Electrochemical Performance For Lithium-ion Batteries Research Articles

A Novel 4-Fluorophenyl Isocyanate Additive Constructing Solid Cathodes-Electrolyte Interface for High-Performance Lithium-Ion Batteries.

Building a stable cathode-electrolyte interface (CEI) is crucial for achieving high-performance layered metal oxide cathode materials LiNixCoyMn1-x-yO2 (NCM). In this work, a novel 4-fluorobenzene isocyanate (4-FBC) electrolyte additive that contains isocyanate and benzene ring functional groups is proposed, which can form robust and homogeneous N-rich and benzene ring skeleton CEI film on the cathode surface, leading to significant improvement in the electrochemical performance of lithium-ion batteries. Taking LiNi0.5Co0.2Mn0.3O2 (NCM523) as an example, the NCM523/SiO@Graphite pouch full cells with electrolytes containing a mass fraction of 1% 4-FBC additives demonstrate improved capacity retention after 200 cycles, retaining capacity retention rates of 81.3%, which is much higher than that of 39.1% without additive. The improvement can be ascribed to the mitigation of electrolyte decomposition and inhibition of transition metal ions the dissolution from the cathode material due to the stable CEI film. Moreover, the electrochemical performance enhancement can also be achieved in high voltage and Ni-rich cathode materials, indicating the universality and effectiveness of this strategy for the practical applications of high energy density lithium-ion batteries.

The Effect of a Dual-Layer Coating for High-Capacity Silicon/Graphite Negative Electrodes on the Electrochemical Performance of Lithium-Ion Batteries

Silicon-based electrodes offer a high theoretical capacity and a low cost, making them a promising option for next-generation lithium-ion batteries. However, their practical use is limited due to significant volume changes during charge/discharge cycles, which negatively impact electrochemical performance. This study proposes a practical method to increase silicon content in lithium-ion batteries with minimal changes to the manufacturing process by using dual-layer electrodes (DLEs). These DLEs are fabricated with two slurries containing silicon and graphite as active materials. Notably, the electrode with the silicon as the outermost layer on top of the graphite layer (Si-on-top) demonstrated a superior initial capacity of 935 mAh/g and retained 70% of its capacity (537 mAh/g) after 100 cycles at 0.5 C. In contrast, a single-layered electrode (SLE) with a silicon–graphite mixture retained only 50.3% of its capacity (370 mAh/g) under the same conditions. These findings suggest that DLEs, particularly with the silicon layer located on top, effectively increase silicon content in the negative electrode while remaining compatible with existing manufacturing processes. This approach offers a realistic strategy for enhancing the performance of lithium-ion batteries without significant process modifications.

A high-safety lithium-ion battery electrospun separator with Si3N4-assisted sulfonated poly(ether ether ketone) for regulating lithium flux

The uncontrolled lithium (Li) dendrite growth significantly impacts the safety performance of polymer separators. To mitigate this growth, this study introduces Si3N4 into sulfonated poly(ether Ether Ketone) (SPEEK) and prepares Si3N4/SPEEK composite separators via electrospinning. At the interface between the Si3N4/SPEEK separator and the Li anode, the Si nanowires that form impede Li dendrite growth, thereby enhancing the electrochemical performance of lithium-ion batteries (LIBs). The Li deposition test of the 10 % Si3N4/SPEEK separator can operate for 1000 h without short-circuiting. Additionally, the LiFePO4||Li cell with the 10 % Si3N4/SPEEK separator shows improved initial discharge capacity (157.8 mAh g−1 at 1C) and superior rate performance (125 mAh g−1 at 10C). Moreover, the nano-scale Si3N4 endows the separator with robust thermal and mechanical properties. The FLIR observations reveal that the 10 % Si3N4/SPEEK separator maintains uniform thermal distribution and structural integrity even at 300 °C, ensuring safe battery operation at high temperatures. The additional load of the 10 % Si3N4/SPEEK separator can reach 10.2 mN, which enhances the puncture resistance of the separator. This work provides a solid approach for the application of SPEEK as a high-safety and high-rate LIB separator.

