Advanced Lithium-ion Battery Anode Research Articles

N-doped C encapsulated Li2TiSiO5 nanoparticles for high-rate highly stable lithium storage

Achieving high charging rates (≤ 15 min) in lithium-ion batteries (LIBs) is imperative for their widespread implementation in all-electric vehicles. However, the pursuit of elevated charging rates often leads to compromises in capacity and cycling stability. In this manuscript, we present a groundbreaking approach utilizing a composite material composed of nitrogen-doped carbon-encapsulated Li2TiSiO5 nanoparticles (LTSO@C-N) as the anode material for LIBs, offering rapid and exceptionally stable lithium storage. The encapsulation of Li2TiSiO5 nanoparticles by nitrogen-doped carbon is realized via a facile liquid-phase polymerization and the following pyrolysis route. The uniformly deposited nitrogen-doped carbon layer on the surface of Li2TiSiO5 nanoparticles within LTSO@C-N serves a dual purpose: enhancing the conductive properties of Li2TiSiO5 to ensure efficient charge transfer and Li+ transport, while concurrently inhibiting grain pulverization over extended cycling periods. The deliberate incorporation of nitrogen-doped carbon optimizes Li2TiSiO5 anode electrochemical performance, simultaneously reducing structural degradation during prolonged cycling. This enhances the lithium-ion battery system's long-term stability and reliability. While exhibiting an average operational potential of approximately 0.28 V in comparison to Li+/Li, the LTSO@C-N electrode manifests a commendable specific capacity of 345 mAh g-1 at a current density of 0.1 A g-1. Notably, it attains a robust lithium storage capability even under high-rate conditions, exemplified by a sustained capacity of 205 mAh g-1 over 1000 cycles at 2 A g-1, devoid of any discernible decay. The electrode's impressive electrochemical performance highlights its potential as an advanced anode for high-performance lithium-ion batteries, ensuring stability.

Design of Supported–Coated Structure Silicon/Carbon Composites Using Industrial Waste Micrometer-Sized Silicon for an Advanced Lithium-Ion Battery Anode

Design of Supported–Coated Structure Silicon/Carbon Composites Using Industrial Waste Micrometer-Sized Silicon for an Advanced Lithium-Ion Battery Anode

Three-Dimensional Self-Supported Ge Anode for Advanced Lithium-Ion Batteries.

Three-dimensional (3D) self-supported Ge anode is one of the promising candidates to replace the traditional graphite anode material for high-performance binder-free lithium-ion batteries (LIBs). The enlarged surface area and the shortened ions/electrons transporting distance of the 3D electrode would greatly facilitate the rapid transfer of abundant lithium ions during cycling, thus achieve enhanced energy and power density during cycling. Cycle stability of the 3D self-supported Ge electrode would be improved due to the obtained enough space could effectively accommodate the large volume expansion of the Ge anode. In this review, we first describe the electrochemical properties and Li ions storage mechanism of Ge anode. Moreover, the recent advances in the 3D self-supported Ge anode architectures design are majorly illustrated and discussed. Challenges and prospects of the 3D self-supported Ge electrode are finally provided, which shed light on ways to design more reliable 3D Ge-based electrodes in energy storage systems.

MOF-Derived Bimetallic Selenide CoNiSe2 Nanododecahedrons Encapsulated in Porous Carbon Matrix as Advanced Anodes for Lithium-Ion Batteries.

Transition metal selenides have received considerable attention as promising candidates for lithium-ion battery (LIB) anode materials due to their high theoretical capacity and safety characteristics. However, their commercial viability is hampered by insufficient conductivity and volumetric fluctuations during cycling. To address these issues, we have utilized bimetallic metal-organic frameworks to fabricate CoNiSe2/C nanodecahedral composites with a high specific surface area, abundant pore structures, and a surface-coated layer of the carbon-based matrix. The optimized material, CoNiSe2/C-700, exhibited impressive Li+ storage performance with an initial discharge specific capacity of 2125.5 mA h g-1 at 0.1 A g-1 and a Coulombic efficiency of 98% over cycles. Even after 1000 cycles at 1.0 A g-1, a reversible discharge specific capacity of 549.9 mA h g-1 was achieved. The research highlights the synergistic effect of bimetallic selenides, well-defined nanodecahedral structures, stable carbon networks, and the formation of smaller particles during initial cycling, all of which contribute to improved electronic performance, reduced volume change, increased Li+ storage active sites, and shorter Li+ diffusion paths. In addition, the pseudocapacitance behavior contributes significantly to the high energy storage of Li+. These features facilitate rapid charge transfer and help maintain a stable solid-electrolyte interphase layer, which ultimately leads to an excellent electrochemical performance. This work provides a viable approach for fabricating bimetallic selenides as anode materials for high-performance LIBs through architectural engineering and compositional tailoring.

