Anode For LIBs Research Articles

Organic Anodes with Nearly 100% Initial Coulombic Efficiency Enabled by Wet‐Chemically Constructed Artificial Solid‐Electrolyte Interphase Film toward High‐Energy‐Density Organic Full Batteries

AbstractLithium‐ion batteries (LIBs) built on inorganic anodes have achieved great commercial success. By contrast, the practical application of organic anode materials encounters key bottlenecks including electronic insulation, high solubility, and poor initial coulombic efficiency (ICE). Among them, improving ICEs (normally 30–60%) faces enormous challenges in both theory and technology, and there has been no substantial breakthrough yet. Herein, a wet chemical pretreatment technology to increase the ICE of maleic acid (MA)‐based anodes from 43.2% to nearly 100% is proposed for the first time, and this strategy demonstrates universal applicability. Typically, the wet chemical pretreatment involves reacting with lithium‐biphenyl to form LixMA intermediates (x = 4–6) and further forming a compact artificial solid‐electrolyte interphase (SEI) film through the spontaneous reaction between active LixMA and battery organic electrolytes. This wet chemically‐constructed artificial SEI layer can almost completely suppress lithium loss in the initial cycle of the MA electrode and significantly boost the actual output energy density, rate capability, and cycling durability of MA anode‐based full batteries. Significantly, the study further demonstrated that a series of organic anode materials with high ICEs can be achieved through similar wet chemical pretreatment. This work will open up the true application of high‐ICE organic anodes in LIBs.

A new anode material for high rate and long life lithium/sodium storage

It is imperative to design suitable anode materials for both lithium-ion (LIBs) and sodium-ion batteries (SIBs) with a high-rate performance and ultralong cycling life. We fabricated a MoO2/MoS2 heterostructure that was then homogeneously distributed in N,S-doped carbon nanofibers (MoO2/MoS2@NSC) by electrospinning and sulfurization. The one-dimensional carbon fiber skeleton serves as a conductive frame to decrease the diffusion pathway of Li+/Na+, while the N/S doping creates abundant active sites and significantly improves the ion diffusion kinetics. Moreover, the deposition of MoS2 nanosheets on the MoO2 bulk phase produces an interface that enables fast Li+/Na+ transport, which is crucial for achieving high efficiency energy storage. Consequently, as the anode for LIBs, MoO2/MoS2@NSC gives an excellent cycling stability of 640 mAh g−1 for 2 000 cycles under 5.0 A g−1 with an ultralow average capacity drop of 0.002% per cycle and an exceptional rate capability of 614 mAh g−1 at 10.0 A g−1. In SIBs, it also produces a significantly better electrochemical performance (reversible capacity of 242 mAh g−1 under 2.0 A g−1 for 2 000 cycles and 261 mAh g−1 under 5.0 A g−1). This work shows how introducing a novel interface in the anode can produce rapid Li+/Na+ storage kinetics and a long cycling performance.

Cu/Co binary‐transition metal glycerolates as anode materials for lithium‐ion batteries

AbstractThe energy density of Lithium‐ion batteries (LiBs) fails to keep pace with the growing demand for long‐driving range EVs. Developing novel anode materials with high specific capacities is one of the most effective ways to increase the energy density of LiBs. Herein, a series of Cu and Co binary‐transition metal glycerolates (labeled as CuxCoy/G) were prepared as the anodes for LiBs. It was observed that CuxCoy/G exhibited a distinctive yolk‐shell architecture, which significantly differed from the solid spherical structure of Cu/G and Co/G counterparts. X‐ray powder diffraction and Scanning electron microscope studies suggested that Cu element existed as Cu2+1O in CuxCoy/G, and the Co element was in the form of amorphous glycerolates. Electrochemical studies showed that Cu0.4Co1/G delivered a high capacity over 1000 mAh g−1 at the first discharge, and it exhibited the most stable cycling performance over 200 cycles. Mechanism study suggested both Cu and Co elements contributed to lithium storage capacities in CuxCoy/G at the initial discharging process. Experimental results revealed that Co exhibited reversible capacity while Cu element was reduced to metallic Cu which contributed to the electronic conductivity, rendering Cu0.4Co1/G exhibited a better long‐term cycling stability than Co/G. This work explored a new type of anode material with high specific capacity for LiBs, paving the way to high energy density LiBs.