Surface functionalization of cellulose derived from hemp by tetraethyl orthosilicate (TEOS) and poly vinylidene fluoride (PVDF)-based composite separator membrane for lithium-ion batteries (LIBs)

Separators play a crucial role in enhancing the electrochemical performance of lithium-ion batteries (LIBs). However, achieving separators with exceptional electrochemical performance and high stability remains a significant challenge. In this study, we meticulously designed composite membranes based on polyvinylidene fluoride (PVDF) with varying contents of microcrystalline cellulose/tetraethyl orthosilicate (MCC/TEOS). The increase in hydrophilicity of PVDF by adding MCC-TEOS weight contents endowed the 3 wt% MCC/TEOS-based PVDF separator membrane with superior electrolyte absorption and reduced resistance, resulting in an impressive ionic conductivity of 0.514 mS/cm higher than the pristine PVDF membrane (0.253 mS/cm). Furthermore, the LIB cell utilizing the 3 wt % MCC/TEOS-based PVDF separator membrane consistently demonstrated stable charge/discharge profiles at a rate of 0.2C, achieving a specific capacity of 98 mAh/g, compared to only 43 mAh/g for the pristine PVDF membrane. These findings underscore the significant potential of MCC/TEOS as a biofiller for bio-membranes, making it an optimal choice for applications in LIBs.

Unraveling the impact of pore length on the conversion reaction of Fe3O4/carbon anodes in lithium-ion batteries

Despite numerous studies investigating Fe3O4/porous carbon anode materials for high-performance lithium-ion batteries (LIBs), the inherent limitations of the Fe3O4 conversion reaction, such as low reversibility and sluggish kinetics, continue to pose significant challenges. While modifying the porous structure of Fe3O4 anodes has demonstrated considerable promise in overcoming these limitations, the precise relationship between the porous structure and Fe3O4 conversion behavior still remains unclear. Here, we explore the impact of the pore length of the anode active material on the electrochemical performance of LIBs. Using two different composites of Fe3O4 and porous carbon with varying pore lengths as model materials, we conduct various in-depth electrochemical and ex-situ analyses. Our findings confirm that a shorter pore length facilitates higher Li+ ion diffusivity compared to longer pore length. Consequently, the conversion reaction of Fe3O4 to Fe and Li2O during lithiation process can be expedited, leading to a decrease in the resistance at the solid electrolyte interphase. As a result, we demonstrate that shortening the pore length of the porous anode composite materials can enhance the initial Coulombic efficiency (CE), reversible capacity, and rate capability of LIBs.

Influence of Mechanical Degradation in Polycrystalline NMC Particles on the Electrochemical Performance of Lithium-Ion Batteries

Lithium-ion batteries (LIBs) have gained widespread popularity for energy storage systems owing to their high coulombic efficiency and energy density. Within the cathode electrode materials of LIBs, the structural integrity of secondary particles, composed of randomly oriented single-crystal primary active particles, is crucial for sustained performance. The fracture of these particles can occur due to both mechanical stress and chemical interactions within the solid. Modeling LIBs presents a multiphysics challenge as it involves addressing the electro-chemo-mechanical phenomena and their interactions across various length scales. During electrochemical cycling, volume changes in active particles induce mechanical stresses, while the mechanical state of the battery influences the diffusion of lithium.This study proposes a numerical modeling framework to investigate the degradation of active material particles and its impact on electrochemical performance. The model integrates mechanical and electrochemical processes, solving nonlinear equations related to surface charge transfer, lithium diffusion, and mechanical stresses. By incorporating phase field damage, the model tracks crack evolution and mechanical failure of active particles. The coupled equations are solved within a finite element framework using COMSOL Multiphysics.Notably, the model offers numerical insights into intergranular and transgranular fracture within secondary active material particles. The infiltration of liquid electrolyte into cracks is identified as a positive effect, reducing electrochemical overpotential by increasing electrochemically active surface area from particle cracking. However, prolonged cycling with particle cracking poses a notable threat to battery performance and capacity. This comprehensive numerical modeling approach provides valuable insights into the intricate interplay of mechanical and electrochemical factors governing LIB performance and degradation.

