Next-generation Lithium-ion Batteries Research Articles

Embedment of Molybdenum Disulfide in Electrospun Fibers as an Integrated Cathode for Lithium-Ion Batteries

As an important component of LIBs, the electrode material plays a crucial role in determining the lithium (Li) storage performance in LIBs. In this study, MoS2 nano-flowers were synthesized using a one-pot hydrothermal method. The resulting MoS2 nano-flower, along with PAN, were used as raw materials for electrospinning. After annealing treatment, MoS2/(carbon nanofibers) CNFs nano-composites coated with carbon fibers were formed. The CNFs coating exhibited electrical conductivity and enhanced structural stability of the MoS2 due to the stabilizing effect of the carbon fibers. Additionally, electrochemical tests, including CV and GCD, indicated that the optimal capacity and cycling stability were achieved when the MoS2 content was 10%. The results indicated that the charge/discharge capacity of MoS2/CNFs-10% at a current density of 100 mA/g was ~650 mAh/g. After the cycling current returned to 100 mA/g, the current recovery was ~600 mAh/g, thereby indicating outstanding cycling stability. Accordingly, our fabrication technique and new insight could both widen design strategy of multicomponent composite electrode materials and promote the practical applications of the latest emerging transition metal sulfides in next-generation high-performance lithium-ion batteries.

Entropic Design of Anionic Site to Improve Anionic Redox Stability in Lithium-Rich Cathode.

Cobalt-free manganese-rich layered oxide is considered one of the most promising cathode materials for next-generation lithium-ion batteries due to its high capacity and low cost. However, irreversible anionic redox (OAR) leads to serious failure problems and hinders its wide application. To solve the above problems, the entropy design strategy of anionic sites is proposed, which is more direct and relevant to the regulation of the OAR process compared to the traditional entropy design of TM sites. The entropic design improves the structural diversity and long-range disorder of the material, which effectively inhibits oxygen release and drastic structural strain, and alleviates structural degradation. After 400 cycles at 1C, the capacity and voltage decay per cycle are only 0.092 mAhg-1 and 1.36mV, respectively. The long cycle test (10C and 1000 cycles) at high current shows that the voltage and capacity decay are only 0.04 mAhg-1 and 0.66mV per cycle, respectively. Meanwhile, the rate performance at 10C reaches 175 mAhg-1. The charge compensation regulation and performance enhancement mechanism are investigated by systematic in-situ/ex-situ characterization and theoretical calculation. This research provides new ideas for the design of lithium-rich cathodes with stable OAR and high structural adaptability.

Unveiling the potential of lithium fluoride phosphate (Li2MPO4F, M = Fe, V, Mn) for the next generation of lithium-ion batteries: A comparative study based on first principles and molecular dynamic simulations

LiFePO4 (LFP) cathode with olivine crystal structure has been a key player in safe and affordable energy storage, owing to its low-cost iron and high electrochemical stability within a voltage range of commercial electrolytes (2.8–3.4 V). To maintain these benefits while enhancing its energy density, Li2MPO4F was developed by introducing fluorine (F) and replacing iron with other transition metals (M). However, previous studies on these materials primarily measured performance within a limited voltage window (e.g., 2.5–4.5 V), making it challenging to analyze their performance under advanced electrolytes with a broader voltage range. In this study, we took a novel approach by utilizing first principles and molecular dynamic calculations to investigate the electrochemical performance of Li2MPO4F with three types of transition metals (M = V, Fe, Mn). This unique methodology, which includes calculations on theoretical voltages, atomic structures, and diffusion coefficient after structural optimization, allowed us to predict the impact of transition metals on cathode performance. By closely comparing the expected results, this study discusses the pros and cons of each cation substitution and suggests suitable cathode materials for batteries with high energy density and superior rate capability.

Effect of the succinonitrile additive, electrode processing, and N/P ratios in the performance of high‐voltage lithium‐ion batteries using LiNi0.5Mn1.5O4 cathode

AbstractThe progressive improvement in the gravimetric energy density of lithium‐ion batteries (LIBs) leads to electrolyte design, positive electrode, and full‐cell optimization processes. The spinel lithium nickel manganese oxide (LiNi0.5Mn1.5O4, LNMO) is one of the potential candidates for the next generation of LIBs applied for electric vehicles due to high working potential (4.75 V vs. Li+/Li), affordable price, and environmental friendliness. Nevertheless, the degradation of cycling performance at high potential induces massive challenges for commercializing LNMO‐based batteries. This study investigated the impact of succinonitrile (SN), electrode processing, and N/P ratios to strengthen the LNMO half‐cell and graphite||LNMO full‐cell performance. According to the performance in half‐cell, the sample contained 85 wt% LNMO: 7.5 wt% C65: 7.5 wt% PVDF/NMP combining with the electrolyte 1.5 M LiPF6 in EC:EMC:DMC (2:1:7 – v/v) at 0.5 wt% SN seems to be the optimal condition for further full‐cell. In addition, the full‐cell with N/P = 1.3 displays a remarkable initial capacity of 118.75 mAh g−1, a Coulombic efficiency of 91.64%, and a superior gravimetric energy density of 537.71 mWh g−1. Moreover, it maintains a capacity retention of around 58% at the current density of 0.1C after 100 cycles. As a result, this study presents an optimal solution to augment the material's potential for commercialization in the immediate future.