PEG-PVP-Assisted Hydrothermal Synthesis and Electrochemical Performance of N-Doped MoS2/C Composites as Anode Material for Lithium-Ion Batteries.

Molybdenum disulfide shows promise as an anode material for lithium-ion batteries. However, its commercial potential has been constrained due to the poor conductivity and significant volume expansion during the charge/discharge cycles. To address these issues, in this study, N-doped MoS2/C composites (NMC) were prepared via an enhanced hydrothermal method, using ammonium molybdate and thiourea as molybdenum and sulfur sources, respectively. Polyethylene glycol 400 (PEG400) and polyvinylpyrrolidone (PVP) were added in the hydrothermal procedure as soft template surfactants and nitrogen/carbon sources. The crystal structure, morphology, elemental composition, and surface valence state of the N-doped MoS2/C composites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS), respectively. The results indicate that the NMC prepared by this method are spherical particles with a nanoflower-like structure composed of MoS2 flakes, having an average particle size of about 500 nm. XPS analysis shows the existence of C and N elements in the samples as C-N, C-C, and pyrrolic N. As anodes for LIBs, the NMC without annealing deliver an initial discharge capacity of 548.2 mAh·g-1 at a current density of 500 mA·g-1. However, this capacity decays in the following cycles with a discharge capacity of 66.4 mAh·g-1 and a capacity retention rate of only 12% after 50 cycles. In contrast, the electrochemical properties of the counterparts are enhanced after annealing, which exhibits an initial discharge capacity of 575.9 mAh·g-1 and an ultimate discharge capacity of 669.2 mAh·g-1 after 70 cycles. The capacity retention rate decreases initially but later increases and elevated afterward to reach 116% at the 70th cycle, indicating an improvement in charge-discharge performance. The specimens after annealing have a smaller impedance, which indicates better charge transport and lithium-ion diffusion performance.

Heterostructure MnO/MnSe nanoparticles encapsulated in a nitrogen-doped carbon shell for high-performance lithium/sodium-ion batteries

Heterostructure MnO/MnSe nanoparticles, encapsulated in a nitrogen-doped carbon shell (MnO/MnSe@NC), were synthesized as anode materials using a hydrothermal approach followed situ calcination and selenization process. The NC shell, possessing high electronic conductivity, can function as a substrate to prevent nanoparticle agglomeration and mitigate volume variations. The porous nanostructures can shorten the ion diffusion path and increase active sites, thereby accelerating ion migration and ultimately enhancing battery capacity. Moreover, the MnO/MnSe heterostructure can facilitate Li+/Na+ diffusion, leading to improved rate performance. Benefiting from the structural advantage of MnO/MnSe heterostructure nanoparticles encapsulated within a nitrogen doped carbon shell, this electrode demonstrates exceptional electrochemical performance as an anode for LIBs, including a high discharge capacity (1740 mAh g−1 at 0.1 A g−1), remarking rate capability (849.9 mAh g−1 at 15.0 A g−1), and superior cycling stability (802 mAh g−1 over 1500 cycles at 5.0 A g−1). Meanwhile, the MnO/MnSe@NC serves as an anode material in SIBs, demonstrating a remarkable reversible specific capacity of 902.8 mAh g−1 at 0.1 A g−1 and excellent rate capability (681.6 mAh g−1 at 15.0 A g−1). The present study presents a straightforward approach for fabricating the anode electrode of high-performance lithium/sodium ion batteries.