Hierarchical flower-like N-doped Nb2O5@N-doped carbon composites as superior anodes for advanced lithium-ion batteries

Hierarchical flower-like N-doped Nb2O5@N-doped carbon composites as superior anodes for advanced lithium-ion batteries

G–C3N4–assisted synthesis of ultrafine Mn2O3 nanoparticles embedded into N–doped carbon for advanced lithium–ion battery anode

The construction of advanced transition metal oxide (TMO)/carbon anodes to substitute graphite is always being an enormous challenge for the evolution of lithium–ion batteries (LIBs). Herein, a g–C3N4–assisted pyrolysis strategy is exploited to produce Mn2O3 nanoparticles embedded into N–doped carbon (Mn2O3@NC) hybrids. The results confirm that g–C3N4 plays three critical roles (dispersing agent, pore–forming agent and doping agent) in producing Mn2O3@NC hybrids. In the meantime, it is verified that the feed of Mn source greatly affects the synthesis of Mn2O3@NC hybrids. As a consequence, the resultant Mn2O3@NC–M (M means medium loading of Mn source) reaches a balanced proportion of Mn2O3 and NC, and contemporaneously displays a series of intriguing features, including ultrafine Mn2O3 nanoparticles, large specific surface area, rich mesopores and much high N doping amount. Benefitting from these advantages, the obtained Mn2O3@NC–M shows much enhanced cycling stability and rate performance when engaged as an battery anode.

Urchin flower-like SnO2 nanosheets anchored on waste biomass carbon as advanced anode for lithium-ion batteries

Although SnO2 is considered a desirable anode for lithium-ion batteries benefitting from its high theoretical capacity, yet the low electrical conductivity and associated volume expansion substantially hinder the commercialization. Here, urchin flower-like SnO2 nanosheets were anchored on biomass porous carbon material converted from spent disposable bamboo chopsticks via a simple strategy. The prepared SnO2@carbon material could be regarded as a superior anode in lithium-ion batteries. The SnO2@carbon anode delivered an initial specific capacity of 1182.5 mAh g−1 under a current density of 0.1 A g−1 and maintained 275.8 mAh g−1 at 3 A g−1, suggesting the prominent rate capability. Notably, the SnO2@AC anode exhibited 570.5 mAh g−1 after 500 cycles at 0.5 A g−1. The remarkable performances are attributed to the nano-size of SnO2, which shortens the ion transport length and increases the active sites. Besides, the porous carbon material as anchoring substrate boosts the overall conductivity, promotes electrolyte penetration, and buffers volume expansion. Finally, a highly reversible conversion reaction between Li2O/Sn and SnO2, and mitigation of the agglomeration of SnO2 could be realized. The work can provide potential inspiration for waste resource recovery and development of metal oxide-based conversion-type materials for energy storage.

Fluffy ultrathin WO3 nanoneedle clusters in-situ grown in mesoporous hollow carbon nanospheres as advanced anode for lithium-ion batteries

Fluffy ultrathin WO3 nanoneedle clusters are in-situ grown in mesoporous hollow carbon nanospheres (MHCSs) via unique material impregnation and confined molten reaction in MHCS nanoreactors. Through transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Raman spectra and X-ray photoelectron spectroscopy analyses, it can be found that WO3 nanoneedles with 5–10 nm in thickness and ∼140 nm in length are encapsulated within each MHCS with 150–250 nm in diameter and 30–40 nm in shell thick. Thermal gravimetric analysis reveals the WO3 content of 83.5 wt%. Lithium storage performance was evaluated by galvanostatic charge/discharge cycling, cyclic voltammogram and electrochemical impedance spectroscopy. The composite exhibits remarkable rate performance (average discharge capacity of 1352 mAh g−1 at 0.1 A g−1 and 105 mAh g−1 at 10 A g−1) and excellent cycling performance (1094 mAh g−1 at 0.2 A g−1 after 50 cycles, 760 mAh g−1 at 1 A g−1 after 500 cycles, 351 mAh g−1 at 5 A g−1 after 2000 cycles). The composite also presents outstanding kinetics properties, such as high Li+ diffusion coefficient, strong capacitive effect, and low electrochemical impedance. The superior electrochemical performance is attributed to unique “ship-in-a-bottle” structure. MHCSs facilitate electron transfer and ion diffusion, buffer volume change of WO3 and maintain the integrity of WO3. Furthermore, fluffy ultrathin nanoneedle cluster structure endows WO3 with high electrochemical activity.

