High-performance Lithium-ion Battery Anodes Research Articles

N, P Co-Doped Hard Carbon Anodes for High-Performance Lithium-Ion Batteries with Enhanced Capacity Retention and Cycle Stability.

Compared to the traditional graphite anode, heteroatom-doped polymer carbon materials have high capacity retention due to their high porosity and porous structure. Therefore, they have great potential for application in lithium-ion battery (LIB) anodes. In this work, an N, P co-doped precursor polymer material (MBPp), synthesized via a one-pot method using bisphenol-A (C-source), melamine (N-source), and 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (P-source). The resulting N, P-co-doped hard carbon materials (MBPs) were prepared at various pyrolysis temperatures, yielding microporous, mesoporous, and macroporous structures. MBP materials demonstrated excellent electrochemical performance as LIB anodes. Notably, MBP-900 achieved a reversible capacity of 262 mAh g-1 at 1000 mA g-1 (in 0.005-2.0 V voltage range) with a capacity retention rate of 97.1 % after 1000 cycles. These findings highlight the significance of MBP materials, which possess numerous defects, large layer gaps, and excellent cycle stability, in advancing the development of polymer anode materials for LIBs.

Perovskite-Type CaVO3 Nanocomposite as High-Performance Anode Material for Lithium-Ion Batteries.

Electric vehicles' rapid development has put higher requirements on the performance of lithium-ion batteries (LIBs). However, the specific capacity of a commercial graphite anode (372 mAh g-1) has become the bottleneck for further improvement. Therefore, it is urgent to develop novel anode materials with superior performance. Herein, we propose crystalline-amorphous dual-phase CaVO3 nanocomposites as LIB anodes. Benefiting from the stable perovskite structure and high conductivity of CaVO3, the nanocomposite follows the intercalation mechanism, resulting in no capacity decay during 5000 cycles. In addition, due to the multielectron transfer provided by amorphous high-valent vanadium oxide, the nanocomposite can provide a high specific capacity of 442.8 mAh g-1 with a suitable average working potential of 0.95 V. The ingenious strategy of constructing nanocomposites through spontaneous oxidation of nanoparticles is expected to be extended to the perovskite oxide family, inspiring the development of more high-performance LIB anodes.

Cross-linking γ-Polyglutamic Acid as a Multifunctional Binder for High-Performance SiOx Anode in Lithium-Ion Batteries.

SiOx is a highly promising anode material for realizing high-capacity lithium-ion batteries owing to its high theoretical capacity. However, the large volume change during cycling limits its practical application. The development of a binder has been demonstrated as one of the most economical and efficient strategies for enhancing the SiOx anode's electrochemical performance. In this work, a multifunctional binder (T-PGA) is fabricated by cross-linking γ-polyglutamic acid (PGA) and tannic acid (TA) for SiOx anodes. The introduction of TA into PGA helps to buffer the volume changes of the SiOx anodes, facilitate diffusion of Li+, and construct stable SEI layers. Benefiting from this proposed binder, the SiOx anode maintains a reversible capacity of 973.0 mAh g-1 after 500 cycles at 500 mA g-1 and the full cell, pairing with LiNi0.5Co0.2Mn0.3O2 cathode, delivers a reversible capacity of 133 mA h g-1 (73.2% retention) after 100 cycles. This study offers valuable insights into advanced binders that are used in high-performance Li-ion batteries.

SiO2/C double-layer-coated SiO as a high-performance anode for lithium-ion batteries

Silicon monoxide (SiO) has a high theoretical capacity as an anode for lithium-ion batteries, but its poor conductivity and bulk effect can cause the capacity to plummet. The combination of SiO and other materials to form a core–shell mechanism on the surface of SiO can effectively alleviate these problems. In this work, a silicon dioxide (SiO2)/carbon (C) bilayer core–shell structure coated on SiO anode material was designed and synthesized to address the issues inherent in core–shell structures. When the temperature was 900 °C, SiO@SiO2@C exhibited an excellent reversible capacity of 2500.08 mAh·g−1 and a first coulombic efficiency of 75.92 %. After 100 charge/discharge cycles, it still retained 1298.25 mAh·g−1 of its capacity. Compared with those of pure SiO, its cycling stability and capacity retention are significantly improved, providing a new approach for anode materials in lithium-ion batteries.

