Advanced Lithium-ion Battery Anode Research Articles

All biomass-derived autogenous nitrogen-doped porous carbon with pseudo-graphitic structure for advanced lithium-ion battery anodes

The trade-off between pseudo-graphitic and porosity of hard carbon is very significant for improving the lithium storage, yet challenging. Herein, a series of N-doped pseudo-graphitized porous carbon (NPCn, n = 11, 13 and 15) are prepared by calcining chlorella and oyster shell powder. When the mass ratio of the above is 1:3 (NPC13), a sharp band at 26.0° (002) in XRD was observed, meaning that partial sp3-carbon were transformed into short-range ordered pseudo-graphitic carbons, where the formation process of NPC13 is explored by operando pyrolysis analysis. As a result, NPC13 as lithium-ion battery (LIBs) anode exhibits the best electrochemical performances with a high initial Coulombic efficiency (ICE) of 77 %, an exceptional specific capacity of 1384.9 mA h g−1 at 0.1 A g−1 after 150 cycles, and an outstanding cycle life with 737.6 mA h g−1 at 1.0 A g−1 after 1000 cycles, attributed to rich porosity, abundant N-doping (8.83 at%), and excellent electrical conductivity provided by the pseudo-graphite structure. Furthermore, the Li+ storage mechanisms and migration kinetics of NPC 13 are further analyzed. This innovative strategy paves the way for new avenues in the preparation and application of NPC anodes.

Polythiophene side chain chemistry and its impact on advanced composite anodes for lithium-ion batteries.

In the development of high-performance lithium-ion batteries (LIBs), the design of polymer binders, particularly through manipulation of side-chain chemistry, plays a pivotal role in optimizing electrode stability, ion transport, and adaptability to the volume changes during cycling. In particular, poly[3-(potassium-4-butanoate)thiophene-2,5-diyl] (P3KBT) increases magnetite and silicon capacity and cycling stability. This work explores the impact of polythiophene alkyl sidechain length on anode characteristics, aiming to enhance performance in LIBs. P3KBT and its alkyl chain alternatives, poly[3-(potassium-5-pentanoate)thiophene-2,5-diyl] (P3KPT) and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT) were systematically investigated over 300 charge-discharge cycles. The experiments were designed to assess how varying side-chain length affects the stability, ion transport, and capacity retention of the electrodes. The results revealed that P3KHT, with its longer alkyl chain, exhibited superior capacity retention and reduced charge-transfer resistance after 300 cycles compared to its shorter chain analogs. The findings demonstrate that tailored side chains can improve ion transport, structural integrity, and capacity retention, addressing critical challenges in LIBs such as capacity fade and electrode degradation. This research contributes to the development of next-generation LIBs with enhanced performance and reliability.

Bi2O3/Bi quasi-nanospheres in-situ embedded in N-doped porous carbon and reinforced via Bi-O-C bonding towards improved lithium storage performance

To mitigate the volume swelling and poor conductivity issues faced by Bi2O3 during Li storage, this work prepares an efficient Bi2O3-based composite through a simple freeze-drying and subsequent carbonization method, which improves the electrochemical performance of Bi2O3. The findings confirm that in this composite (Bi2O3/Bi@PC) the Bi2O3 (containing small amounts of Bi) quasi-nanospheres are embedded within an N-doped porous carbon matrix (PC) and formation of Bi-O-C chemical bonding between Bi2O3/Bi and carbon matrix. The electrochemical characterization results demonstrate that PC physical embedding and Bi-O-C chemical bonding dual combination endows Bi2O3/Bi@PC with enhanced conductivity, improved Li+ diffusion coefficient and reinforced structural stability during cycle. As a result, Bi2O3/Bi@PC exhibits outstanding electrochemical performance, with 451.4 and 309.3 mAh g-1 after 400 and 600 cycles at 200 and 1000mAg-1, respectively. This study may provide essential guidance for future preparing advanced Bi-based anodes for lithium-ion batteries through a simple and efficient strategy.

Artificial Graphite-Based Silicon Composite Anodes for Lithium-Ion Batteries.

