Anode For Lithium Ion Battery Application Research Articles

W-based MOF derived ZnWO4/ZnO@C hierarchical nanoflakes with superior lithium storage performance

Tungstate-based materials as lithium-ion battery anodes have drawn multitudinous attention owing to their great theoretical capacity and typical multielectron transfer process. Nevertheless, their slow electrochemical reaction kinetics and big volume variation often trigger poor lithium storage properties. Herein, novel ZnWO4/ZnO@C hierarchical nanoflakes are engineered via a facile W-based metal-organic framework (W-MOF) template method. The ZnWO4/ZnO@C nanoflakes with a rectangular shape and high porosity are constructed by carbon-coated nanocrystal subunits. The unique composition and microstructure of ZnWO4/ZnO@C can shorten the pathway for Li+/electron transport, expand the contact with the electrolyte, improve the electrical conductivity, and fortify structural stability. Consequently, the ZnWO4/ZnO@C material as LIBs anodes delivers a high reversible capacity of 734 mAh g-1 after 150 cycles at 200 mA g-1, decent rate capability (426 mAh g-1 at 1000 mA g-1), and outstanding cyclic stability (93.8 % capacity retention over 350 cycles at 500 mA g-1). The in-situ XRD combined with ex-situ XPS and FT-IR was performed to elucidate the lithium storage mechanism of ZnWO4/ZnO@C. This work presents a simple and efficient approach for the synthesis of novel tungstate-based anodes for lithium-ion battery applications.

Green Synthesis of CoZn-Based Metal-Organic Framework (CoZn-MOF) from Waste Polyethylene Terephthalate Plastic As a High-Performance Anode for Lithium-Ion Battery Applications.

The recycling of discarded polyethylene terephthalate (PET) plastics produced metal-organic frameworks can effectively minimize environmental pollution and promote sustainable economic development. In this study, we developed a method using NaOH in alcohol and ether solvent environments to degrade PET plastics for synthesizing terephthalic acid. The method achieved a 97.5% degradation rate of PET plastics under a reaction temperature of 80 °C for 60 min. We used terephthalic acid as a ligand from the degradation products to successfully synthesize two types of monometallic and bimetallic CoZn-MOF materials. We investigated the impact of different metal centers and solvents on the electrochemical performance of the MOF materials. The result showed that the MOF-DMF/H2O material maintained a specific capacity of 1485.5 mAh g-1 after 100 cycles at a current density of 500 mA g-1, demonstrating excellent rate capability and cycling stability. In addition, our finding showed that the performance difference might be attributed to the synergistic effect of bimetallic Co2+ and Zn2+ in MOF-DMF/H2O, rapid lithium-ion diffusion and electron transfer rates, and the absence of coordinating solvents. Additionally, the non-in situ X-ray powder diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis results showed that lithium storage in the MOF-DMF/H2O electrode mainly depended on the aromatic C6 ring and carboxylate portions of the organic ligands in different charge and discharge states. Lithium ions can be reversibly inserted/removed into/from the electrode material. The physical adsorption on the MOF surface through electrostatic interactions enhanced both capacity and cycling stability. This research provides valuable insight for mitigating solid waste pollution, promoting sustainable economic development, and advancing the extensive applications of MOF materials in lithium-ion batteries.

Upcycling electrode materials from spent single-use zinc‑carbon/alkaline batteries into rechargeable lithium-ion battery application