Interface Controls Large-Volume Change Anodes Pulverization

Micron sized alloys have been considered as the most attractive candidates for advanced lithium or sodium ion battery anodes due to their high capacity, cost effectiveness, and ease of mass production. However, their large volume variation during (de)alloying reaction with Li or Na ions causes severe mechanical degradation of anode materials, resulting in particle pulverization and loss of electrical interparticle contact. In addition, this substantial volumetric fluctuation leads to newly exposed anode surface to electrolyte and instability of solid-electrolyte interphase (SEI), which can bring about continuously formation of SEI layers. To mitigate the large volume change issues of micron sized alloys, various approaches have been studied such as introducing various electrolytes and additives for stabilizing the SEI layers. However, these modified SEI layers are still not enough to suppress the large volume fluctuation of micron sized alloys.Here, we demonstrate that the effect of interface between electrolyte and anode surface on anode pulverization. With micron sized alloying anodes for sodium-ion batteries (Bi and Sn), we observed substantially different pulverization behavior as a choice of electrolyte solvents leading to different anode-electrolyte interface. This different interface reactivity between solvents has a big impact on not only pulverization behavior of alloying anodes but also formation and growth of SEI layers on the surface of anode. Thus, the electrochemical performances of the alloying anodes also can be influenced by its interface characteristics. We thoroughly analyzed the effect of interface of alloying anode from electrode-level to nanoscale by various characterization tools such as Scanning electron microscopy (SEM), X-ray computed tomography (X-ray CT), X-ray photoelectron spectroscopy (XPS), Atom probe tomography (APT), and cryo-transmission electron microscopy (TEM). Moreover, we clarified the mechanism of the interface reaction and pulverization pathway by theoretical simulations. We believe this study can help researchers to understand the degradation behavior of large volume change alloy anodes.

Thermochemical Cyclization Forms Core-Shell Structured Rutile TiO2@C-PAN as an Advanced Anode for Lithium-Ion Batteries

Rutile TiO2 is a prospective lithium-ion anode material, which has the advantages of small volume change and excellent cycling performance. The low theoretical capacity and poor conductivity, however, prevent further application. In this work, we proposed a thermochemical cyclization coating strategy and successfully prepared rutile titanium dioxide anode material coated with conductive polymer Polyacrylonitrile (PAN). The coated material has an initial capacity of 246.5 mAh/g and a stable capacity of 125.5 mAh/g after 100 cycles. It is worth noting that this simple and effective coating method will contribute to the further application of rutile TiO2 materials.

Conductive Polymer Frameworks in Silicon Anodes for Advanced Lithium-Ion Batteries

Silicon anode is endowed with a high theoretical specific capacity. Unfortunately, its applicability in lithium-ion batteries is hindered by several inevitable problems, which are associated with volume changes (i.e., particle pulverization, solid electrolyte interphase layer instability, and electrode failure) and low electrical conductivity of silicon. Among the accessible strategies to enhance the anode performance, conductive polymer frameworks have been envisioned as solutions to overcome the problems. Conductive polymers can jointly bind and electronically connect silicon particles to regulate extensive volume changes while providing pathways for charge transport in a low-cost fashion. This review starts with a detailed summary of conductive polymer framework features in silicon anodes. The main section presents an in-depth discussion and current advancements of the most widely used conductive polymers in silicon anodes [i.e., polyfluorene, polyaniline, polypyrrole, polythiophene, and poly(3,4-ethylenedioxythiophene)] and several other conductive polymers. In the penultimate part, we review the performance evaluation of silicon anodes with five main conductive polymers and provide perspectives on future challenges of batteries from the standpoint of device manufacturing scale-up. In the final part, we briefly summarize the discussed advancements of conductive polymer frameworks in silicon anode for lithium-ion batteries.

