Anode For Li-ion Batteries Research Articles

Rapid ultrasound driven self-assembled nanoarchitectonics iron oxide-reduced graphene oxide as an anode for Li-ion battery and its electrochemical performance studies

With the scope of identifying an effective nanomaterial as an anode for Li-ion battery under economic synthesis factors, here, high crystalline mesoporous magnetite nanoparticles (m-Fe3O4 NPs) with an average diameter of 45 ± 10 nm were successfully synthesized through facile, one-pot sonoelectrochemical method in 15 min, and it was structurally anchored into sonochemically exfoliated reduced graphene oxide nanosheets (m-Fe3O4@rGO). The morphological studies through FESEM and HRTEM analysis confirm that the m-Fe3O4 were well anchored into rGO nanosheets, and it has maximum magnetic saturation value of 39 emu g−1 and high surface area of 254 m2 g−1. The performance analysis results of m-Fe3O4@rGO nanocomposite as an anode material in half-cell configuration with Li-metal had demonstrated that around 11 % enhancement in first discharge capacity (1440.79 mAh g−1 at 0.2 A g−1 current density), ~50 % increased rate capability (356 mAh g−1 at 5.0 A g−1 current density) than bare m-Fe3O4 electrode and had maintained nearly 441 mAh g−1 after 500 cycles at 2.0 A g−1 current density. These results suggest that the sonochemical method could be a better alternate method when compared to other time-consuming processes like solvothermal method where high temperature is required to fabricate effective nanocomposite for high-rate performance in real time applications of Li-ion battery.

Optimization of Pore Characteristics of Graphite-Based Anode for Li-Ion Batteries by Control of the Particle Size Distribution

We investigate the reassembly techniques for utilizing fine graphite particles, smaller than 5 µm, as high-efficiency, high-rate anode materials for lithium-ion batteries. Fine graphite particles of two sizes (0.4–1.2 µm and 5 µm) are utilized, and the mixing ratio of the two particles is varied to control the porosity of the assembled graphite. The packing characteristics of the assembled graphite change based on the mixing ratio of the two types of fine graphite particles, forming assembled graphite with varying porosities. The open porosity of the manufactured assembled graphite samples ranges from 0.94% to 3.55%, while the closed porosity ranges from 21.41% to 26.51%. All the assembled graphite shows improved electrochemical characteristics properties compared with anodes composed solely of fine graphite particles without granulation. The sample assembled by mixing 1.2 µm and 5 µm graphite at a 60:40 ratio exhibits the lowest total porosity (27.45%). Moreover, it exhibits a 92.3% initial Coulombic efficiency (a 4.7% improvement over fine graphite particles) and a capacity of 163.4 mAh/g at a 5C-rate (a 1.9-fold improvement over fine graphite particles).

Metal oxide- and metal-loaded mesoporous carbon for practical high-performance Li-ion battery anodes

The rapidly expanding Li-ion battery market needs new materials that can satisfy the increasing energy storage demand. Metal oxides and some metals such as tin are viable alternatives to graphite as Li-ion battery anodes, but their low conductivity and large volume change during cycling impose severe challenges that need to be overcome. Confinement of metal oxide and metal nanomaterials within mesoporous carbon (MC) is an effective strategy in this regard, but complex synthesis and nanoparticle aggregation have hindered its application. Herein, we report a facile, scalable and generalized methodology for the room-temperature synthesis of metal oxide and metal nanoparticles within a MC host. The approach has been successfully applied to achieve uniform distribution and prevent aggregation of a large variety of metal oxide and metal nanomaterials in MC support. These nanocomposites were screened as Li-ion battery anodes, and the optimal candidates were shown to be superior to previously reported systems. Our synthesis method was scaled up using commercial MC. The nanocomposites were validated in a high-loading electrode (4 mg/cm2) with a practical voltage range (< 2 V vs. Li+/Li), showing impressive initial Coulombic efficiency (> 100%), and excellent stability (∼ 500 mAh/g after 250 cycles at 0.2 A/g), which was 1.5–2x better than commercial graphite at the same testing conditions. The facile nature, universality and versatility of our approach make it possible to load various metal oxide and metal nanomaterials within different types of MC. These nanocomposites would be of significant interest to different fields, such as energy storage and conversion, sensing, and catalysis.