A Novel Gelatin Binder with Helical Crosslinked Network for High-Performance Si Anodes in Lithium-Ion Batteries.

Silicon(Si) is a promising anode material for lithium-ion batteries, but its large volume expansion during cycling poses a challenge for the binder design. In this study, a novel gelatin binder is designed and prepared with a helical crosslinked network structure. This gelatin binder is prepared by enzymatic crosslinking and immersion in Hofmeister salt solution, which induces the formation of network and helical secondary structures. The helical crosslinked network structure can be analogous to a spring group system to effectively dissipate the stress and strain caused by the Si expansion. The gelatin binder is further partially carbonized by low-temperature pyrolysis, which improves its conductivity and stability. The Sianode with the optimized gelatin binder exhibits high initial coulombic efficiency, excellent rate performance, and long-term cycling stability. This study provides an innovative approach for the preparation of high-performance Si anodes, namely by controlling the molecular configuration of the binder to significantly improve the cycle stability, which can also be applied to other high-capacity anode materials that suffer from large volume changes during cycling.

Rational Synthesis of Spongy Fe3N@N-Doped Carbon Nanorods with Controlled Topography and Porosity for Enhanced Energy Storage Anodes in Lithium-Ion Batteries.

Iron nitrides with the merits of high theoretical capacities, cost-effectiveness, and good electronic/ionic conductivity have been recognized as attractive anode candidates for lithium-ion batteries (LIBs). Carbon compositing, pore engineering, and nanostructure construction have proved to be effective strategies to prepare high-performance metal nitride anodes for LIBs. Herein, we synthesized a series of Fe3N-embedded and N-doped carbon nanorods (Fe3N@NCNR) with a hierarchical porous system and controllable topography by metal-catalyzed graphitization-nitridization of the Fe(III)-triazole framework (Fe-MOF) and thermal evaporation of the triblock copolymer F127 template assembled in Fe-MOF via hydrogen bonding interaction, followed by the air oxidation and urea-assisted ammonolysis processes. The Fe3N@NCNR as anodes for LIBs display extraordinary lithium storage capabilities with a high reversible capacity of 830 mA h g-1 at 0.1 C, a good rate performance of 576 mAh g-1 at 5 C, and a long-term cycling stability of 742 mA h g-1 over 600 cycles at 1 C. Such outstanding performance benefits from the spongy carbon nanorods with rich macropores for rapid electronic/ionic transport and effective accommodation of electrode volume expansion, abundant N-doped meso-/microporous carbon for the additional storage of Li+ via capacitive effect, and the efficient utilization of Fe3N nanoparticles uniformly distributed through carbon nanorods. Importantly, this work introduces an effective strategy to construct superior performance nitride anodes from MOF surfactants based on hydrogen bonding-driven interface self-assembly and provides insight into the preparation of highly efficient nanoarchitectures for Li+ storage.

Incorporation of SnSe2/SnO2 heterostructures in carbon nanotubes for excellent lithium storage performance

