Rechargeable Lithium Batteries Research Articles

Spontaneous electrochemical stabilization of nanostructured organic electrodes by field-induced charge-transfer

Organic electrodes are promising candidates for the next-generation energy storage system of rechargeable lithium-ion batteries (LIBs) due to their natural abundance and lightweight. However, they have weaknesses: low electrochemical capacity, low capacity retention, and elution of active electrode materials. In this study, the field-induced charge-transfer route and nanostructuring are developed to resolve the poor electrochemical performance. When the 5,10-Dihydro-5,10-dimethylphenazine (DMPZ) with a nanoporous structure is homogeneously mixed with organic and metal nanoparticles (perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), perylenetetracarboxylic diimide (PTCDI), Flavanthrone, and Aluminum), the organic nanocomposite cathodes exhibit a remarkable enhancement in electrochemical performance: unprecedented cycling stability with capacity retention over 90% up to 600 redox cycles, a high specific capacity of 215 mA·h·g−1 at the current density of 150 mA·g−1, and an excellent rate-capability for the DMPZ and PTCDA nanocomposite cathode. The excellent specific capacity and retention of the redox reaction are due to the fast charge transport through the nanoporous network of the nanocomposites with a high specific surface area. The charge-transfer between the vicinal organic materials with different ionization energies is induced by the charging potential of the redox reaction, which suppresses the elution during the oxidation process and leads to the remarkable cyclability. The all-organic pouch-type full-cell, composed of a PTCDI anode and the nanocomposite cathode, is realized with excellent cyclability of 76% capacity retention at the 200th cycle. This work provides a promising way of developing stable organic electrodes for electrocatalytic applications as well as LIBs.

Layer-By-Layer (LBL) hybrid MOF coating for graphene-based multilayer composite: Synthesis and application as anode for lithium ion batteries

The hybrid anodic materials with high porosity and low charge resistance exhibit high specific capacity and stable cyclic stability for lithium ion battery (LIBs). For this purpose, three-dimensional hollow material, metal organic framework (MOF-199) was coated over the active surface of oxidized derivative of graphene (Graphene oxide, GO), via layer-by-layer (LBL) coating method. Cupric acetate and benzene-1,3,5-tricarboxylic acid [Cu3(BTC)2], were alternatively coated on the active surface of GO as an anode material, to enhance the structural diversity and reduce the synergistic effect of insertion and extraction of Li+ ions for LIBs. Sharp absorption peaks from 1620 cm−1 to 1360 cm−1 and intense ring bends ∼1000 cm−1 was identified through FTIR. Powder XRD provides the evidence for size reduction of Cu3(BTC)2@GO composite (32.6 nm) comparative to GO (43.7 nm). Outcome of EIS analysis shows the charge transfer resistance of simple GO is 2410 Ω, which is 4 times higher than Rct of Cu3(BTC)2@GO composite (590 Ω). Similarly the Warburg impedance co-efficient for simple GO (448.8 Ωs−1/2) is also higher than Aw of Cu3(BTC)2@GO composite (77.64 Ωs−1/2). The synthesized material show high initial charge/discharge capacity, 1200/1420 mAh/g with 85% Coulombic efficiency and reversible discharge capacity, 1296 mAh/g after 100 cycles at 100 mA/g current density. The 98.9% Coulombic efficiency and 91% retaining capacity of composite at 100th cycle with cyclic stability, provides the phenomenon approach towards the rechargeable LIBs for industrial technology.