Metal sulfides encapsulated in doped carbon aerogel towards superior and safe energy storage: Two birds with one stone

Up to now, lithium/sodium ion batteries (LIBs/SIBs) are deemed as the ideal candidates for traditional fossil energy. However, the absence of suitable Li+/Na+ reservoirs and the hazard of thermal runway have plagued their usages. Using Li4Ti5O12 or TiO2 anode promotes the thermal safety of LIBs/SIBs but reduce their electrochemical property. How to achieve the balanced performances has been an urgency. Here, we have delicately designed a 3D micro-nanostructure of CoS2/doped carbon aerogel (CoS2@NCA), via “killing two birds with one stone” strategy. When used as LIBs anode, CoS2@NCA delivers a high capacity of 639.5 mAh g−1 after operating at 1 A g−1 for 250 cycles, giving a low-capacity attenuation rate of 0.048 % per cycle. Meanwhile, the reduced maximum temperature and maximum heating rate of thermal runaway (TR) are observed for cell. When used as SIBs anode, CoS2@NCA delivers a high capacity of 620.9 mAh g−1 at 100th cycle as working at 1 A g−1. Likewise, the activation energy for TR is promoted. Overall, the utilization of CoS2@NCA enables the superior and safe energy storage.

TiB4 and SrB8 monolayers: high capacity and zero strain-like anode materials for Li/Na/K/Ca ion batteries.

Storage capacity, average open circuit voltage (OCV), diffusion barrier, lattice parameter changes, etc. are key indicators of whether a material would be suitable for use as a Li-ion or non-Li-ion battery (LIB or NLIB) anode. The rapid development of 2D materials over the past few decades has opened up new possibilities for these metrics. Using first-principles calculations, we prove that two 2D materials, TiB4 and SrB8, show excellent performance in terms of the above metrics when used as anodes for LIBs or NLIBs. As detailed, TiB4 has an Li\Na\K\Ca storage capacity of 588 mA h g-1, 588 mA h g-1, 588 mA h g-1, and 1176 mA h g-1, respectively, and SrB8 has an Li\Na\K\Ca storage capacity of 308 mA h g-1, 308 mA h g-1, 462 mA h g-1, and 616 mA h g-1, respectively, and they show good electrical conductivity whether existing Li, Na, K or Ca is adsorbed or not. The diffusion barriers on both surfaces are low, indicating good rate performance. The average OCV is also very low. In particular, the lattice parameters of the two materials change very little during the embedding of Li\Na\K\Ca. For Ti9B36 the corresponding values are about 0.37% (Li), 0.33% (Na), 0.64% (K) and 0.03% (Ca), and for Sr8B64 the corresponding values are about 0.70% (Li), 0.16% (Na), 0.13% (K) and 0.004% (Ca), which imply zero strain-like character and great cycling performance. All the above results show that TiB4 and SrB8 monolayers are very promising Li\Na\K\Ca ion battery anodes.

Chromium tetraphosphide (CrP4) as a high-performance anode for Li ion and Na ion batteries

The CrP4 nanoparticles and CrP4/C nanocomposite were synthesized via high-energy mechanical milling and applied as anodes for LIBs and SIBs.

Mesoporous Co3O4@CdS nanorods as anode for high-performance lithium ion batteries with improved lithium storage capacity and cycle life.

Transition metal oxides based anodes are facing crucial problems of capacity fading at long cycles and high rates due to electrode degradations. In this prospective, an effective strategy is employed to develop advanced electrode materials for lithium-ion batteries (LIBs). In the present work, a mesoporous Co3O4@CdS hybrid sructure is developed and investigated as anode for LiBs. The hybrid structure owning porous nature and large specific surface area, provides an opportunity to boost the lithium storage capabilities of Co3O4 nanorods. The Co3O4@CdS electrode delivers an initial discharge capacity of 1292 mA h g-1 at 0.1C and a very stable reversible capacity of 760 mA h g-1 over 200 cycles with a capacity retention rate of 92.7%. In addition, the electrode exhibits excellent cyclic stability even after 800 cycles and good rate performance as compared to previously reported electrodes. Moreover, density functional theory (DFT) and electrochemical impedance spectroscopy (EIS) confirm the enhanced kinetics of the Co3O4@CdS electrode. The efficient performance of the electrode may be due to the increased surface reactivity, abundant active sites/interfaces for rapid Li+ ion diffusion and the synergy between Co3O4 and CdS NPs. This work demonstrates that Co3O4@CdS hybrid structures have great potential for high performance batteries.