As a new type of negative electrode material, tin-based material exhibits a high theoretical capacity. However, tin-based anode materials always undergo severe volume change upon alloying reaction during lithium insertion and extraction, which leads to the pulverization of the active materials and poor electrochemical performance, seriously hampering its practical application. In this work, oxygen-containing group functionalized carbon nanotubes (FCNTs) were facilely obtained, and the three-dimensional crosslinked SnSe2-SnO2@FCNTs multiphase materials were prepared by solvothermal and high-temperature heat treatment. The formation of Sn-O-C bonds from oxygen-containing functional groups of FCNTs combined with Sn can promote the electric connection and integrity of the composites. The implanted defects in FCNTs can not only be beneficial to anchoring SnO2 and SnSe2 nanoparticles, but also helpful to the penetration of Li+ ions into the electrodes from electrolyte. In addition, the large Fermi energy difference between SnSe2 and SnO2 nanoparticles results in the formation of a built-in electric field at the interface of the multiphase materials, accelerating the diffusion of ions. The smaller size of the multiphase materials leads to significant pseudocapacitive behavior, which facilitates the highly reversible surface/interface adsorption. Under the multiple effects of FCNTs, SnSe2, and SnO2, the SnSe2-SnO2@FCNTs multiphase materials exhibited excellent electrochemical performance. At a current density of 0.1 A·g−1, a discharge specific capacity of 898.0 mA h·g−1 was achieved. When the current density was increased to 2 A·g−1, it still exhibited a discharge specific capacity of 443.9 mA h·g−1. After a long charge/discharge cycling at 1 A·g−1 over 450 cycles, it still showed a specific capacity of ∼ 400 mA h·g−1. This work significantly demonstrated the enhanced Li-storage performance of SnSe2-SnO2 heterostructures incorporated in the functionalized multi-walled CNTs. This opens a new way to synthesize advanced tin-based materials as high-performance anodes for high-energy density lithium-ion batteries.

Effect of Various Carbon Coating Techniques on the Electrochemical Performance of Li4Ti5O12 Synthesized by Sol-Gel Method

This study aimed to prepare spinel carbon-coated Li4Ti5O12 (LTO/C) via sol-gel reaction and applied as a high-performance lithium-ion battery anode. The LTO powder was coated using various carbon sources, super P (SP), sugar and PVDF-assisted SP. The crystal structure, morphology, conductivity and electrochemical performance of the samples were examined using X-ray diffraction (XRD), Field Emission scanning electron microscopy (FESEM), Fourier Transform Infrared (FTIR) spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry/Charge-discharge (CV/CD), respectively. The XRD analysis results showed that the samples contain highly crystalline spinel LTO as the main phase and rutile as impurity. The FESEM image showed that SP covers the entire LTO surface more homogenous than sugar. However, sugar carbon makes roughness on the LTO surface. FTIR spectra showed that the coating using sugar and PVDF still contain hydrocarbon element. Electrochemical performance evaluations showed that SP carbon-coated-LTO possesses higher lithium diffusion and specific capacity than pure LTO, while sugar-coated-LTO shows the lowest specific capacity. Moreover, the SP carbon-coated-LTO sample high-rate capability has improved during full cell evaluation, delivering a discharge capacity of 249, 231, 211, 194, 58, and 23 mAhg-1 at the charge or discharge current density of 0.05, 0.1, 0.5, 1, 5, and 10 C, respectively.

Utilizing copper waste to develop silicon-carbon anode materi als for lithium-ion batteries

This study dedicated to a novel method for synthesizing silicon-carbon (Si/C) and silicon dioxide-carbon (SiO2/C) nanocomposite anodes for lithium-ion batteries, utilizing industrial copper slags from the Almalyk Mining and Metallurgical Complex as a cost-effective source of SiO2. The synthesized nanocomposites address key challenges in lithium-ion battery anodes, including the volumetric expansion of silicon and its low conductivity, by leveraging the high lithiation capacity of silicon combined with the structural stability and conductivity of carbon. Amorphous SiO3 was extracted from copper slags via ammonium fluoride (NH4F) treatment and subsequently reduced to metallurgical-grade silicon through carbothermal reduction. The resulting SiO2/C and Si/C composites were thoroughly characterized using SEM, XRD, and electrochemical analyses, demonstrating improved electrochemical performance, favorable particle size distribution, and stability. This approach not only reduces material costs but also promotes environmental sustainability by repurposing industrial waste, offering promising candidates for high-performance lithium-ion battery anodes.