Preparation and electrochemical performance of foam–like CeO2 nanofoam as negative electrode material for rechargeable lithium–ion batteries

Oxides of transition metal oxides have been discovered as candidate anode materials for lithium–ion batteries (LIBs) owing to their extraordinary specific capacity. Moreover, to improve the electrochemical performance of energy–storage devices, the use of porous electrode materials is considered one of the most effective strategies. Herein, we report highly porous cerium oxide (CeO2) nanofoam synthesized using a facile and simple solution combustion technique (SCT). In this technique, we use two different fuels to synthesis CeO2. The prepared S–CeO2 nanofoam delivers the highest specific surface area of 142.99 m2 g−1 with a highly enhanced contact area between the electrolyte and electrode. The prepared S–CeO2–based anode offers an initial specific capacity of 1154 mAh g−1 at 100 mA g−1, which is three times higher than that of carbon–based materials. Additionally, the mesoporous S–CeO2 nanofoam exhibits good rate capability at high current densities. These attractive results suggest that S–CeO2 has great potential for use in high–performance LIB applications.

Density Functional Theory Study of Bilayer Borophene-Based Anode Material for Rechargeable Lithium Ion Batteries.

The bilayer borophene has been successfully fabricated in experiments recently and possesses superior antioxidation and robust metallic properties, which holds great promise for the future anode materials of Li-ion batteries. Herein, using first-principles calculations, two bilayer borophenes including P6/mmm or P6̅m2 symmetry groups with or without vacancy defects are comprehensively explored and acted as electrode materials with high performance in Li-ion batteries. The charge density difference, adsorption energies, and Bader charge analysis are calculated and discussed for single lithium adsorbed on bilayer borophene. The results shown that with the increase of lithium concentration, the adsorption energies are rapidly decreased due to the repulsion of boron atoms except for the P6̅m2 systems with double side adsorption and corresponding energies remain the narrow range. Meanwhile, the partial density of states shows metallic character after lithium adsorption and indicates good conductivity for the charge-discharge process. Furthermore, small diffusion barriers, low average open-circuit voltage, can be achieved, and large storage capacity is up to 930.2 mA h/g at the lower lithium content of 0.375. These results propose that bilayer borophene might be a good choice for anode material applications in future Li-ion batteries with fast ion diffusion and high power density.

One pot green synthesis of few-layer graphene (FLG) by simple sonication of graphite and Azardirachta Indica resin in water for high-capacity and excellent cyclic behavior of rechargeable lithium-ion battery

A simple, green, and eco-friend route is employed for the preparation of few-layer graphene using Azardirachta Indica resin (AZIr) in water. In addition, the preparation of the solvent (AZIr) for the exfoliation of graphene involves various steps, including vacuum filtration and surface tension optimization by the capillary rise method. It has been demonstrated that the 4 h sonication effectively exfoliated graphite to form a Few-Layer Graphene (FLG) sheet. Structural, morphological, and surface topographical analysis were performed using X-ray diffraction, Raman spectrum, FTIR spectrum, atomic force microscopy, and Scanning electron microscope. The as-prepared FLG was demonstrated as anode material for lithium-ion batteries¸ exhibiting a high initial capacity of 464 mAh g−1 at 0.1C and excellent cyclic performance of 527 mAh g−1 at 200th cycle with 100 % capacity retention. The maximum capacity of 281 mAh g−1 was achieved when tested at a high current rate of 10C. These results suggest that few-layer graphene is a promising material for high-performance Li-ion battery applications.

Surface modification of lithium metal anode with lithium silicate-lithium phosphate composite layer for enhanced cycling stability

Lithium metal anode with exceptionally high capacity is very attractive for next-generation anode material of lithium rechargeable batteries, but the safety problems and low Coulombic efficiency have retarded its commercialization. Despite the enormous efforts made to solve the problem of lithium metal anode, its practical use still appears to have a long way to go. In this study, to expedite the problem-solving, we suggest the use of a lithium silicate-lithium phosphate (SP) composite layer to suppress the dendritic growth of lithium and the formation of dead lithium. The composite layer is formed by simply dipping lithium metal in a mixed solution of tetraethyl orthosilicate and phosphoric acid. The synergistic effect of lithium silicate and lithium phosphate – high Li-ion conductivity and high Young's modulus of the inorganic layer – results in enhanced cycling stability of Li || Li symmetric cell and LiFePO4 || Li cell. The change in morphology of the lithium metal anode surface after cycling confirms that the SP layer mitigates the excessive dendritic growth of lithium and dead lithium formation, stabilizing the interface of lithium metal anode/electrolyte.