The Role of Electrolyte Composition in Enhancing the Performance of Graphene Batteries

Graphene is a promising anode material for the next generation batteries. Understanding the interactions of the graphene surface with common and novel electrolyte solvents and additives is important in improving the overall electrochemical performance of lithium-ion batteries. Electrolyte additives play important role in the formation of solid-electrolyte interface (SEI) on the anode surface and can increase the capacity and cycling stability of the battery. This presentation will discuss the design strategy of electrolyte formulations for long-cycle high-energy graphene-based batteries and report results on the cycling stability of the graphene batteries for Low Earth Orbit satellites.

Vanadium-doped Li6.7La3Zr1.7V0.3O12 and PVDF-HFP enhanced the ionic conductivity and cycling stability of composite solid electrolytes for All-Solid-State lithium batteries

Solid electrolytes receive widespread attention due to their high safety, high energy density and simplicity of processing. However, the poor interface stability between the solid electrolyte and the electrode leads to a significant increase in interface resistance, greatly reducing the electrochemical performance of lithium-ion batteries (LIBs). Here we designed and prepared a new type of solid composite electrolytes (SCEs), which were composed of poly (ethylene oxide) (PEO) blended with poly (vinylidene fluoride-hexafluoro propylene) (PVDF-HFP) and doped with cubic phase Li6.7La3Zr1.7V0.3O12 (LLZVO) particles. Compared with our previous work, the addition of PVDF-HFP can further reduce the crystallinity of PEO, limit the formation of lithium dendrites, and make the electrolyte/electrode interface more stable. The SCEs had better ionic conductivity of 2.04 × 10-4 S cm−1 and 2.03 × 10-3 S cm−1 at 30 ℃ and 80 ℃, respectively, and the Li/SCEs/Li symmetrical battery cycled for 1800 h without short circuit. Moreover, the coulombic efficiency of LiFePO4/SCEs/Li battery remained at 98 % after 300 cycles. This opens up a new direction for the research of garnet-type composite solid electrolytes with lower interface resistance.

Predicting doping strategies for ternary nickel–cobalt–manganese cathode materials to enhance battery performance using graph neural networks

The exceptional electrochemical performance of lithium-ion batteries has spurred considerable interest in advanced battery technologies, particularly those utilizing ternary nickel–cobalt–manganese (NCM) cathode materials, which are renowned for their robust electrochemical performance and structural stability. Building upon this research, investigators have explored doping additional elements into NCM cathode materials to further enhance their electrochemical performance and structural integrity. However, the multitude of doping strategies available for NCM battery systems presents a challenge in determining the most effective approach. In this study, we elucidate the potential of ternary NCM systems as cathode materials for lithium-ion batteries. We compile a comprehensive database of lithium-ion batteries employing NCM systems from various sources of prior research and develop a corresponding data-driven model utilizing graph neural networks to predict optimal doping strategies. Our aim is to provide insights into the NCM-based battery systems for both fundamental understanding and practical applications.

Enhancing electrochemical performance of lithium-ion batteries with diverse nanomaterials

Abstract Although lithium-ion batteries (LIBs) can be widely used, there are some challenges such as safety risks, lower energy density compared to fossil fuels, high cost, long charging times and limited range in electric vehicles. Nanomaterials, with their unique properties and surface effects, can effectively address these challenges and improve the electrochemical performance of LIBs. This research introduces six types of nanomaterials used in LIBs, including TiS3 nanoflakes, ZnMn2O4 nanobundles, ZrO2 surface-modified cathode material, nitrogen-doped carbon fibers with tin (Sn) nanoparticles, carbon nanosheets, and nanostructured bismuth-carbon composites. These recent advancements in nanomaterials can improve electrochemical performance of LIBs, such as specific capacity, cycling ability and stability. The study offers some innovative insights and approaches in using nanomaterials and synthesizing them for emerging battery technologies. In addition, this research is wished to provide a fresh perspective and methodology that can advance the performance and design of LIBs, and provide a new design approach for nanomaterials.