Preparation of core-shell Si/C/graphene composite for high-performance lithium-ion battery anodes

One of the important objectives for the development of enhanced lithium-ion batteries is developing high-performance silicon-based anodes with durable operational capability. Herein, a three-dimensional graphene-decorated core-shell Si/C composite is fabricated by the in-situ polymerization of organic pyrrole molecule and pyrolysis process, in which the melamine formaldehyde resin is subtly used as three-dimensional porous framework to offer abundant loading area for the uniform dispersion of active silicon nanoparticles. Meanwhile, the core-shell structure deriving from polypyrrole in the composite can effectively buffer the volume change of silicon ingredient and avoid the direct contact with the electrolyte during the cycling process, leading to the improved structural stability and electrochemical performance. The outermost layer of graphene nanosheets is designed to enhance the electrical conductivity of the electrode. As a result, the synthesized Si/C/graphene composite exhibits a high capacity and excellent cycling performance. This work reveals that combining a three-dimensional carbon substrate with a core-shell structure might be a promising solution for anode materials with obvious volume transformation.

High-entropy chemistry enhanced pyrochlore (Y0.2La0.2Ce0.2Nd0.2Ca0.2)2Sn2O7 for high-performance lithium-ion battery anode

High-entropy chemistry enhanced pyrochlore (Y0.2La0.2Ce0.2Nd0.2Ca0.2)2Sn2O7 for high-performance lithium-ion battery anode

Carbon matrix NiFeP/C nanoparticles anchored on Ti3C2Tx nanosheets as heterostructure high-performance anode for lithium-ion batteries

Engineered micro-nano heterogeneous architectures for transition metal phosphide (TMPs) anode materials in lithium-ion batteries (LIBs) provide multifunctional active components. These components synergistically interact to address pivotal challenges of pronounced volume expansion and sluggish reaction kinetics within the electrode. Consequently, this engineering design approach significantly enhances the overall battery performance. In this study, a self-assembled approach is employed to integrate hybridized NiFe-PBA nanocubes with two-dimensional (2D) monolayer MXene (Ti3C2Tx), producing a heterostructured NiFeP/C@Ti3C2Tx composite. In this meticulously engineered architecture, the interface between the outer MXene layer and NiFeP embedded within the carbon matrix exhibits several distinct superiorities, such as rapid interfacial ion migration, multidirectional migration pathways, and strong spatial adaptability. The resulting non-uniform phase structure effectively mitigates electrode expansion and enhances electronic conductivity. Consequently, the NiFeP/C@Ti3C2Tx-15 composite demonstrates distinct performance advantages over NiFeP/C without MXene. The composite achieves a specific capacity of 689.4 mAh g⁻¹ at 200 mA g⁻¹ over 300 cycles, double that of NiFeP/C. Furthermore, density functional theory (DFT) calculations validate the electronic conductivity facilitated by the heterointerface between MXene and NiFeP, substantiating the strategic significance of the heterostructure in advancing high-performance anode materials for lithium-ion batteries.

Dramatic Enhancement Enabled by Introducing TiN into Bread-like Porous Si-Carbon Anodes for High-Performance and Safe Lithium Storage.

Doping modifications and surface coatings are effective methods to slow volume dilatation and boost the conductivity in silicon (Si) anodes for lithium-ion batteries (LIBs). Herein, using low-cost ferrosilicon from industrial production as the energy storage material, a bread-like nitrogen-doped carbon shell-coated porous Si embedded with the titanium nitride (TiN) nanoparticle composite (PSi/TiN@NC) was synthesized by simple ball milling, etching, and self-assembly growth processes. Remarkably, the porous Si structure formed by etching the FeSi2 phase in ferrosilicon alloys can provide buffer space for significant volume expansion during lithiation. Highly conductive and stable TiN particles can act as stress absorption sites for Si and improve the electronic conductivity of the material. Furthermore, the nitrogen-doped porous carbon shell further helps to sustain the structural stability of the electrode material and boost the migration rate of Li-ions. Benefiting from its unique synergistic effect of components, the PSi/TiN@NC anode exhibits a reversible discharge capacity up to 1324.2 mAh g-1 with a capacity retention rate of 91.5% after 100 cycles at 0.5 A g-1 (vs fourth discharge). Simultaneously, the electrode also delivers good rate performance and a stable discharge capacity of 923.6 mAh g-1 over 300 cycles. This research can offer a potential economic strategy for the development of high-performance and inexpensive Si-based anodes for LIBs.