Mesoporous Cr2O3/MWCNTs/PANI nanocomposite as a high performance anode material for rechargeable lithium ion batteries

Chromium oxide (Cr2O3) has been considered as a promising anode material for lithium-ion batteries (LIBs). However, it is accompanied by a large volumetric expansion which compromises battery performance by damaging internal structure of the material. In this study, dual modification is achieved by developing Cr2O3 nanocomposite with multi-walled carbon nanotubes (MWCNTs) by inexpensive and reproducible co-precipitation method which reduces volume changes by enhancing electronic conductivity and mechanical strength. Meanwhile, polyaniline (PANI) coating was employed by in-situ polymerization of aniline monomer that promotes lithium-ion conductivity and facilitates high electron transportation, thus resulting in excellent stability. This research mainly signifies the effect of PANI coating, where PANI offers conductive contact between active material and electrolyte. The homogenous nanocomposite of Cr2O3-MWCNTs and PANI exhibit good electrochemical performance. A discharge capacity of Cr2O3-MWCNTs(12%)-PANI is found to be 815 mAh g−1 at 100 mA g−1 with coulombic efficiency of 97.5 %. Moreover, the nanocomposite exhibits good rate capability and cyclic stability.

Sodium and potassium ion storage in cation substituted 2D MoWSe2: insights into the effects of upper voltage cut-off

The superior properties, such as large interlayer spacing and the ability to host large alkali-metal ions, of two-dimensional (2D) materials based on transition metal di-chalcogenides (TMDs) enable next-generation battery development beyond lithium-ion rechargeable batteries. In addition, compelling but rarely inspected TMD alloys provide additional opportunities to tailor bandgap and enhance thermodynamic stability. This study explores the sodium-ion (Na-ion) and potassium-ion (K-ion) storage behavior of cation-substituted molybdenum tungsten diselenide (MoWSe2), a TMD alloy. This research also investigates upper potential suspension to overcome obstacles commonly associated with TMD materials, such as capacity fading at high current rates, prolonged cycling conditions, and voltage polarization during conversion reaction. The voltage cut-off was restricted to 1.5 V, 2.0 V, and 2.5 V to realize the material’s Na+ and K+ ion storage behavior. Three-dimensional (3D) surface plots of differential capacity analysis up to prolonged cycles revealed the convenience of voltage suspension as a viable method for structural preservation. Moreover, the cells with higher potential cut-off values conveyed improved cycling stability, higher and stable coulombic efficiency for Na+ and K+ ion half-cells, and increased capacity retention for Na+ ion half-cells, respectively, with half-cells cycled at higher voltage ranges.

Facile Synthesis of Ordered Mesoporous Orthorhombic Niobium Oxide (T-Nb2O5) for High-Rate Li-Ion Storage with Long Cycling Stability

Herein, we describe the synthesis and evaluation of hierarchical mesoporous orthorhombic niobium oxide (T-Nb2O5) as an anode material for rechargeable lithium-ion batteries (LIB). The as-synthesized material addresses key challenges such as beneficial porous structure, poor rate capability, and cycling performance of the anode for Li-ion devices. The physicochemical characterization results reveal hierarchical porous nanostructure morphology with agglomerated particles and a 20 to 25 nm dimension range. Moreover, the sample has a high specific surface area (~65 m2 g−1) and pore volume (0.135 cm3 g−1). As for the application in Li-ion devices, the T-Nb2O5 delivered an initial discharging capacity as high as 225 mAh g−1 at 0.1 A g−1 and higher rate capability as well as remarkable cycling features (~70% capacity retention after 300 cycles at 250 mA g−1) with 98% average Coulombic efficiency (CE). Furthermore, the scan rate-dependent charge storage mechanism of the T-Nb2O5 electrode material was described, and the findings demonstrate that the electrode shows an evident and highly effective pseudocapacitive Li intercalation behaviour, which is crucial for understanding the electrode process kinetics. The origin of the improved performance of T-Nb2O5 results from the high surface area and mesoporous structure of the nanoparticles.