Nickel-doped Li2MoO4 as a high-performance anode material for rechargeable lithium-ion batteries

A nickel doping strategy has been developed to prepare Li2NixMo1−xO4 as an anode for LIBs. The as-prepared Ni-doped Li2Ni0.05Mo0.95O4 shows a stable lithium storage capacity of 686.6 mA h g−1, much higher than 365 mA h g−1 for a Li2MoO4 anode.

Layered MoxBy (MBenes) derived by a molten-salt method and their application in advanced LIB anodes

A typical accordion structure MBene prepared by molten salt method and its performance as advancde anode in LIBs.

3D hierarchical Ti3C2/TiO2 composite via in situ oxidation for improved lithium-ion storage.

To address the intrinsic limitations of both TiO2 and MXenes, we propose an effective strategy for the engineering of a 3D Ti3C2/TiO2 nanorod hybrid, where the in situ synthesized TiO2 nanorods are homogeneously decorated onto the surface of 3D Ti3C2 MXene via simple oxidation. As the LIB anode, it demonstrates exceptional long-term cycling stability with a specific capacity of 384.1 mA h g-1 after 600 cycles at 1.0 A g-1.

Comprehensive recycling of spent lithium-ion battery cathodes and anodes via a targeted electrochemical redox process

A targeted electroredox approach is reported, which has the potential to generate electricity during the leaching process in order to achieve comprehensive recycling of spent LIB cathodes and anodes with simple pre-treatment under mild conditions.

Design principle of disordered rocksalt type overlithiated anode for high energy density batteries.

Rechargeable lithium-ion batteries with high energy density and fast-charging capability are vital for commercial applications. Disordered rocksalt (DRX) materials with a cation/anion ratio greater than one, achieved through additional lithium insertion, have emerged as promising high-rate anode candidates. Inspired by the previously reported Li3+xV2O5 (0 ≤ x ≤ 2) anode, a comprehensive search was conducted for all potential redox centers using high-throughput density functional theory (DFT) computations. This study examined 23 redox centers in a prototype formula Li3+xV2O5 (0 ≤ x ≤ 2) with the DRX structure, analyzing aspects such as voltage curve, theoretical capacity, energy density, phase stability, electronic conductivity, and volumetric change during cycling. Promising candidates were identified with redox centers including V, Cr, Nb, Mn, and Fe, marking them as potential anode materials. Additionally, this research revealed the origin of the low voltage in DRX anodes and proposed a method to optimize the average voltage by tuning the relative energies among structures with varying lithium contents. This work provides compositional design principles for the new promising DRX anode of LIBs with high energy density, fast-charging capability, and good cycling stability.

Understanding of Polyacrylic Acid as Binder for High Silicon Containing Anodes and Ni-Rich Cathodes