Porous silicon/carbon composites as anodes for high-performance lithium-ion batteries

Silicon anodes are promising for use in lithium-ion batteries. However, their practical application is severely limited by their large volume expansion leading to irreversible material fracture and electrical disconnects. This study proposes a new top-down strategy for preparing microsize porous silicon and introduces polyacrylonitrile (PAN) for a nitrogen-doped carbon coating, which is designed to maintain the internal pore volume and lower the expansion of the anode during lithiation and delithiation. We then explore the effect of temperature on the evolution of the structure of PAN and the electrochemical behavior of the composite electrode. After treatment at 400 -, the PAN coating retains a high nitrogen content of 11.35%, confirming the presence of C―N and C―O bonds that improve the ionic-electronic transport properties. This treatment not only results in a more intact carbon layer structure, but also introduces carbon defects, and produces a material that has remarkable stable cycling even at high rates. When cycled at 4 A g−1, the anode had a specific capacity of 857.6 mAh g−1 even after 200 cycles, demonstrating great potential for high-capacity energy storage applications.

Oxygen Self-Doping Bi2S3@C Spheric Successfully Enhanced Long-Term Performance in Lithium-Ion Batteries.

High theoretical capacity of Bi2S3 propels it toward an ideal anode material for lithium-ion batteries (LIBs); however, rapid capacity attenuation and poor long-term stability are major barriers to widespread application. In this work, an oxygen self-doping strategy was utilized to synthesize O-Bi2S3@C, significantly increasing the amount of active sites for lithium-ion storage. Meanwhile, sulfur vacancies were formed to improve the electrical conductivity and ionic transport efficiency, enhance the long-term stability, and accelerate the electrochemical kinetics of Bi2S3@C. O-BSC-S1:3 anode exhibits a reversible capacity of 673.1 mAh g-1 at 0.2 A g-1. It retains a long-term capacity of 596.3 mAh g-1 over 1100 cycles at a high density of 3 A g-1 in LIBs. Moreover, the installed O-Bi2S3@C//LiCoO2 full battery offers exceptional reversible capacity and remarkable cyclability (325.2 mAh g-1 after 200 cycles) at 0.2 A g-1. The combined strategy of oxygen self-doping and sulfur vacancy effectively enhances the reversible capacity and cycling life of Bi2S3, providing an approach for the design of high-performance transition metal sulfide anodes for LIBs.

CoO nanocrystals dispersed in N-doped carbon networks as enhanced anode for lithium storage

CoO emerges as a promising anode material for lithium-ion batteries (LIBs) because of high theoretical specific capacity and rich resource. However, its practical application is impeded by significant volume expansion and poor electrical conductivity during the charging and discharging cycles. Herein, we construct a nanocomposite of CoO nanocrystals and N-doped carbon serving as an enhanced anode for LIBs by a facile strategy. In the nanocomposite, CoO nanocrystals with average size of 60 nm uniformly were dispersed in N-doped carbon networks. The synergy effects of CoO nanocrystals and N-doped carbon networks can extremely enhance electronic conductivity, relieve volume expansion, and effectively protect CoO nanocrystals from aggregating. Hence, the composite anode delivers large reversible capacity (1190 mAh g−1 at 0.3 A g−1 after 100 cycles), remarkable rate capability (592 mAh g−1 at 5 A g−1), and long cycling ability. This offers a simple approach for designing high-performance anodes for LIBs.