Empowering lithium-ion batteries: The potential of 2D o-Al2N2 as an exceptional anode material through DFT analysis

Finding an appropriate new anode material with high electrochemical performance for lithium-ion batteries (LIBs) is considered one of the significant challenges for both the academic and industrial research communities. Herein, we propose to explore the efficiency of a newly designed two-dimensional (2D) material, named orthorhombic dialuminium dinitride (o-Al2N2), as an alternative anode material for LIB systems through first-principles calculations and ab initio molecular dynamics (AIMD) simulations. The obtained results show that orthorhombic-Al2N2 exhibits a high specific capacity of 1144.2913 mAhg−1, an operating voltage around 0.575 V, and a low kinetic diffusion barrier of 0.26 eV. These results prove the suitability of the o-Al2N2 monolayer as a promising anode material for LIBs with high structural stability, strong binding energy towards lithium adsorbent, fast lithium diffusion, and a high theoretical capacity. These features rank the 2D o-Al2N2 monolayer among the best choices for the anode part of the next-generation rechargeable LIBs.

Impact of Mechanical Degradation in Polycrystalline NMC Particle on the Electrochemical Performance of Lithium-Ion Batteries

Lithium-ion batteries (LIBs) are widely chosen for energy storage owing to their high coulombic efficiency and energy density. Within the positive electrode materials of LIBs, the structural integrity of secondary particles, composed of randomly oriented single-crystal primary particles, is crucial for sustained performance. These particles can fracture as a result of both mechanical stress and chemical interactions within the solid. Modelling LIBs is a complex task involving electro-chemo-mechanical phenomena and their interactions on different length scales. This study proposes a numerical modeling framework to investigate the active particle degradation and its impact on electrochemical performance. The model integrates mechanical and electrochemical processes, tracking crack evolution and mechanical failure through phase field damage. The coupled time-dependent non-linear partial differential equations are solved in a finite element framework using COMSOL Multiphysics. The model offers numerical insights into intergranular and transgranular fracture within secondary particles. The electrolyte infiltration into cracks reduces the electrochemical overpotential due to the increase in electrochemically active surface area, positively affecting performance. However, prolonged cycling with particle cracking poses severe threat to the battery performance and capacity. This comprehensive numerical modeling approach provides valuable insights into the intricate interplay of mechanical and electrochemical factors governing LIB performance and degradation.

Halloysite nanotubes enhanced polyimide/oxidized-lignin nanofiber separators for long-cycling lithium metal batteries

The high energy density and robust cycle properties of lithium-ion batteries contribute to their extensive range of applications. Polyolefin separators are often used for the purpose of storing electrolytes, hence ensuring the efficient internal ion transport. Nevertheless, the electrochemical performance of lithium-ion batteries is constrained by its limited interaction with electrolytes and poor capacity for cation transport. This work presents the preparation of a new bio-based nanofiber separator by combining oxidized lignin (OL) and halloysite nanotubes (HNTs) with polyimide (PI) using an electrospinning technique. Analysis was conducted to examine and compare the structure, morphology, thermal characteristics, and EIS of the separator with those of commercially available polypropylene separator (PP). The results indicate that the PI@OL and PI-OL@ 10 % HNTs separators exhibit higher lithium ion transference number and ionic conductivity. Moreover, the use of HNTs successfully impeded the proliferation of lithium dendrites, hence exerting a beneficial impact on both the cycle performance and multiplier performance of the battery. Consequently, after undergoing 300 iterations, the battery capacity of LiFePO4|PI-OL@ 10 % HNTs|Li stays at 92.1 %, surpassing that of PP (86.8 %) and PI@OL (89.6 %). These findings indicate that this new bio-based battery separator (PI-OL@HNTs) has the great potential to serve as a substitute for the commonly used PP separator in lithium metal batteries.

Continuum insight into the effects of electrode design parameters on the electrochemical performance of lithium-ion batteries

Lithium-ion batteries energy and power density strongly depend on the type of active material and the electrode design parameters. An in-depth understanding of the effect of battery design parameters on their electrochemical performance is experimentally expensive and hence requires the utilization of cheaper continuum scale models. Here, using a lithium-ion cell composed of LiFePO4 cathode, Li4Ti5O12 anode and a porous separator filled with a liquid electrolyte as an example, we demonstrate the use of an experimentally validated pseudo-two-dimensional (P2D) model in one-dimension to explore the effects of different cell design parameters on the discharge capacity at different current rates. The model is simulated in two-dimensional to instantly visualize the concentration distribution of Li ions in the electrode at high discharge current rates. The continuum model unravels that the solution phase diffusion limitation is the main factor inhibiting the performance of thick electrodes at high current rates and the Li4Ti5O12 anode is the limiting electrode. These findings using continuum models provide guidance for and accelerate the optimization of electrode architecture for enhancing the performance of lithium-ion batteries.