To develop an advanced anode for lithium-ion batteries, the electrochemical performance of a novel material comprising a porous artificial carbon (PAC)-Si composite was investigated. To increase the pore size and surface area of the composite, ammonium bicarbonate (ABC) was introduced during high-energy ball-milling, ensuring a uniform distribution of silicon within the PAC matrix. The physical and structural properties of the developed material were evaluated using several advanced techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), and galvanostatic intermittent titration (GITT). Artificial graphite contains several macropores that can accommodate volume hysteresis and provide effective sites for anchoring Si nanoparticles, enabling efficient electrochemical reactions. GITT analysis revealed that the PAC-Si-CB-ABC composite exhibited superior lithium-ion diffusion compared to conventional graphite. The developed PAC(55%)-Si(45%)-CB-ABC electrode with PAA as the binder demonstrated a reversible capacity of 850 mAh g-1 at 100 mA g-1 and a high-rate capability of 600 mAh g-1 at 2000 mA g-1. A full cell employing the NCM622 cathode exhibited reversible cyclability of 128.9 mAh g-1 with a reasonable energy density of 323.3 Wh kg-1. These findings suggest that the developed composite is a useful anode system for advanced lithium-ion batteries.

Pillared Graphene Nanostructures for Electrochemical Energy Storage

The global electrochemical energy storage market ranging from electric vehicles and personal electronics to physical grid storage and defense applications demands the development of new classes of materials for fabricating high performance batteries and supercapacitors. I will begin by describing innovative approaches for the design and synthesis of nanostructured carbon materials towards enhanced reversible capacity; superior rate performance and cycling stability; and superior gravimetric capacitance. A novel 3D architecture called a pillared graphene nanostructure (PGN) is a combination of two allotropes of carbon, including graphene and carbon nanotubes possessing ultra large surface area, tunability, mechanical durability and high conductivity can be grown on a variety of substrates, which are appealing to diverse energy storage systems. Another type of 3D superporous carbonaceous architecture called chrysanthemum nanofibers can be grown in roll-to-roll form on commercial nickel foams. Integration of nanostructured pseudocapacitive metal oxides to such 3D templates can provide superior electrochemical performance in supercapacitor applications. PGN templates can also be transformed into cone-shaped clusters decorated with amorphous silicon for advanced lithium ion (Li-ion) battery anodes. Single and multilayer stacked 3D carbonaceous architectures could also be envisioned for further future applications in hydrogen storage. I will also describe recent advancements in upcycling polyethylene terephthalate (PET) waste into active nano-carbon electrode materials for energy storage. For PET plastic-waste, materials are dissolved in a mixture of trifluoroacetic acid and dichloromethane, followed by carbonization under an argon/hydrogen atmosphere. Electrodes derived from PET are employed in supercapacitors and Li-ion battery anodes. Our studies pave the way for scaled up manufacturing of energy storage devices with enhanced energy density and power density.

Pre-lithiation synergized with magnesiothermic reduction to enhance the performance of SiO anode for advanced lithium-ion batteries

Due to its high theoretical specific capacity, micron-sized silicon monoxide (SiO) is regarded as one of the most competitive anode materials for lithium-ion batteries with high specific energy density. However, originating from the low initial Coulombic efficiency (ICE) and large volume expansion, its large-scale application is seriously hindered. Herein, an easy-to-implement solid-state pre-lithiation method synergized with the magnesiothermic reduction process was performed to enhance the ICE of SiO and a common bimetallic hydride was used as a prelithiation reagent. Moreover, the effects of different pre-lithiation reagent amounts on the physical and electrochemical properties of SiOx are investigated. Notably, the SiOx-LA@C composite anchored by in-situ generated LiAl(SiO3)2 shows a more stable microstructure and excellent electrochemical properties, which delivers an ultrahigh ICE of 89.4 % and an excellent initial capacity of 1864.4 mAh g−1. Furthermore, the full cells were successfully assembled by using the prepared anodes, which exhibit relatively stable cycle performance over 150 cycles. This work suggests a safe and feasible route to enhance the ICE of SiOx for the applicable SiO-based anode materials.

Roles of MXene-Based Hybrids in Fabricating Flexible Anodes for Advanced Lithium-Ion Batteries: A Mini Review

Roles of MXene-Based Hybrids in Fabricating Flexible Anodes for Advanced Lithium-Ion Batteries: A Mini Review

Construction of ternary Sn/SnO2/nitrogen-doped carbon superstructures as anodes for advanced lithium-ion batteries

Construction of ternary Sn/SnO2/nitrogen-doped carbon superstructures as anodes for advanced lithium-ion batteries

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).