Graphene nanonetwork embedded with polyaniline nanoparticles as anode of Li-ion battery

A simple and solvent-free approach is proposed to prepare graphene nanonetwork-polyaniline (PANI) nanocomposite with enhanced electrical conductivity and Li-ion storage performance. To this end, acidic graphene oxide (AGO) and PANI are ball-milled followed by low-temperature chemical expansion leading to the formation of chemically expanded graphene (CEG) in the form of mesoporous nanonetworks with the lattice layer spacing of 0.362 nm embedded with PANI nanoparticles. CEG-PANI nanocomposite outperforms CEG, exhibiting a specific reversible capacity of 664 mAh·g−1 at 200 mA·g−1 after 150 cycles, and the discharge capacity of 253 mAh·g−1 after 350 cycles at 2000 mA·g−1. The enhanced electrochemical performance of CEG-PANI can be attributed to its large specific surface area, mesoporous structure and conductive homogeneous graphene nanonetwork doped with of N heteroatoms embedded with polyaniline, providing sufficient active sites for facile Li-ion storage. Nanostructured CEG-PANI is a promising candidate for anode of Li-ion batteries.

Prospective utilization of boron nitride and beryllium oxide nanotubes for Na, Li, and K-ion batteries: a DFT-based analysis.

In the present work, we investigated the adsorption mechanism of natural sodium (Na), potassium (K), and lithium (Li) atoms and their respective ion on two nanostructures: boron-nitride nanotubes (BNNTs) and beryllium-oxide nanotubes (BeONTs). The main goal of this research is to calculate the gain voltage for Na, K, and Li ionic batteries. Density function theory (DFT) calculations indicated that the adsorption energy between Na + is higher than that of the other cations, and this is particularly clear in the BeONT. Furthermore, gain voltage calculations showed that BNNTs generate a higher potential than BeONTs, with the most significant difference observed in BNNT/Na + . This research provides theoretical insights into the potential uses of these nanostructures as anodes in Na, K, and Li-ion batteries. Density function theory used to compute the ground state properties for BeONT and BNNT with and without selected atoms and their ions (Li, K, and Na). B3LYP used for exchange correlation between electrons and ions, and 6-31G* basis set used for all atoms and ions. Gauss Sum 2.2 software used for estimate the density of state (DOS) for all structure under investigation.

Cationic surfactant assisted electrostatic self-assembly of nitrogen-rich carbon enwrapped silicon anode: Unlocking high lithium storage performance

Nitrogen-rich carbon (N-rich-C) coating is attractive to enhance capacity, reduce resistance, and alleviate volume expansion of silicon anode in Li-ion batteries. However, the non-uniform coating of N-rich-C on silicon might restrict its optimum performance. In this study, poly(diallyldimethylammonium chloride) (PDDA) is employed as a cationic surfactant to tailor the surface potential of bare ball-milled Si particles, enabling the electrostatic self-assembly between Si particles and graphitic carbon nitride as the N-rich-C precursor. Continuous N-rich-C enwrapped ball-milled silicon (Si@N-rich-C) has been obtained after pyrolysis with a high N to C ratio of 0.65 and abundant pyridinic-N and pyrrolic-N, facilitating fast kinetic transport and accommodating more Li+ ion storage. Combined with the high capacity of Si, Li-ion cell with Si@N-rich-C electrode exhibits a high capacity of 1732 mAh g−1 after 200 cycles of charge-discharge at 400 mA g−1. At high-rate testing, Si@N-rich-C also maintains a high capacity of 1673 mAh g−1 at 1000 mA g−1. This study provides an effective approach for synthesizing high-capacity silicon anode for Li-ion batteries.