Importance of heat transfer in membrane extrusion process involving flow-induced crystallization

In this work, a recently proposed viscoelastic non-isothermal extrusion film casting model, which accounts for flow-induced crystallization, was generalized by including heat transfer coefficient considering radiation, natural and forced convection. This variable heat transfer coefficient (HTC) based model was found to have the ability to predict the measured temperature, velocity, width and crystallization profile for process conditions typical for the production of polypropylene energy storage membranes. The difference between variable and constant HTC based models was investigated in more details by using systematic parametric study. The obtained results suggest that the use of the variable-HTC model should be preferred for polymer energy membrane production over the constant-HTC models, and flow-induced crystallization should always be included, otherwise the extrusion film casting model loses its ability to describe experimental reality. It is believed that the proposed model and the obtained results can help to understand the optimal process conditions for the production of polymer membranes for energy storage due to their use in rechargeable lithium-ion batteries and special energy storage.

Sulfurized poly(o-phenylenediamine) as a novel high-performance solid-phase conversion sulfur cathode

The combination of sulfurized polymer cathode and ester-type electrolyte can realize the solid-phase conversion of sulfur cathode, which is a promising solution of the dissolution issue of Li–S batteries. In this regard, sulfurized polyacrylonitrile (SPAN) is the most famous material and few attempts have been made to challenge it in the past two decades. Herein, we report sulfurized poly(o-phenylenediamine) (SPoPDA) as its supplement or alternative for rechargeable lithium batteries. Compared with SPAN, SPoPDA shows higher ability to covalently bond with sulfur (from ∼50 to ∼60 wt%), similar reversible capacity (∼600 mAh g−1), better cycling stability (with only 2% loss of charge capacity during 100 cycles), and faster reaction kinetics. The molecular structures and electrochemical reaction mechanisms of them have been quantitatively analyzed, and the electrode structure variation of SPoPDA during discharge–charge process has been thoroughly investigated. This work provides not only a novel sulfurized polymer cathode material with low cost, easy synthesis, and high electrochemical performance, but also clearer mechanism understanding of solid-phase conversion sulfur cathode, which are of significant importance for the development of Li–S batteries towards practical application.

Electron-donating/withdrawing groups functionalized porphyrin complex as high performance organic lithium batteries

Organic electrode materials exhibit wide application prospects in the electrochemical energy storage devices, owing to their adjustable structure, low cost and environmental friendliness. Though organic electrode materials delivered high theoretical energy density, but suffer from low electronic conductivity and high solubility. In order to decrease the solubility and regulate redox potential of the porphyrin molecule, electron-donating group and electron-withdrawing group were functionalized on bipolar porphyrin complex. Herein, we report two novel cathodes of [5,15-bis(ethynyl)-10,20-bis(5-methylthienyl) porphinato] copper(II) (CuDETMP) and [5,15-bis(ethynyl)-10,20-bis(5-chlorothienyl)porphinato]copper(II) (CuDETCP). Strong electron withdrawing effect of chlorine functionalized groups enables higher reversible capacity (≈125 mAh/g vs 100 mAh/g at 1 A/g), while with electron donating group of CuDETMP showed stable cycling capability. Extremely cycling stability up to 2000 cycles with capacity retention more than 80% was achieved in both electrodes. Compared to CuDETMP, higher capacity of CuDETCP benefits from reaction between chlorine atoms and Li cations, which can be a partially reversible process lead to degraded capacity. Nevertheless, CuDETMP and CuDETCP can deliver reversible capacity and provide multiple-redox sites enabling high energy density in respective proper voltage ranges. Through comparison towards physical and electrochemical properties of two molecules, mechanism between substituent and electrochemical performance was clarified. This work not only elaborates the significant correlation between different substituents and electrochemical performance, but also provides a novel strategy to tunable molecular design of organic electrode materials for high-energy rechargeable organic lithium batteries.