Co(OH)2 derived from in-situ conversion of metal Co confined within a spongy porous carbon for high-performance lithium-ion battery anode

Fabricating Co(OH)2/C composites is considered as an efficient solution to poor conductivity and significant volume expansion issues of Co(OH)2 anode during cycle, but the easy conversion of Co(OH)2 into cobalt oxides during thermal treatment process limits structural design of materials and selection of carbon precursors, hence constricting the diversified design and structural optimization of the Co(OH)2/C composites. Herein, a distinctive method is demonstrated to embed Co(OH)2 nanoparticles (NPs) into a porous carbon (PC), which involves in-situ conversion of the metallic Co NPs confined within a spongy PC into Co(OH)2 NPs by simple H2O2 treatment under hydrothermal conditions. The as-prepared composite is referred as Co(OH)2@PC. This method avoids the conversion of Co(OH)2 into cobalt oxides during preparation of Co(OH)2/C. Moreover, the findings verify that the rational combination of porous carbon and nanoscale Co(OH)2 NPs endows Co(OH)2@PC with enhanced conductivity, improved Li+ diffusion coefficient, high capacitive contribution, stable structure and a LiF-rich SEI layer during cycle. As a result, the Co(OH)2@PC exhibits outstanding electrochemical performance, displaying 815.8 and 543.4 mAh g−1 after 120 cycles at 0.2 and 1.0 A g−1, respectively. This work may broaden the way for diversified design and structural optimization of Co(OH)2/C anodes of lithium-ion batteries.

Magnesiothermic reduction SiO coated with vertical carbon layer as high-performance anode for lithium-ion batteries

Silicon monoxide (SiO), as one of the most competitive anode materials for lithium-ion batteries (LIBs), has received considerable attention. Nevertheless, poor initial Coulombic efficiency (ICE) and larger volume change are the main obstacles to the application of SiO. Here, we suggest a controllable route for the modification of micro-sized SiO via magnesiothermic reduction. To prevent the excessive growth of Si grains caused by the overheating reaction, the solid-state thermal reaction between Mg and SiO is achieved by mixing a certain proportion of NaCl at a suitable temperature, resulting in a loose surface and porous structure of SiO particles, which is conducive to the transportation of lithium ions and electrons. Combined with chemical vapor deposition (CVD), the carbon-coated SiOx composites (M-SiOx@C-R, where R is the molar ratio for Mg and SiO) exhibit unique morphology structure and remarkable electrochemical characteristics. As expected, the vertical carbon network improves the conductivity and alleviates the volume expansion of SiOx. Notably, the M-SiOx@C-0.75 electrode offers a large initial specific capacity of 2283.17 mAh g−1 with a higher ICE of 86.03 % at 100 mA g−1. Furthermore, the full cells using M-SiOx@C-0.75 composite as the negative electrode and LiNi0.8Co0.1Mn0.1O2 (NCM811) as the positive electrode were assembled. After 150 cycles, the full cell still delivers a high specific capacity of 72.22 mAh g−1 (with a retention rate of 47 %). This work provides a feasible route for the fabrication of applicable SiO-based anode materials.

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.

Consecutive covalent bonds reconstruct robust dual-interfaces by carbonized binder to enable conductive-additive-free durable silicon anode

The substantial volume expansion and poor electrical conductivity tremendously hinder the utilization of high silicon (Si) content anode with compelling capacity. Herein, we propose an efficient strategy to stabilize Si-based anodes by carbonization of the slurry-casting Si electrode with a conductive polyoxadiazole (POD) binder. Such POD-derived materials can form a nitrogen/sulfur-rich carbon network, not only serving as a resilient scaffold to buffer the volume swelling and firmly adhere the Si to the current collector by robust dual-interfaces bonding but also evolving into a conductive matrix to facilitate the electron/ion transport. The conductive-additive-free Si electrode possesses a high Si content of up to 84 %. It exhibits a high initial Coulombic efficiency (86.34 %), competitive gravimetric capacity (3340 mAh g−1), stable cycling performance (the capacity retention rate reaches 79 % after 1000 cycles), commercial-level areal capacity (5.32 mAh cm−2), and outstanding rate capability (1673 mAh g−1 at 5.0 A g−1). This work offers a scalable modification idea and forward-looking perspective for high-performance Si-based anodes in next-generation lithium-ion batteries.