SnO2 nanotubes with N-doped carbon coating for advanced Li-ion battery anodes

SnO2 nanotubes with N-doped carbon coating for advanced Li-ion battery anodes

Superb Li-Ion Storage of Sn-Based Anode Assisted by Conductive Hybrid Buffering Matrix.

Although Sn has been intensively studied as one of the most promising anode materials to replace commercialized graphite, its cycling and rate performances are still unsatisfactory owing to the insufficient control of its large volume change during cycling and poor electrochemical kinetics. Herein, we propose a Sn-TiO2-C ternary composite as a promising anode material to overcome these limitations. The hybrid TiO2-C matrix synthesized via two-step high-energy ball milling effectively regulated the irreversible lithiation/delithiation of the active Sn electrode and facilitated Li-ion diffusion. At the appropriate C concentration, Sn-TiO2-C exhibited significantly enhanced cycling performance and rate capability compared with its counterparts (Sn-TiO2 and Sn-C). Sn-TiO2-C delivers good reversible specific capacities (669 mAh g-1 after 100 cycles at 200 mA g-1 and 651 mAh g-1 after 500 cycles at 500 mA g-1) and rate performance (446 mAh g-1 at 3000 mA g-1). The superiority of Sn-TiO2-C over Sn-TiO2 and Sn-C was corroborated with electrochemical impedance spectroscopy, which revealed faster Li-ion diffusion kinetics in the presence of the hybrid TiO2-C matrix than in the presence of TiO2 or C alone. Therefore, Sn-TiO2-C is a potential anode for next-generation Li-ion batteries.

Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste

A novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre‑carbonized PW with factors of temperature (1100–1300 °C), hold time (1–5 h), and iron catalyst loading (0.5–1.5× fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340–355 mAh g−1 with 99 % capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre‑carbonized biographites, however, are 77 % and 75 %, respectively, suggesting parasitic reactions including electrolyte decomposition.

Candle soot-metal-organic framework-based hierarchical electrode as high-performance anode for Li-ion batteries

Recently, cobalt oxide-based materials have been considered high-performance anode materials. However, cobalt oxide materials display drawbacks such as capacity fade, poor cycle life, and substantial structural strain. In this work, we report a facile synthesis of carbon-cobalt oxide composite to improve the electrode's storage capabilities and cycle life. First, metal–organic framework-based cobalt oxide nano leaves are synthesized by simple coprecipitation followed by calcination. After that, candle soot-derived carbon nanoparticles are uniformly deposited on the cobalt oxide nano leaves by a simple flame synthesis method to form a composite electrode. The fractal-like interconnected carbon nanoparticles improve the electron conducting pathways. In contrast, metal–organic framework-derived porous cobalt oxide nano leaves enhance energy storage abilities through reversible conversion reactions. The superior performance of the composite electrode is established from the galvanostatic charge–discharge experiments. Also, the composite electrode has delivered outstanding specific capacities of 811 and 503 mAh g−1 at 50 and 1000 mA g−1 current densities, respectively. Furthermore, the composite electrode exhibited good cyclic stability at 1000 mA g−1 current density by delivering an excellent specific charge capacity of 490 mAh g−1 even after 400 cycles. Therefore, these superior electrochemical properties confirm the potential applicability in high-performance and stable Li-ion batteries.

Design and Performance of a New Zn0.5Mg0.5FeMnO4 Porous Spinel as Anode Material for Li-Ion Batteries.