Mo-doping modulated cationic vacancy in Zn3V2O8 with enhanced electrochemical performance for lithium-ion batteries

Given diverse redox reactions and abundant raw materials, Zn3V2O8 with high specific capacity is considered as a potential anode material for lithium-ion batteries. Same as other transition metal oxides, Zn3V2O8 suffers from infertile conductivity, sluggish ion diffusion and fast capacity loss derived from volume expansion during discharge/charge process, further hindering its application. In this work, a novel Mo doped Zn3V2O8 (Zn3V2-xMo5x/6O8) anode material with cationic vacancy (V vacancy) has been designed through a facile sol-gel method. It is found that a small Mo-doping amount has nearly no influence on the crystal structure, morphology and element valence states of Zn3V2O8. Mo doped Zn3V2O8 samples possess smaller charge transfer resistance and higher lithium ion diffusion coefficient. The results of electrochemical performance illustrate that Mo doped Zn3V2O8 can deliver higher reversible specific capacities and better rate capability compared with Zn3V2O8, which can be ascribed to the introduction of V vacancy. In particular, when Mo-doping amount is set as 0.03, the obtained Zn3V1.97Mo0.025O8 exhibits a reversible capacity of 481.1 mAh g−1 after 600 cycles at 1 A g−1. It is believed that this work could provide an effective and feasible strategy to construct high performance transition metal vanadate anode materials for lithium-ion batteries.

Designing high-chaos mixed-salt electrolytes for enhancing graphite-electrolyte interfacial stability in lithium-ion batteries

The interfacial stability between graphite anodes and electrolytes is crucial for the electrochemical performance of lithium-ion batteries, particularly at low temperatures. This study investigates the effect of incorporating four common Solid-Electrolyte Interphase (SEI) components—LiF, LiNO3, Li2O, and Li2CO3—directly into two types of commercial electrolytes: carbonate-based (1.0 M LiPF6-EC/DMC, LP30) and ether-based (1 M LiTFSI-DOL/DME+2 % LiNO3, LDD) both with 5 % FEC (v/v) to create high-chaos mixed-salt electrolytes (LP30-FEC-4S and LDD-FEC-4S). Our findings show that Li/graphite cells exhibit significantly enhanced rate performance in both LP30-FEC-4S and LDD-FEC-4S electrolytes, compared to commercial LP30 and LP57 electrolytes. LiFePO4/graphite full cells using LP30-FEC-4S and LDD-FEC-4S electrolytes also showed excellent electrochemical performance (124.73 mAh g−1 and 119.21 mAh g−1 specific capacities at 0.5C). Remarkably, stable SEIs form rapidly on the graphite anode surfaces in the designed electrolytes even at low temperatures of −10 °C. Moreover, we demonstrate that the Li+ solvation structure is fundamental in determining the overall electrochemical performance. This study suggests that enhancing the mixing entropy of the system by adding multiple lithium salts to a commercial electrolyte is an effective and cost-efficient strategy for improving graphite-electrolyte compatibility.

Design and Mechanism Study of High-Safety and Long-Life Electrolyte for High-Energy-Density Lithium-Ion Batteries.

Although nonflammable electrolytes are beneficial for battery safety, they often adversely affect the electrochemical performance of lithium-ion batteries due to their poor compatibility with electrodes. Herein, we design a nonflammable electrolyte consisting of cyclic carbonate and 2,2-difluoroethyl acetate (DFEA) solvents paired with several surface-film-forming additives, significantly improving the safety and cycling performance of NMC811||SiOx/graphite pouch cells. The DFEA solvent exhibits not only good flame retardancy but also lower lowest unoccupied molecular orbital (LUMO) energy, promoting the formation of a robust inorganic-rich and gradient-architecture hybrid interface between the SiOx/graphite anode and electrolyte. The double insurance of good flame retardancy of the DFEA solvent and decreased exothermic effects of both bulk electrolyte and DFEA-derived solid electrolyte interphase (SEI) can ensure the high safety of the pouch cell. Moreover, the highly robust SEI can prevent the excessive reduction decomposition of the electrolyte and alleviate the structural decay of the anode, which can restrain the formation of lithium deposition on the anode surface and further suppress the structural decay of NMC materials. This contributes to the unprecedented cycling performance of the NMC811||SiOx/graphite pouch cells with a capacity retention of 80% after 1000 cycles at a 0.33C rate.