With the increased demand on electric vehicles, portable devices and energy storage systems, a great attention is being drawn to improve the energy density of lithium-ion batteries (LiBs) [1]. The commercial LiBs anodes are usually consisted of graphite-based material, which limits the energy density due to its relatively low theoretical capacities. Silicon (Si) has been recognized as an alternative anode material with its high theoretical capacity, natural abundance, and low discharge potential. Despite the above-mentioned advantages, Si undergoes a substantial volume expansion (300% approximately) during the battery operation [2]. There are some approaches to mitigate the adverse of expansion, whereas the cost and scalability of these techniques are the bottlenecks to solve this issue [3]. In this work, we focus on maintaining the structural integrity, along with the coordination of Li as functional binder which could be an effective solution to the abovementioned challenges.In addition to the energy density and capacity targets, considering more environmentally friendly approaches is also one of the key topics for battery manufacturing. Aqueous processing of the anodes is already state-of-the-art whilst, the cathode has its own challenges to be overcome. Ni-rich transition oxide active materials, such as LiNi0.8MN0.1Co0.1 (NMC811), are attractive for high-capacity target applications. Due to the high reactive surface of the active material, during the slurry processing, NMC811 reacts with water, which leads to Li+/H+ exchange [4]. Thus, the slurry results in high pH which can corrode the aluminum foil current collector and cause poor capacity due to Li loss. The advantage of using polyacrylic acid (PAA) is to employ COOH, in which the leached Li+ can bond to the backbone. Hence, the pH of slurry is maintained on desirable coating range and the capacity loss can be reduced due to the proposed aqueous processing.In this study, we explore the utilization of a well-known polymer, polyacrylic acid, as binder for both negative and positive electrodes. On the anode, PAA is functionalized with Li+ and used LiPAA prior to electrode production. It is highly crucial to observe how the dynamics of Si and LiPAA impacts the anode performance during the cycling. To comprehend this, post mortem, scanning electron microscopy (SEM) was performed to detect the positioning and concentration of Si on pristine and cycled anodes. On the cathode side, the focus is to utilize the leached Li+ during the slurry processing by having PAA as binder. This technique has been already successfully implemented by our group on the research pilot scale [5]. The idea is to make pH stable slurry without using any additional acid, in conjunction with creating in situ functional binder (LiPAA). Deep understanding of functional binders is to serve as a guide for the rational design of Si-electrode and aqueous NMC811 cathodes for LiBs.

Facile synthesis and electrochemical studies of Mn-Zn ferrite as anode for Li-ion batteries

In this study, Zn1-xMnxFe2O4 (x = 0.0,0.01,0.03,0.05) has been synthesized via a simple and facile high-energy ball milling route. X-ray Diffraction (XRD) analysis revealed the good highly crystalline phase with spinel structures for all the prepared samples with no traces of impurity except for x = 0.05, which shows an impurity peak of α-Fe2O3. The morphological studies were investigated to confirm the shape and size of the prepared samples using SEM and TEM. The average particle size estimated from SEM and TEM was found to be in the range of 100–200 nm. Energy Dispersive Spectroscopy (EDS) analysis confirms the homogeneous mixing of the elements in the prepared sample. The electrochemical performance of prepared Mn-doped ZnFe2O4 was analyzed using Galvanostatic Charge-Discharge (GCD), Electrochemical Impedance Spectroscopy (EIS), and Cyclic Voltammetry (CV). The pseudocapacitive and diffusive contribution for the charge storage mechanisms has also been analyzed. The results indicate that the Zn1-xMnxFe2O4 (x = 0.03) electrode exhibits excellent electrochemical behavior as compared to other prepared electrodes. Zn1-xMnxFe2O4 (x = 0.03) delivers excellent initial charge-discharge capacity of 1405 mAhg−1 and 900 mAhg−1 with a coulombic efficiency of 64.2%. After 200 cycles Zn1-xMnxFe2O4 (x = 0.03) delivered the discharge capacity of 502 mAhg−1 with capacity retention of 35%. The rate capability of Zn1-xMnxFe2O4 (x = 0.03) at a current density of 1000 mAg−1 was observed to be 434 mAhg−1. The EIS study revealed that Zn1-xMnxFe2O4 (x = 0.03) has the lowest Rct value and faster diffusion of Li-ions which amplified its capacity retention even at higher current density, making it a suitable anode for LIBs.