Battery recycling/upcycling is a key component of modern e-waste reduction by transforming discarded electrode powder to value-added materials and chemical feedstocks for the proposed applications. In this study, electrode powder from spent zinc‑carbon/alkaline batteries was upcycled into LiMn2O4 cathode and carbon anode for rechargeable lithium-ion battery. The main metallic contents (zinc and manganese) in electrode powder were quantitatively leached using diluted H2SO4 with the presence of H2O2 as a reducing agent. By applying sequential precipitation, ZnS nanospheres and MnCO3 nanocubes were obtained as determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The recovered MnCO3 was heated with a stoichiometric amount of Li2CO3 to produce high crystalline and pure LiMn2O4. For the electrochemical performance, the results show that upcycled LiMn2O4 exhibits initial discharge capacity of 99.0 mAh g−1 for zc-LiMn2O4 and 111.0 mAh g−1 for al-LiMn2O4, compared to 90.4 mAh g−1 for pristine LiMn2O4. Moreover, recovered carbon materials obtained as an insoluble powder after acid leaching possess unique morphology and crystallinity. The zc‑carbon shows superior cycling performance with reversible charge capacity of 552 mAh g−1 at 1C rate after 100 cycles. This study provides the great potential for upcycling waste battery electrodes to high-value LiMn2O4 cathode and carbon anode for lithium-ion battery application.

Synthesis and Electrochemical Properties of Co3O4@Reduced Graphene Oxides Derived from MOF as Anodes for Lithium-Ion Battery Applications

In this study, we utilized nano-sized Co3O4 and reduced graphene oxides (rGOs) as composite anode materials for Li-ion batteries. The Co3O4/C composite anode was derived from ZIF67 (Zeolitic Imidazolate Framework-67) and was wrapped in rGOs through precipitation. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to identify the crystal structure, phase purity, and surface morphology of the composite. The composition-optimized Co3O4/rGO/C composite anode exhibited a reversible capacity of 1326 mAh/g in the first cycle, which was higher than that of the Co3O4/C composite anode with a capacity of 900 mAh/g at a current density of 200 mA/g. Moreover, after 80 cycles, Co3O4/rGO/C maintained a capacity of 1251 mAh/g at the same current density, which was also higher than the bare Co3O4/C composite (595 mAh/g). Additionally, the Co3O4/rGO/C composite exhibited a good capacity retention of 98% after 90 cycles, indicating its excellent cycling stability and high capacity. Therefore, the Co3O4/rGO/C electrode has great potential as a promising anode material for Li-ion batteries.

Rice husk derived graphene and zinc oxide composite anode for high reversible capacity lithium-ion batteries

Due to the low toxicity, high theoretical capacity, abundant resources, low potential, of zinc oxide (ZnO), it is regarded as the next-generation lithium-ion battery anode material. However, because of the significant drawback in terms of volume expansion during the charge-discharge cycles, ZnO is easily pulverized and agglomerated. In this research work, we synthesize 0.5 g of rice husk-derived graphene (R0.5) and 1.0 g of ZnO (Z1.0) composite (R0.5Z1.0) to accommodate the volume expansion of ZnO during the charge-discharge process as a next-generation lithium-ion battery anode. Rice husk as a graphene source will support the future usage of bio-based materials for active material synthesis. The samples were characterized via SEM, XRD, and Fourier infrared spectroscopy, and with a discharge capacity of 895.2 mAhg−1 at a current density of 200 mAg−1 after 110 cycles, the composite material demonstrated remarkable Li storing characteristics and electrochemical performance as an anode for lithium-ion battery application.

Rapid fabrication of tin-copper anodes for lithium-ion battery applications

The intermetallic Cu6Sn5 is ubiquitous in electronic interconnects where research has focused on controlling the size and distribution of this phase for improved performance. Cu6Sn5 also finds application as an anode material for advanced lithium-ion batteries. Cu6Sn5 anodes can be fabricated via an in-situ growth method involving the reaction between molten Sn and the Cu current collector. This manufacturing route offers some advantages over traditional anode fabrication however the process is slow, limiting its practical application. In this work we show the addition of 6 wt% Ni to the Cu current collector greatly accelerates the growth of (Cu,Ni)6Sn5 in Cu-xNi/Sn solid-melt couples, leading to a growth rate of up to 50x faster, reducing the processing time above 200 °C to less than 10 min. This research studies the dynamics of the formation of (Cu,Ni)6Sn5 between Cu-xNi alloys and liquid Sn through real-time observation using synchrotron X-ray imaging. The (Cu,Ni)6Sn5 growth dynamics are characterised, and the growth kinetics are analysed. Subsequently, the mechanism of the accelerated growth is investigated with electron backscatter diffraction and transmission electron microscopy. The results show the accelerated growth is due to the formation of η-(Cu,Ni)6Sn5 grains with two distinct Ni concentration ranges, leading to finer grains and spalling, which in turn facilitates the diffusion of Sn, enhancing the η-(Cu,Ni)6Sn5 formation kinetics.