Due to the low capacity, low working potential, and lithium coating at fast charging rates of graphite material as an anode for Li-ion batteries (LIBs), it is necessary to develop novel anode materials for LIBs with higher capacity, excellent electrochemical stability, and good safety. Among different transition-metal oxides, AB2O4 spinel oxides are promising anode materials for LIBs due to their high theoretical capacities, environmental friendliness, high abundance, and low cost. In this work, a novel, porous Zn0.5Mg0.5FeMnO4 spinel oxide was successfully prepared via the sol-gel method and then studied as an anode material for Li-ion batteries (LIBs). Its crystal structure, morphology, and electrochemical properties were, respectively, analyzed through X-ray diffraction, high-resolution scanning electron microscopy, and cyclic voltammetry/galvanostatic discharge/charge measurements. From the X-ray diffraction, Zn0.5Mg0.5FeMnO4 spinel oxide was found to crystallize in the cubic structure with Fd3¯m symmetry. However, the Zn0.5Mg0.5FeMnO4 spinel oxide exhibited a porous morphology formed by interconnected 3D nanoparticles. The porous Zn0.5Mg0.5FeMnO4 anode showed good cycling stability in its capacity during the initial 40 cycles with a retention capacity of 484.1 mAh g-1 after 40 cycles at a current density of 150 mA g-1, followed by a gradual decrease in the range of 40-80 cycles, which led to reaching a specific capacity close to 300.0 mAh g-1 after 80 cycles. The electrochemical reactions of the lithiation/delithiation processes and the lithium-ion storage mechanism are discussed and extracted from the cyclic voltammetry curves.

Preparation of various Co/Cu and Co/Fe molar ratios and gel-modified nanomaterials as anodes for Li-ion batteries

Co-based binary metal oxides with higher theoretical capacity have attracted increasing attention as anodes for lithium-ion batteries (LIBs). In this study, Co-based bimetallic oxides were prepared by optimizing different molar ratios of Cu/Co and Fe/Co using an electroconversion method. The purity and microstructure of the synthesized powders were investigated, and their lithium storage properties were studied by assembling half-cells. Cu/Co oxide exhibited three different microstructures, while Fe/Co oxide showed a nanoparticle morphology. The electrochemical performance results revealed that the optimal molar ratio of Co: Cu was 2:1, and the optimal molar ratio of Fe: Cu was 5:1. Particularly, Fe: Cu = 5:1 exhibited the best electrochemical stability and higher specific capacitance. Therefore, Fe3O4/Co3O4 (Fe: Cu = 5:1) was used as the raw material for modification, and a hydrogel method was employed with sodium alginate (SA) serving as the fixing agent and carbon source to prepare microspheres. Taking advantage of the natural freezing conditions in the winter of Northeast China, the dried microspheres were subjected to calcination to obtain Fe3O4/Co3O4/SA with enhanced conductivity. Even at a current density of 2 A/g, Fe3O4/Co3O4/SA still maintained a discharge capacity of around 280 mAh/g, demonstrating excellent cycling stability and rate capability.

Ab initio study of Li-shrouded Si-doped [formula omitted]-Graphyne nanosheet as propitious anode in Li-ion batteries

Li-ion batteries (LIBs) have become a house-hold name in the energy-storage research community in the wake of their noteworthy attributes. With increasing energy demands, the urgency to develop high performance LIBs is also rising rapidly which has compelled the researchers to design and fabricate new high capacity materials. Bearing that in mind, we have investigated a carbon–silicon based anode, i.e. Si-doped γ-Graphyne (SiG) nanolayer for its applicability as LIB electrode. Carbon and Silicon are two complementary choices for anode material due to the reason that the weakness of one is complemented by the other i.e. the extensive volume changes of Si anodes is compensated by the stable carbon matrix and the lower Li affinity of carbon is complemented by large capacities of Si anode. The Density Functional Theory (DFT) based studies reveal that SiG nanolayer has a dynamically and thermally stable structure with reliable mechanical properties. Density of states (DOS) calculation substantiates the good conductivity of the nanolayer. The binding energy of the Li atom (adatom) is −1.33 eV resulting from a charge transfer of 0.88e from Li to the nanolayer. The SiG anode achieved a specific capacity of 1005.05 mAhg−1 (almost 2.7 times the Graphite anode used in commercial LIBs). Climbing Image-Nudged Elastic Band (CI-NEB) calculations depict an easy migration of the adatoms through the anode with an energy barrier of 0.67 eV having diffusion coefficient (D) as 8.91 × 10−14 cm2/s. A low working voltage of 0.44 V is obtained advocating a safe operation and good cyclability. So, the theoretical investigation presents favorable outcomes for Si-doped γ-Graphyne to be applicable as a progressive anode in next-generation LIBs.

