pseudo-capacitive contribution, and exceptional lithium storage performance. At 0.1 A g−1, NiCo2S4/NC-300 exhibits an initial discharge/charge specific capacity of 1730.1/949.4 mAh g−1 and retains a discharge capacity of 454.4 mAh g−1 after 100 cycles. Even at 0.5 A g−1, it delivers an initial discharge/charge capacity of 1301.1/540.1 mAh g−1 with a capacity retention of 81.2 % after 500 cycles. This study presents significant potential for NiCo2S4/NC as a high-performance anode material for LIBs, providing new strategies and insights into the mechanisms for enhancing the performance of TMS-based bimetallic anode materials.