Correction to “MoS2 Nanoflower-Derived Interconnected CoMoO4 Nanoarchitectures as a Stable and High Rate Performing Anode for Lithium-Ion Battery Applications”

Correction to “MoS₂ Nanoflower-Derived Interconnected CoMoO₄ Nanoarchitectures as a Stable and High Rate Performing Anode for Lithium-Ion Battery Applications”

Excellent performance of a modified graphite anode for lithium-ion battery application

Electrochemical performance of a potential fast-charging graphite material in lithium-ion batteries prepared by the modification of natural flake graphite (FG-1) is investigated. FG-1 displays excellent electrochemical performance than most of the modified NFG materials. Galvanostatic cycling tests performed in half cells give the initial capacity of 382.7/361.1 mAh g−1, delivering a small irreversible capacity (21.6 mAh g−1) and high coulombic efficiency (94.4%). The carbon-coated graphite displays superior rate performance at 2 C and 3 C currents in pouch cells. FG-1 can cycle at ambient temperature for 500 times under 2 C/1 C and 3 C/1 C regimes with capacity retention of 90.24% and 86.83%, respectively. Moreover, 86.93% and 86.65% of capacity are retained after 800 cycles at 45 °C under the same currents. Storage at elevated temperature (60 °C) after 21 days leads to only 2.98% of voltage drop, as well as 75.72% and 86.43% of capacity retention and recovery.

Ion and electron-conducting additive effect on Li-ion charge storage performance of CuFe2O4/SiO2 composite aerogel anode

Series of Li2O loaded CuFe2O4/SiO2 composite aerogels were prepared using a sol-gel process followed by a supercritical drying method. The physical and chemical properties of as-prepared aerogels were studied using different characterization techniques. Based on alternating current (AC) impedance analysis, the best conducting 5 wt% Li2O loaded CuFe2O4/SiO2 composite aerogel with conductivity σ = 2.4 × 10−9 S cm−1 is studied as anode for lithium-ion battery application. The best conducting composite aerogel provides a reversible Li-storage capacity of 605 mA h g−1 at 100 mA g−1 current density, which is more than the three-fold improved specific capacity of CuFe2O4/SiO2 having 182 mA h g−1. The addition of Li2O increases the charge carrier concentration and mobility of lithium-ions in the CuFe2O4/SiO2 composite aerogel matrix. Further, the Li-storage performance of 5 wt% Li2O loaded CuFe2O4/SiO2 composite aerogel is improved by increasing the electron-conducting super-P carbon (SPC) blending ratio from 70: 20: 10 to 40: 50: 10 between active material: SPC: binder during electrode preparation. It delivers a reversible specific capacity of 880 mA h g−1 at 100 mA g−1 current density, and it reaches 98% coulombic efficiency over 50-cycles. The specific capacity and cyclability of Li2O loaded CuFe2O4/SiO2 aerogel are highly dependent on electrical conductivity. The improved electrochemical performance of CuFe2O4/SiO2 aerogel is obtained through the combined effects of Li-ion concentration (Li2O addition) as well as electron conducting (SPC) carbon additives.

Electrochemical performance of pre-lithiated ZnMoO4 and r-GO@ZnMoO4 composite anode for lithium-ion battery application

Exploring a safer replacement of Li metal anode is crucial for technological, and fundamental importance. Li-metal is a preferred choice as anode material for lithium-ion battery (LIB) applications. However, parasitic dendritic growth on the Li metal surface during cycling causes instability and safety dreads. In the present study, we have investigated that the pre-lithiated ZnMoO4 is superior to its carbon-based counterparts (r-GO@ZnMoO4), moreover safer and sustainable than Li metal anode. The pre-lithiated ZnMoO4 delivers a better reversible capacity (∼1000 mAhg−1 at 0.1 Ag−1), superior rate capability (∼400 mAh g − 1 at 2 Ag−1), and excellent cycling stability over 300 cycles at 0.1 Ag−1, as compared to bare ZnMoO4 and r-GO@ZnMoO4 composite. The present investigation is an attempt to provide a substitute for commonly used Li-metal/carbon anodes with better performance.