Ti-Doped Co-Free Li1.2Mn0.6Ni0.2O2 Cathode Materials with Enhanced Electrochemical Performance for Lithium-Ion Batteries

Cobalt-free manganese-based lithium-rich layered oxides (LLOs) have garnered research attention as prospective lithium-ion cathode materials owing to their large specific capacity and low price. However, their large-scale application is hindered by their low Coulombic efficiency, poor cycling performance, voltage attenuation, and structural phase transition. To address these issues, the LLO structure is modified via Ti doping at the manganese site herein. Ti-doped Li1.2Mn0.6−xTixNi0.2O2 (x = 0, 0.03, 0.05, 0.10, and 0.15) is prepared using the high-temperature solid-state method. The Ti-doped Li1.2Mn0.6Ni0.2O2 is calculated via first principles. The results show that Ti4+ doping improves the cycle stability and rate performance of Li1.2Mn0.6Ni0.2O2. Electrochemical test results show that the sample exhibits enhanced electrochemical performance when the Ti doping amount is 0.05. The discharge specific capacity at 0.1C is 210.4 mAh·g−1, which reaches 191.1 mAh·g−1 after 100 cycles, with a capacity retention rate of 90.7%. This study proves the feasibility of using cheap cobalt-free LLOs as cathode materials for LIBs and provides a novel system for exploiting low-cost and high-performance cathode materials.

NiSe2/CoSe2 heterostructure nanoparticles anchoring on graphene for enhanced Li-ions storage

Selenide anodes have been extensively studied due to their exceptional electrochemical performance in lithium-ion batteries (LIBs). However, selenides suffer from inadequate specific capacity and high mechanical stress/strain resulting from significant volume changes during cycling. This leads to a rapid reduction in capacity and reversibility, which limits their practical application. Nanoscale bimetallic heterostructure selenides can effectively reduce the lattice vibration induced by lithiation/delithiation and improve the lithium storage capacity and cycle life. This study describes the preparation of NiSe2 and CoSe2 nanoparticles anchored on graphene (NiSe2/CoSe2/Graphene) using freeze-drying and thermal selenization methods. The graphene, selenide particles, and electric field between heterostructure interfaces significantly enhance electrical conductivity, provide active species storage sites, and improve lithium-ion adsorption ability, resulting in high storage capacity and excellent cycling stability. The NiSe2/CoSe2/Graphene composite exhibited a specific capacity of 929.6 mAh g−1 after 320 cycles at a current density of 100 mA g−1. Even at a high current density of 1000 mA g−1, the composite was stably cycled for 1250 cycles with a continuous increase in specific capacity. This study provides valuable insights into the use of bimetallic selenides for improved lithium storage.

Synthesis of submicron-sized LiNi0.5Co0.2Mn0.3O2 cathode particles via reverse microemulsion method: Tailoring size, interfacial properties, and enhanced electrochemical performance for lithium-ion battery

This study explores the impact of submicron-sized cathode materials on lithium-ion battery performance, an area with limited prior research due to synthetic challenges. Employing the reverse microemulsion method, LiNi0.5Co0.2Mn0.3O2 (NCM) cathode particles with tunable sizes (180 nm to 340 nm) were synthesized. Notably, NCM6.67-4.5, which prepared under the volume ratio of the oil phase to the water phase (i.e. 6.67) and applying 4.5 mL NH4OH as the complexing agent, obtained the largest particle size (340 nm). Further investigation revealed that NCM6.67-4.5 exhibited superior discharge specific capacity (177.54 mAh·g−1) and a high coulomb efficiency (99.5 %). The larger particle size in the submicron range facilitated heightened lithium-ion diffusion rates and reduced polarization. Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) confirmed that increased particle size diminishes specific surface area, mitigating interfacial side reactions during battery cycling. This research underscores the importance of controlling cathode particle size for optimizing electrochemical performance in lithium-ion batteries.