Two-dimensional LiTi2(PO4)3 flakes for enhanced lithium ions battery anode

In this work, the LiTi2(PO4)3 (LTP) flakes have been prepared by employing a template method for lithium-ion batteries with high capacity. The 2D layered structure of LTP offers large aspect ratio and rich active sites, which not only create the large contact area between the electrolyte and electrode, but also promote the diffusion kinetics of Li+. As a result, the Li+ diffusion coefficient of lamellar LTP anode is 3.12 × 10−8 cm2 s−1, while it is only 5.01 × 10−10 cm2 s−1 for granular LTP anode. Further, the lamellar LTP anode delivers a high initial discharge capacity of 986.8 mAh·g−1 at 0.1 A g−1, and remains at 231.1 mAh·g−1 after 100 cycles, which is higher than that of the granular LTP anode (340.5 mAh·g−1 at 1st cycle, 169.3 mAh·g−1 at 100th cycles). Thus, the lamellar LTP should be recommended as a potential anode for high-performance LIBs due to the fast charge-discharge performance and superior cycling stability.

Electrochemical Performance of LIB Anodes Based on Silicon Monoxide: The Effect of Disproportionation and Treatment in HF

Electrochemical Performance of LIB Anodes Based on Silicon Monoxide: The Effect of Disproportionation and Treatment in HF

Amorphous Fe2O3 Porous Films Grown on Multilayer Graphene for High-Performance LIB Anodes

Amorphous Fe2O3 has special high electrochemical performance as anode materials of LIBs due to its disorderly arranged atoms. However, the issue of its low intrinsic electric conductivity should be solved rationally and facilely. In this work, amorphous Fe2O3 porous films are chemically deposited on the mechanically exfoliated multilayer graphene (MLG) nanosheets, forming a Fe2O3/MLG/Fe2O3 sandwich nanostructure. The addition of 10[Formula: see text]mg of EDTA-2Na is crucial for the formation of amorphous nature and holes in Fe2O3 films on MLG. This composite exhibits better electrochemical performance as LIB anodes than well-crystallized Fe2O3 nanoparticles, amorphous Fe2O3 films without holes and amorphous Fe2O3 isolated nanoparticles on MLG, which are prepared using 0[Formula: see text]mg, 5[Formula: see text]mg, 20[Formula: see text]mg of EDTA-2Na, respectively. The optimized composite delivers a reversible discharge capacity of 1067[Formula: see text]mAh g[Formula: see text] at 100[Formula: see text]mA g[Formula: see text] after 100 cycles. Moreover, a capacity of 522 mAh g[Formula: see text] is delivered at a high current density of 2[Formula: see text]A g[Formula: see text]. The high electrochemical performance of the composite is attributed to the amorphous nature and porous film structure of Fe2O3, and well combination of Fe2O3 and highly conductive MLG substrate.

Revealing bimetallic synergy in van der Waals AgInP2Se6 nanosheets for alkali metal ion battery electrodes

We report two-dimensional AgInP2Se6 (AIPSe) bimetallic phosphorus trichalcogenides nanosheets as anodes for advanced alkali metal ion batteries (AMIBs). The intrinsic layered architecture of this compound not only facilitates rapid charge propagation but also accentuates ion storage due to its expansive surface area. The integration of the bimetallic component results in a synergistic enhancement in electronic/ionic conductivity and optimizes the redox dynamics of multi-electronic materials, eventually attaining superior electrochemical characteristics. Moreover, the accompanying deposition of metallic silver during electrochemical processes reduces battery polarization, while the presence of metallic indium acts as an efficacious structural stabilizer, effectively inhibit dendrite proliferation. As an anode electrode coupled with graphite (G) in lithium-ion (LIBs) and potassium-ion batteries (PIBs), AIPSe@G anodes for LIBs achieve 707.8 mA h g−1 at 0.1 A g−1, retain over 900 cycles at 2.0 A g−1, and demonstrate 318.5 mA h g−1 at 3.0 A g−1 rate capability. For PIBs, they reach 480.3 mA h g−1 at 25.0 mA g−1, sustains for 550 cycles at 250 mAg−1, and offers 214.2 mA h g−1 at 3.0 A g−1 rate performance. Comprehensive full cell tests further endure 100 cycles in both LIBs and PIBs under diverse current regimes. Our study pioneers a new direction for AMIB anode materials, emphasizing the advantages of integrating bimetallic features into two-dimensional frameworks to boost electrode dynamics and achieve consistent conversion reactions.