Synthesis and Electrochemical Properties of Bi2MoO6/Carbon Anode for Lithium-Ion Battery Application.

High capacity electrode materials are the key for high energy density Li-ion batteries (LIB) to meet the requirement of the increased driving range of electric vehicles. Here we report the synthesis of a novel anode material, Bi2MoO6/palm-carbon composite, via a simple hydrothermal method. The composite shows higher reversible capacity and better cycling performance, compared to pure Bi2MoO6. In 0–3 V, a potential window of 100 mA/g current density, the LIB cells based on Bi2MoO6/palm-carbon composite show retention reversible capacity of 664 mAh·g−1 after 200 cycles. Electrochemical testing and ab initio density functional theory calculations are used to study the fundamental mechanism of Li ion incorporation into the materials. These studies confirm that Li ions incorporate into Bi2MoO6 via insertion to the interstitial sites in the MoO6-layer, and the presence of palm-carbon improves the electronic conductivity, and thus enhanced the performance of the composite materials.

MoS2 Nanoflower-Derived Interconnected CoMoO4 Nanoarchitectures as a Stable and High Rate Performing Anode for Lithium-Ion Battery Applications.

In recent years, conversion-based mixed transition-metal oxides have emerged as a potential anode for the next generation lithium-ion batteries because of their high theoretical capacity and high rate performance. Herein, an interconnected cobalt molybdenum oxide (CoMoO4) nanoarchitecture derived from molybdenum sulfide (MoS2) nanoflowers is investigated as an anode for lithium-ion batteries. The interconnected CoMoO4 displayed an excellent discharge capacity of 1100 mA h g-1 over 100 cycles at a current rate of C/5. Moreover, the material exhibited an enhanced electrochemical stability, high rate performance, and delivered high discharge capacities of 600 and 220 mA h g-1, respectively, at 5 C and 10 C after 500 cycles. The excellent cycling stability and high rate performance of interconnected CoMoO4 are credited to its unique architecture and porous morphology. The above characteristics and the synergetic effect between the constituting metal ions not only provided a shorter diffusion path for the lithium-ion conduction but also improved the electronic conductivity and mechanical strength of the anode. The field-emission scanning electron microscopy analysis of the electrochemically cycled electrode revealed good structural integrity of the electrode. Further, the practical feasibility of interconnected CoMoO4 in the full cell was analyzed by integrating it with the LiNi0.8Mn0.1Co0.1O2 cathode, which demonstrated excellent cycling stability and high rate performance.

Synthesis of Ni/NiO@MIL-101(Cr) Composite as Novel Anode for Lithium-Ion Battery Application.

The poor conductivity is one of the prime reasons restricted MOFs to be applied in the lithium-ion battery system. For the sake of ameliorate this issue, the Ni/NiO was well loaded on the surface of Cr-based metal organic frameworks (MIL-101) by solution impregnation and in situ reduction method to form Ni/NiO@MIL-101(Cr) composites. The as-synthesized Ni/NiO@MIL-101(Cr) was characterized by X-ray powder diffractions, X-ray photoelectron spectroscopy, field emission scanning electron microscope and transmission electron microscope techniques. When used as anode for LIBs, the Ni/NiO@MIL-101(Cr) composite exhibited high reversible capacity (891 mAh g-1 after 100 cycles at a current density of 200 mA g-1) and stable cycle performance, the coulombic efficiency can maintain in the whole cycle above 95.0%. The reasons for that Ni/NiO@MIL-101(Cr) behaved outstanding electrochemical properties were discussed also. The Ni/NiO@MIL-101(Cr) can be used as promising material for lithium-ion battery application.