Thermal polymerization of ion-modified carbon dots into multi-functional LiF-carbon interface for stabilizing SiO anode

SiO has been demonstrated as one type of promising high-capacity anode for Li-ion batteries. However, the parasitic reactions between the electrolyte and SiO interface, severer than that of the well-developed graphite, are generally overlook. Herein, a multi-functional LiF-carbon co-coating layer on SiO (SiO@LCD) is designed to resist the interfacial reactions, which originates from thermal-assembly of zero-dimensional Li-absorbed and F-doped carbon dots produced by hydro/alcohol-thermal reaction of discarded wood sawdust with a high yield of 96.9 %. Combined with advanced spectroscopy characterizations and theoretical calculations, the LiF-carbon co-coating layer has been determined to induce preferential decomposition of LiPF6 to form a thin and dense solid electrolyte interface (SEI) with LiF-rich inner layer, and promote the rapid transmission of ion/electron. As a result, the initial Coulombic efficiency (CE) of the SiO@LCD increases from 66.1 % to 78.6 %, and the average CE is increased by 0.3 % at 0.2 A g−1 with enhanced rate capability and cycling stability during the (de)lithiation process. More importantly, the assembled 3.7 Ah pouch cell exhibits a long-term cycling life over 400 cycles at 0.2 C with the capacity retention of 85.1 %.

Eco-saving and green anode materials for Li-ion batteries utilizing oxide-decorated biocarbon substrates proceeded from cassava residues

In this work, an eco-saving and green anode structure (CRC) of MnO/Mn3O4 nanoparticles (NPs) anchored on biocarbon substrates derived from cassava residues (CRs) was designed and fabricated successfully by an in-situ method from MnCl2 and CRs. The amount of MnO/Mn3O4 NPs in the CRC can be effectively modulated by altering the mass ratio of MnCl2 to CRs. In Li-ion batteries, CRC anodes exhibit outstanding electrochemical performances such as high Coulombic efficiency, high capacity, excellent rate capacity, and stable cycling. The high reversible capacity of 698 mAh g−1 at 100 mA g−1 can be achieved even after 100 cycles. This could be accredited to the special structure of MnO/Mn3O4 NPs and biocarbon substrates. First, CR-derived biocarbon favors the alleviation of volume change and prevents the aggregation of MnO/Mn3O4 NPs during cycling. Then, an appropriate amount of MnO/Mn3O4 NPs formed on the surface and empty cages of biocarbon generate various free contacting channels between the electrolyte and active materials. Finally, MnO/Mn3O4 NPs intensify the electrochemical activity of biocarbon, leading to an increase in Li-storage capacities. Therefore, the facile in-situ method in this work is quite promising to produce cost-effective and eco-friendly anodes for Li-ion batteries utilizing recycled CRs and simple chemicals.

Freestanding and Consecutive Intermixed N-Doped Hard Carbon@Soft Carbon Fiber Architectures as Ultrastable Anodes for High-Performance Li-Ion Batteries

Freestanding and Consecutive Intermixed N-Doped Hard Carbon@Soft Carbon Fiber Architectures as Ultrastable Anodes for High-Performance Li-Ion Batteries

MnNCN@C nanocomposite as an anode for Li-ion battery

In order to find other anode materials for lithium-ion batteries, manganese carbodiimide with N-doped C coating (MnNCN@C) has been reported. Initially a gel of precursors was prepared and then calcined for 1.5 h at 700 °C in the atmosphere of N2. The MnNCN phase was identified by X-ray diffraction, X-ray Photoelectron Spectroscopy (XPS) and electron diffraction. Further, carbon phase was established by transmission electron microscopy (TEM), FTIR and Raman spectroscopy. The doping of N in carbon phase was confirmed from XPS study. Distribution of pore size as well as specific surface area of MnNCN@C composites were investigated from the BET technique, and their values were 9.19 × 103cm2/g and 7.512 nm, respectively. The cell with this material as anode could be cycled for 100 times. After 100 cycles, the capacity turns out to be around 200 mAh/g. However, the cell was capable to deliver suitable capacity at even higher currents.