Semi-Ionic C-F bond enabling fluorinated carbons rechargeable as Li-ion batteries cathodes

Fluorinated carbon (CFx) cathodes possess the highest theoretical energy density among lithium primary batteries. However, achieving reversibility in CFx remains a significant challenge. This work employs a high-voltage sulfolane electrolyte and achieves a highly reversible CFx cathodes in lithium-ion batteries (LIBs) via fine modification of the C-F bond character. The improved reversibility of CFx originates from the semi-ionic CFx phase, with a superior bond length and weaker bond energy than a covalent bond. This characteristic significantly mitigates the challenges encountered during the charging process. We screen and identify the fluorinated graphene CF1.12 as a suitable cathode, providing an appropriate fluorine content and sufficient semi-ionic C-F bonds for rechargeable LIBs. This fluorinated graphene CF1.12 exhibits an initial discharge specific capacity of 814 mAh g−1 and a reversible discharge specific capacity of 350 mAh g−1. This work provides a new clue for chemical bond regulation studies and provides insights into stimulating reversibility of primary-cell cathodes.

Freestanding hybrid electrospun membranes consisting of TiO2 nanotube-core nanocarbon as high-performance and long-lifespan anodes for lithium-ion batteries

To develop an efficient anode for lithium ion batteries (LIBs), we prepare an ultralong oxygen-deficient titanium dioxide nanotubes (TNTs)-based hybrid electrospun carbon nanofibers (CNFs) membrane (TNT@CNFs). As an anode, this membrane possesses several advantages, including fast ion/electron transport path due to the TNTs’ novel structure, protection from direct contact between TNTs and electrolyte owing to the carbon skeleton, improved electrical conductivity on account of the internal structural consistency of TNTs, and enhanced ion transport because of oxygen vacancies. As a result, the anode with a relatively low content of TNT (33TNT@CNFs) exhibits an ultra-high reversible specific capacity of 350 mAh/g after 200 cycles at a relatively low current density (0.2 A/g), while the anode with a high content of TNT (50TNT@CNFs) exhibits an ultra-high rate performance of 187 mAh/g at 10 A/g after 10,000 cycles, indicating its superior electrochemical kinetics at high-rate and long cyclic lifespan. This can find proof from the dynamic analysis that both the surface capacitance process and the diffusion-controlled insertion have a great contribution. The strategy employed in this work can facilitate access to a variety of one-dimensional (1D) nanostructured composites and can promote new research on electrodes for ultrafast rechargeable LIBs.

PVDF-HFP/LLZTO composite electrolytes with UV cure for solid-state lithium rechargeable batteries

PVDF-HFP/LLZTO composite electrolytes with UV cure for solid-state lithium rechargeable batteries

Li–O2/Air Batteries Using Ionic Liquids – A Comprehensive Review

AbstractThe remarkable surge in energy demand has compelled the quest for high‐energy‐density battery systems. The Li–O2 battery (LOB) and Li–air battery (LAB), owing to their extremely high theoretical energy density, have attracted extensive research in the past two decades. The commercial development of LOB is hampered due to the numerous challenges its components present. Ionic liquids (ILs) are considered potential electrolyte solvents of LOBs and LABs due to their excellent electrochemical stability, thermal stability, non‐flammability, low flammability, and O2 solubility. In addition to electrolyte solvents, ILs also have other applications in LOB and LAB systems. This review reports the progress of IL‐based LOBs and LABs over the years since treported for the first time in 2005. The impact of the physiochemical properties of ILs on the performance of LOB and LAB at various operating conditions is thoroughly discussed. The various methodologies are also summarized that are employed to tune ILs’ physiochemical properties to render them more favorable for rechargeable lithium batteries. Tunable properties of ILs create the possibility of designing cost‐effective batteries with excellent safety, high energy density and high power density, and long‐term stability.