Facile preparation of silicon/carbon composite with porous architecture for advanced lithium-ion battery anode

Silicon is a potential anode material for Li battery due to its high theoretical specific capacity (4200 mAh g−1). However, Si is hampered for practical application in Li-battery due to its enormous volume alternation causing instability. Herein, we demonstrated a novel carbon-coated porous structure (C@void/Si-G) synthesized by uniformly wrapping Si into pitch pyrolytic carbon shells and then in-situ removing the sodium chloride template can overcome the bottleneck. It is worth noting that our process for C@void/Si-G also offers a simple route for cost down and mass production of anode material. The C@void/Si-G anodes exhibit an excellent capacity of 1082.7 mAh g−1 at 0.2 C after 200 cycles. Furthermore, it holds a high capacity retention of 81.9 % after 500 cycles at 0.5 C. We found that C@void/Si-G composite only rises about 41% volumetric expansion during 500 operation cycles. This can effectively avoid direct contact between silicon and electrolyte to form a stable solid electrolyte interphase (SEI) film. Especially, practical application of the C@void/Si-G anode is demonstrated in a full cell pairing with LiNi0.3Co0.3Mn0.3O2 cathode. The full cell presents great cycle retention of 90.1 % at 0.2 C after 100 cycles and a high energy density (446 Wh kg−1).

Nanoscale Borate Coating Network Stabilized Iron Oxide Anode for High-Energy-Density Bipolar Lithium-Ion Batteries.

High-capacity metal oxides based on non-toxic earth-abundant elements offer unique opportunities as advanced anodes for lithium-ion batteries (LIBs). But they often suffer from large volumetric expansion, particle pulverization, extensive side reactions, and fast degradations during cycling. Here, an easy synthesis method is reported to construct amorphous borate coating network, which stabilizes conversion-type iron oxide anode for the high-energy-density semi-solid-state bipolar LIBs. The nano-borate coated iron oxide anode has high tap density (1.6g cm-3 ), high capacity (710 mAh g-1 between 0.5 - 3.0V, vs Li/Li+ ), good rate performance (200 mAh g-1 at 50 C), and excellent cycling stability (≈100% capacity resention over 1,000 cycles at 5 A g-1 ). When paired with high-voltage cathode LiCoO2 , it enables Cu current collector-free pouch-type classic and bipolar full cells with high voltage (7.6V with two stack layers), achieving high energy density (≈350Wh kg-1 ), outstanding power density (≈6,700W kg-1 ), and extended cycle life (75% capacity retention after 2,000 cycles at 2 C), superior to the state-of-the-art high-power LIBs using Li4 Ti5 O12 anode. The design and methodology of the nanoscale polyanion-like coating can be applied to other metal oxides electrode materials, as well as other electrochemical materials and devices.

Hydrothermal fabrication of Sn/SnO/SnO2 hybrid nanocomposites as highly reliable anodes for advanced lithium-ion batteries

We report the creation of novel materials via a Li-ion-battery-compatible, inexpensive, and simple process. Urea and SnCl2 were used as the precursors in the effective hydrothermal synthesis of a novel hybrid nanocomposite made of Sn, SnO, and SnO2.

Blue phosphorene/graphdiyne heterostructure as a potential anode for advanced lithium-ion batteries: First-principle investigation

Blue phosphorene has triggered enormous research effort as an anode for Li-ion batteries due to its large surface and high capacity. However, its application is hindered by poor electrical conductivity, mechanical properties and mobility. Graphdiyne exhibits excellent mechanical properties and high storage capacity but low Li-ion mobility. Herein, we designed blue phosphorene/graphdiyne (BlueP/GDY) heterostructure as a potential anode material for LIB based on denstity functional theory. We demonstrated that BlueP/GDY heterostructure exhibits good thermodynamics stability and enhanced elastic stiffness (Young’s modulus is 215.9 N/m), which can effectively avoid electrode cracking and pulverization. Synergistic effect between BlueP and GDY significantly enhanced binding strength of Li for composite compared with isolated BlueP and GDY. The transition of semiconducting to metallic induced by Li intercalation suggested better metallic conductivity for fast electron transport. Furthermore, BlueP/GDY heterostructure delivers high theoretical specific capacity (761.76 mA·h·g−1) and rather small Li-ion diffusion energy barriers (0.11 eV), which is estimated to be 105 times faster than that on isolated BlueP and GDY at room temperature, indicating excellent rate performance for BlueP/GDY anode. Therefore, it is expected that BlueP/GDY heterostructure has great potential in LIBs with excellent mechanical stability, good electrical conductivity, high capacity and fast Li-ion mobility.