Tin oxide evolution by heat-treatment with tin-aminoclay (SnAC) under argon condition for lithium-ion battery (LIB) anode applications

A layered tin-aminoclay structure of high specific surface area and offering great mechanical resistance to stretching is used as an improved anode for lithium-ion battery application. The active nanoparticles (Sn/SnO/SnO2 nanoparticles) are evolved by a heat-treatment process through direct conversion of Sn species within tin-aminoclay structure. Besides, this heat treatment process facilitates removal of oxygen functionalities and homogenization of the tin-aminoclay surface, and also provides great synergistic effects, all leading to improved theoretical specific capacity and electrochemical performance in lithium-ion battery applications. Thus, tin-aminoclay heat-treated at 500 °C under the argon condition is considered to be a most promising candidate anode material one that can deliver a highest initial discharge capacity value of 1,400 mAh g−1, good stability after 95 repeated cycles, and a high reversible capacity of about 500 mAh g−1 at a current density of 100 mA g−1.

Fabricating and probing additive-free electrophoretic-deposited black phosphorus nanoflake anode for lithium-ion battery applications

We, for the first time, report fabrication of additive-free black phosphorous (BP) Li-ion battery without conductive agents and binders in which BP nanoflakes in solution are deposited using electrophoretic deposition (EPD). Addition of NaOH in pure 1-methyl-2-pyrrolidinone (NMP) solution containing BP nanoflakes facilitates the formation of smaller BP nanoflakes from bulk crystals allowing for the use as a battery anode. A remarkable increase in the initial discharging capacity from 91 to 954 mAh/g through simple treatments including the addition of NaOH followed by thermal annealing results from initiation of the multistep reactions associated with the formation of LiP, Li2P, and Li3P.

Effects of thermal annealing on performance of silicon nitride anode for lithium-ion battery applications

The effects of thermal annealing on the performance of hydrogenated silicon nitride anode (prepared by plasma enhanced chemical vapor deposition, PECVD) are investigated by varying annealing temperatures. The relationship between the annealing temperatures, microstructures and electrochemical behaviors of the anodes is revealed. The capacity of the anodes with low-temperature annealing (≤400°C) is quite low firstly but increases abruptly after several charge/discharge activation processes. Due to weak strength of hydrogen-containing bonds in the PECVD silicon nitride, dehydrogenation occurs with cycling, which is effective to activate the anodes and thus result in the abrupt increase in the anode capacity. With increasing the annealing temperature to 450°C, the thermal treatment can break the hydrogen-containing bonds (induce dehydrogenation) and activate the anodes; therefore, the anodes with relatively high-temperature annealing (≥450°C) exhibit a high capacity even with no electrochemical activation processes needed. The mechanical properties of the anodes also depend on the thermal treatment and the anode elastic modulus and hardness increase with increasing the annealing temperature, which results in a poor mechanical stability and thus poor cycling performance of the anode with high-temperature annealing (~600°C). Compared with the anode with lower- or higher-temperature annealing, the anode with an appropriate annealing (~450°C) shows higher and more stable reversible capacity (~1001mAhg−1 at 0.6C over 200cycles) and better rate performance (~327mAhg−1 at 6.0Ag−1).

Binder-free SnO2-TiO2 composite anode with high durability for lithium-ion batteries.

A SnO2–TiO2 electrode was prepared via anodization and subsequent anodic potential shock for a binder-free anode for lithium-ion battery applications. Perpendicularly oriented TiO2 microcones are formed by anodization; SnO2, originating in a Na2SnO3 precursor, is then deposited in the valleys between the microcones and in their hollow cores by anodic potential shock. This sequence is confirmed by SEM and TEM analyses and EDS element mapping. The SnO2–TiO2 binder-free anode is evaluated for its C-rate performance and long-term cyclability in a half-cell measurement apparatus. The SnO2–TiO2 anode exhibits a higher specific capacity than the one with pristine TiO2 microcones and shows excellent capacity recovery during the rate capability test. The SnO2–TiO2 microcone structure shows no deterioration caused by the breakdown of electrode materials over 300 cycles. The charge/discharge capacity is at least double that of the TiO2 microcone material in a long-term cycling evaluation.