NbO2 a Highly Stable, Ultrafast Anode Material for Li- and Na-Ion Batteries.

Anode materials with fast charging capabilities and stability are critical for realizing next-generation Li-ion batteries (LIBs) and Na-ion batteries (SIBs). The present work employs a simple synthetic strategy to obtain NbO2 and studies its applications as an anode for LIB and SIB. In the case of the LIB, it exhibited a specific capacity of 344 mAh g-1 at 100 mA g-1. It also demonstrated remarkable stability over 1000 cycles, with 92% capacity retention. Additionally, it showed a unique fast charging capability, which takes 30 s to reach a specific capacity of 83 mAh g-1. For the SIB, NbO2 exhibited a specific capacity of 244 mAh g-1 at 50 mA g-1 and showed 70% capacity retention after 500 cycles. Furthermore, detailed density functional theory reveals that various factors like bulk and surface charging processes, lower ion diffusion energy barriers, and superior electronic conductivity of NbO2 are responsible for the observed battery performances.

Selenium enriched over-oxidized Mo3Se4 decorated MXene as a high-performance Li-ion battery anode material

The anode materials in Li-ion battery (LIB) are key components that define the performance of the cell. We have developed new selenium enriched and over-oxidized Mo3Se4 decorated MXene (Mo3Se4@Ti3C2Tx) composite as a promising anode material for Li-ion battery (LIB). By using selective experimental conditions, Mo3Se4@ Ti3C2Tx was successfully developed with unique structural and morphological features. When being employed as anode material in LIB, Mo3Se4@Ti3C2Tx delivered high stable reversible specific discharge capacity of 1250 mAh/g at 0.1C, which is significantly higher than traditional carbon-based anode materials. In addition, the composite retained 84.53 % of initial specific capacity when the C-rate was increased from 0.1C to 1.5C, implying excellent rate performance. The Mo3Se4@Ti3C2Tx composite also demonstrated remarkable cycling stability with negligible loss after 378 cycles. This exceptional electrochemical performance can be assigned to the exclusive architecture of Mo3Se4@Ti3C2Tx composite, leading to increase in exposure of active Li+ sites and structural stability.

Electrical bridging effects of dual-carbon microsphere frameworks in Si-based composite anodes for high-performance Li-ion batteries

Herein, the successful fabrication of a high-performance Si-based composite Li-ion battery (LIB) anode, comprising a dual-carbon framework of reduced graphene oxide (r-GO) and oxidized single-walled carbon nanohorns (o-NHs), was demonstrated using a simple and scalable spray-drying process followed by heat treatment (h-s-GO/Si/NH). The r-GO nanosheets in the h-s-GO/Si/NH anode acted as a robust spherical framework that facilitated the mechanical and electrical connection between the carbon-coated Si (c-Si) nanoparticles, homogeneous dispersion of c-Si and o-NH nanoparticles, and suppression of the volume expansion and pulverization that occur during lithiation/delithiation. Additionally, the o-NH nanoparticles incorporated in the h-s-GO/Si/NH composite served as electrical bridges between the r-GO nanosheets, resulting in enhanced electrical conductivity and effortless Li-ion shuttling. The h-s-GO/Si/NH composite anode exhibited high electrochemical performance with a very high initial gravimetric charge capacity (2961 mAh g−1 at 0.1 A g−1), stable initial Coulombic efficiency (80.6% at 0.2 A g−1), and high cycling stability (983 mAh g−1 at 0.2 A g−1 after 50 cycles). This study highlights the importance of the effective design of electrically conductive three-dimensional frameworks in Si-based composite anodes, which may contribute to the development of high-performance LIB anode materials.