3D MoS2/graphene nanoflowers as anode for advanced lithium-ion batteries

Vertical MoS2 nanosheets were controllably patterned onto graphene as nanoflowers through a two-step hydrothermal method. The interconnected network and intimate contact between MoS2 nanosheets and graphene by vertical channels enabled a high mechanical integrity of electrode and cycling stability. In particular, MoS2/graphene nanoflowers anode delivered an ultrahigh specific capacity of 901.8 mA·h/g after 700 stable cycles at 1000 mA/g and a corresponding capacity retention as 98.9% from the second cycle onwards.

The pursuit of commercial silicon-based microparticle anodes for advanced lithium-ion batteries: A review

Silicon (Si) is one of the most promising anode materials for high-energy lithium-ion batteries. However, the widespread application of Si-based anodes is inhibited by large volume change, unstable solid electrolyte interphase, and poor electrical conductivity. During the past decade, significant efforts have been made to overcome these major challenges toward industrial applications. This review summarizes the recent development of microscale Si-based electrodes fabricated by Si microparticles or other industrial bulk materials from the perspective of industrialization. First, the challenges for microscale Si anodes are clarified. Second, structural design strategies of stable micro-sized Si materials are discussed. Third, other critical practical metrics, such as robust binder construction and electrolyte design, are also highlighted. Finally, future trends and perspectives on the commercialization of Si-based anodes are provided.

Design of Cuboidal FeNi2S4-rGO-MWCNTs Composite for Lithium-Ion Battery Anode Showing Excellent Half and Full Cell Performances

Ternary metal sulfides are projected as advanced lithium-ion battery (LIB) anodes due to their superior electronic conductivity and specific capacity compared to their respective oxide counterparts. Herein, a porous composite of cuboidal FeNi2S4 (FNS) with 2D reduced graphene oxide (rGO) and 1D multi-walled carbon nanotubes (MWCNTs) (composite name: FNS@GC) synthesised by an in-situ single-step hydrothermal process. The 1D/2D combined thin carbon coatings on the FeNi2S4 prevent aggregation during battery performance by increasing conductivity and resisting the volume changes at lithiation/de-lithiation processes. Consequently, the FNS@GC composite exhibits a commending electrochemical performance with a charge capacity of 797 mAh g−1 and a first cycle coulombic efficiency of ~67% with reversible capacity restoration property and excellent long-term cycling stability. Furthermore, FNS@GC//LiFePO4 full cell reveals its practical applicability as a LIB anode with a reversible capacity of 77 mAh g−1 at 50 mA g−1 current density.

Self-template synthesis of peapod-like MnO@N-doped hollow carbon nanotubes as an advanced anode for lithium-ion batteries

Self-template synthesis of peapod-like MnO@N-doped hollow carbon nanotubes as an advanced anode for lithium-ion batteries

Controlled prelithiation of siloxene nanosheet anodes enables high performance 5 V-class lithium-ion batteries

Two-dimensional siloxene nanosheet has attracted great attention as an advanced anode for lithium-ion batteries (LIBs) due to its special characters. However, the high surface area leads to a low initial Coulombic efficiency (ICE) and large irreversible capacity, impeding the further application of siloxene. In this work, controlled chemical prelithiation is designed to overcome the issue. The influences of prelithiated conditions on physical and electrochemical performance are researched. Uniform SEI film and high coulombic efficiency is obtained with a 15 min prelithiation process. The prelithiated siloxene anode shows high ICE, superior rate performance and stable cycling performance. When coupled with 5 V-class LiNi0.5Mn1.5O4 cathodes, an enhanced capacity retention of 94.3 % is achieved after 200 cycles. This work may be useful for designing advanced anodes for rechargeable batteries.