Biosynthesized Co-doped TiO2 nanoparticles based anode for lithium-ion battery application and investigating the influence of dopant concentrations on its performance

TiO2 is a good alternative anode material for lithium-ion battery application because of its incomparable high structural stability and safety during the charge/discharge cycles. However, the low intrinsic conductivity of TiO2 has been a limiting factor affecting its cycling and rate capability performance. Here in this work, we present Co-doped TiO2 nanoparticles based anode with good reversibility, cycling stability and rate capability performance for its envisaged application in lithium-ion battery. The Co-doped TiO2 nanoparticles with different Co concentrations (3%, 5%, and 7%) are synthesized using simple and economic biomediated green approach, wherein TiCl4 and Co precursors are allowed to react in Bengal gram bean extract containing biomolecules which act as natural capping agents to control the size of nanoparticles. Among the pure TiO2 and different Co-doped TiO2 samples, the 7% Co-doped TiO2 anode show the highest capacity of 167 mAh g−1 (88.3%) after 100 cycles at the 0.5C current density. The Co-doped TiO2 shows higher and stable coulombic efficiency up to 100 GCD cycles indicating good reversibility. Based on the results, it is expected that the Co-doped TiO2 nanoparticles might be contributing to the enhanced electronic conductivity providing an efficient pathway for fast electron transfer.

Practical considerations of Si-based anodes for lithium-ion battery applications

Using Si-based anodes in Li-ion batteries is one of the most feasible approaches to achieve high energy densities despite their disadvantages, such as low conductivity and massive volume expansion, which cause unstable solid electrolyte interphase layers with mechanical failure. The forefront in research and development to address the above challenges suggests the possibility of fully commercially viable cells using various structural and interfacial modifications. In particular, we present a discussion of each dimension of Si-based anodes in multiple controlled systems, including plain, hollow, porous, and uniquely engineered structures, which are further evaluated based on their anode performances, such as initial reversibility, capacity retention for extended cycles with its efficiency, degree of volume expansion tolerance, and rate capabilities, by several practical standards in half cells. With these practical considerations, multi-dimensional structures with uniform size distributions (micrometers, on average) are strongly desired to satisfy the rigorous requirements for widespread applications. Furthermore, we closely examined several full cells composed of Si-based multicomponent anodes coupled with suitable cathodes based on practical standards to propose future research directions for Si-based anodes to keep pace with the rapidly changing market demands for diverse energy storage systems.

High Rate Performance of a Mn3O4/C Anode Material Prepared By One-Step Pyro-Synthesis for Lithium-Ion Batteries

In response to the ever-increasing global demand for electronic devices, Lithium-ion batteries have taken an important place in meeting this demand since they provide high voltage, high energy density, and are light weight. Nanostructured binary metal oxides (BMOs) which exhibit high theoretical capacity as a result of a conversion reaction. Among the BMOs, the manganese-based oxide hausmannite (Mn3O4) has attracted much attention due to it being low –cost and environmentally benign. A nanostructured Mn3O4/C electrode was prepared by a one-step polyol-assisted pyro-synthesis without any post-heat treatments. The as-prepared Mn3O4/C revealed nanostructured morphology comprised of secondary aggregates formed from carbon-coated primary particles of average diameters ranging between 20 and 40 nm, as evidenced from the electron microscopy studies. The N2 adsorption studies reveal a hierarchical porous feature in the nanostructured electrode. The nanostructured morphology appears to be related to the present rapid combustion strategy. The nanostructured porous Mn3O4/C electrode demonstrated impressive electrode properties with reversible capacities of 666 mAh/g at a current density of 33 mA/g, good capacity retentions (1141 mAh/g with 100% Coulombic efficiencies at the 100th cycle), and rate capabilities (307 and 202 mAh/g at 528 and 1056 mA/g, respectively) when tested as an anode for lithium-ion battery applications.