Understanding and Controlling Structural Defects and Disordering in LiNi0.5Mn1.5O4 Cathodes for Direct Recycling.

Despite significant progress in recycling spent lithium-ion batteries (LIBs), nondestructive, direct recycling methods still face untenable discrepancies in multiple cathode chemistries, which primarily originate from a variety of structure stabilities during the recycling process. Through systematic investigation of the microstructure evolution during the relithiation treatment, we observed the inevitably induced defects and Li/Mn disordering in the LiNi0.5Mn1.5O4 cathode, contributing to the sluggish Li+ transport and irreversible capacity loss. Employing a defect engineering approach to achieve twin boundaries and preferred grain orientation, we show the regenerated cathodes demonstrate a substantial enhancement of Li+ diffusion and cycling stability, retaining 97.4% capacity after 100 cycles and 87.96% after 200 cycles at C/3. This work not only elaborates on a systematic investigation of defect inducement and structural restoration mechanism but also provides an effective approach to directly recycle high-voltage spinel-type cathodes, contributing to the sustainability of next-generation LIBs.

Structural design and investigation of Ti3C2 MXene as a conductive interlayer for improving the lithium-storage performance of PSi@C anode material

Silicon stands out as an ideal anode material for the next generation of lithium-ion batteries (LIBs) due to its abundant sources, low lithiation/delithiation potential, and high specific capacity. However, its practical application is impeded by significant volume expansion, leading to electrode structure damage. In this study, the Porous silicon(PSi)@C/Ti3C2 MXene composite was developed by dispersing porous micro-silicon@carbon (PSi@C) particles into layered stackable Ti3C2 MXene sheets using ultrasonic and freeze drying. The Ti3C2 MXene interlayer played a crucial role in enhancing the conductive crosslinking network between PSi@C particles, and providing efficient channels for electron transport/ion diffusion. Additionally, the Ti3C2 MXene interlayer served as a buffer to accommodate the substantial volume changes in silicon during electrochemical cycling. Consequently, the PSi@C/Ti3C2 MXene composite electrode demonstrated rapid electron/ion conduction and maintained structural stability. Remarkably, the electrode exhibited outstanding long cycle stability with 952 mAh g-1 at 0.5 A g-1 after 200 cycles and excellent rate performance with 542 mAh g-1 at 2 A g-1.

Electrochemical in-situ lithiated Li2SiO3 layer promote high performance silicon anode for lithium-ion batteries

Si anode is considered to be one of the most promising candidates for the next-generation lithium-ion batteries (LIBs). However, the severe volume variation of Si (> 300%) during the lithiation/delithiation process results in unstable interface and thus contributes to poor cycling stability. Moreover, the relatively low conductivity derived from the semiconductor nature of Si leads to inferior rate performance. Herein, Li2SiO3 layer with fast lithium-ions transport capability and high mechanical property was formed on Si surface in an in-situ electrochemical method. The relationships between the valence of SiOx and LixSiOy constituents were readily studied. Fortunately, the as-prepared Si@ES-LSO showed great potential to mitigate the expansion and high lithium-ions diffusion coefficient. When employed as anode materials for LIBs, the modified Si anode delivered a specific capacity of 2074.8 mAh g−1 at 1000 mA g−1 with a retention ratio of 98.9% after 100 cycles, demonstrating superior electrochemical performance. This work provides a facial and efficient strategy for the roadmap of Si anode application.

Defect Chemistry in High-Voltage Cathode Materials for Lithium-Ion Batteries.

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. These insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

Recyclability study for the next generation of cobalt-free lithium-ion battery systems with C-LNMO, Si/C- LRLO and TiNbO-LNMO active materials via hydrometallurgical route

The scarcity and uncertain supply of cobalt poses significant challenges for the lithium-ion battery industry. To address this issue, alternative chemistries excluding cobalt have been developed. Despite solving supply issues, these developments raise concerns about recyclability and their impact on current recycling trends.This study presents a recycling strategy and evaluates its performance for next-generation cobalt-free lithium-ion batteries. It focuses on three prototypes that use innovative cathode materials (titanium niobium oxide, carbon, and silicon/carbon) and electrolyte systems (ionic liquid and gelified). The proposed recycling process includes pyrolysis, mechanical separation, neutral and acid leaching, cementation, and neutralisation for selective metal separation.The results indicate that gelified electrolytes exhibit greater thermal stability than their liquid counterparts, indicating an effect on the degradation temperature and gas emissions, which are crucial for metal recovery. This study highlights the reduced toxicity of ionic liquid electrolytes and emphasises the need for strict pyrolysis gas handling due to hazardous emissions. High recovery rates (65–90 %) were achieved for nickel, manganese, lithium, and anode components.With potential for process optimisation to improve the quality of products, this study shows that cobalt-free battery systems can be integrated into existing recycling frameworks with adjustments, supporting progress towards sustainable battery practices.