Ferrite Nanoparticles as Catalysts in Organic Reactions: A Mini Review

Ferrites have excellent magnetic, electric, and optical properties that make them an indispensable choice of material for a plethora of applications, such as in various biomedical fields, magneto–optical displays, rechargeable lithium batteries, microwave devices, internet technology, transformer cores, humidity sensors, high-frequency media, magnetic recordings, solar energy devices, and magnetic fluids. Recently, magnetically recoverable nanocatalysts are one of the most prominent fields of research as they can act both as homogeneous and heterogenous catalysts. Nano-ferrites provide a large surface area for organic groups to anchor, increase the product and decrease reaction time, providing a cost-effective method of transformation. Various organic reactions were reported, such as the photocatalytic decomposition of a different dye, alkylation, dehydrogenation, oxidation, C–C coupling, etc., with nano-ferrites as a catalyst. Metal-doped ferrites with Co, Ni, Mn, Cu, and Zn, along with the metal ferrites doped with Mn, Cr, Cd, Ag, Au, Pt, Pd, or lanthanides and surface modified with silica and titania, are used as catalysts in various organic reactions. Metal ferrites (MFe2O4) act as a Lewis acid and increase the electrophilicity of specific groups of the reactants by accepting electrons in order to form covalent bonds. Ferrite nanocatalysts are easily recoverable by applying an external magnetic field for their reuse without significantly losing their catalytic activities. The use of different metal ferrites in different organic transformations reduces the catalyst overloading and, at the same time, reduces the use of harmful solvents and the production of poisonous byproducts, hence, serving as a green method of chemical synthesis. This review provides insight into the application of different ferrites as magnetically recoverable nanocatalysts in different organic reactions and transformations.

40 Years of Low-Temperature Electrolytes for Rechargeable Lithium Batteries.

Rechargeable lithium batteries are one of the most appropriate energy storage systems in our electrified society, as virtually all portable electronic devices and electric vehicles today rely on the chemical energy stored in them. However, sub-zero Celsius operation, especially below -20 °C, remains a huge challenge for lithium batteries and greatly limits their application in extreme environments. Slow Li+ diffusion and charge transfer kinetics have been identified as two main origins of the poor performance of RLBs under low-temperature conditions, both strongly associated with the liquid electrolyte that governs bulk and interfacial ion transport. In this review, we first analyze the low-temperature kinetic behavior and failure mechanism of lithium batteries from an electrolyte standpoint. We next trace the history of low-temperature electrolytes in the past 40 years (1983-2022), followed by a comprehensive summary of the research progress as well as introducing the state-of-the-art characterization and computational methods for revealing their underlying mechanisms. Finally, we provide some perspectives on future research of low-temperature electrolytes with particular emphasis on mechanism analysis and practical application.

Enabling the reversibility of anhydrous copper(II) fluoride cathodes for rechargeable lithium batteries via fluorinated high-concentration electrolytes

Anhydrous copper(II) fluoride (CuF2) has a high specific capacity of 528 mA h g−1 with an operating voltage of 3.55 V vs. Li/Li+, achieving a high gravimetric energy density of 1874 W h kg−1, which makes it a promising cathode candidate for next-generation rechargeable lithium (Li) batteries. However, the notorious dissolution of Cu during charging triggers the rapid failure of the CuF2 cathode, impeding its development. In this work, the reversibility of the anhydrous CuF2 electrode was enabled via the use of a fluorinated high-concentration (FHC) electrolyte to effectively suppress the dissolution of Cu. With the FHC electrolyte, the CuF2-Ketjen Black nanocomposite cathode delivered a reversible capacity of 228 mA h g−1 after 30 cycles, which nearly tripled that of the baseline electrolyte. Thus, the strategy of electrolyte engineering is proposed to harness CuF2 as a high-capacity cathode material for Li batteries.

Ferrocene-Derived Sulfur-Rich Cathode for High-Performance Rechargeable Lithium Batteries

Ferrocene-Derived Sulfur-Rich Cathode for High-Performance Rechargeable Lithium Batteries