Enhancing Electrochemical Performance of Si@CNT Anode by Integrating SrTiO3 Material for High-Capacity Lithium-Ion Batteries

Silicon (Si) has attracted worldwide attention for its ultrahigh theoretical storage capacity (4200 mA h g−1), low mass density (2.33 g cm−3), low operating potential (0.4 V vs. Li/Li+), abundant reserves, environmentally benign nature, and low cost. It is a promising high-energy-density anode material for next-generation lithium-ion batteries (LIBs), offering a replacement for graphite anodes owing to the escalating energy demands in booming automobile and energy storage applications. Unfortunately, the commercialization of silicon anodes is stringently hindered by large volume expansion during lithiation–delithiation, the unstable and detrimental growth of electrode/electrolyte interface layers, sluggish Li-ion diffusion, poor rate performance, and inherently low ion/electron conductivity. These present major safety challenges lead to quick capacity degradation in LIBs. Herein, we present the synergistic effects of nanostructured silicon and SrTiO3 (STO) for use as anodes in Li-ion batteries. Si and STO nanoparticles were incorporated into a multiwalled carbon nanotube (CNT) matrix using a planetary ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the STO. We discovered that the introduction of STO can improve the electrochemical performance of Si/CNT nanocomposite anodes. Experimental measurements and electrochemical impedance spectroscopy provide evidence for the enhanced mobility of Li-ions facilitated by STO. Hence, incorporating STO into the Si@CNT anode yields promising results, exhibiting a high initial Coulombic efficiency of approximately 85%, a reversible specific capacity of ~800 mA h g−1 after 100 cycles at 100 mA g−1, and a high-rate capability of 1400 mA g−1 with a capacity of 800 mA h g−1. Interestingly, it exhibits a capacity of 350 mAh g−1 after 1000 lithiation and delithiation cycles at a high rate of 600 mA hg−1. This result unveils and sheds light on the design of a scalable method for manufacturing Si anodes for next-generation LIBs.

An Effective Strategy on Synthesizing a Stable SiOx-Based Anode for High Density Lithium-Ion Batteries.

Silicon oxides (SiOx) have received extensive attention as a promising anode candidate for next-generation lithium-ion batteries (LIBs). However, their commercial applications have been seriously hindered by low conductivity, large volume expansion, and unstable solid-electrolyte interface (SEI) layer, which result in low initial coulombic efficiency, poor rate performance, and short cycling lifespan. In this work, we demonstrated a simple way to prepare a series of SiOx materials with lithium fluoride (LiF) modified. When the mass ratio of SiOx and LiF equaled 1 : 0.15, the long-term cycling capacity retention could be greatly improved from 30.1 % to 76.5 % after 300 cycles. The result was primarily because of the enhancement of electrons and Li+-ions transport and the stability of the SEI layer due to LiF addition. However, excess LiF addition could hinder the diffusion of Li+-ions. This study presented the great potential of LiF modified on SiOx anode materials for LIBs.

Enhanced cyclability and energy density of mid-nickel layered oxide cathode material LiNi0.55Mn0.25Co0.20O2 by niobium doping via solvothermal method

Ni-based layered oxide materials are among the most promising cathode materials for the next generation of lithium-ion batteries due to their higher energy capacity. However, capacity decay occurs due to degradation mechanisms that reduce the electrochemical performance of this type of material. This work aims to synthesize Nb-doped LiNi0.55Mn0.25Co0.20O2 (Nb-NCM) materials via the solvothermal method to enhance the cyclability and energy density of the layered oxide cathode. The effects of Nb doping on the microstructure and the electrochemical performance of the cathodes are investigated. The introduction of the contents of Nb expands the structural lattice parameters and decreases the Li+/Ni2+ cation mixing degree of the NCM cathode. Furthermore, the Nb doping enhances the electrochemical activity of LiNi0.55Mn0.25Co0.20O2, increasing its initial discharge capacity to 169.61 mAhg−1 when 1% of Nb was used as a dopant (1%Nb-NCM) in contrast to the capacity of 149.45 mAhg−1 presented by the pristine material. The modified 1.0%Nb-NCM material also exhibits remarkable cycling performance with a capacity retention of 92.7% after 100 cycles at the rate of 1 C (2.8–4.3 V). This work suggests a rational strategy for high-performance cathode for lithium-ion batteries, proposing the extension of Nb doping to enhance Ni-mid material's cyclability.

Electrochemical Performance of LiTa2PO8-Based Succinonitrile Composite Solid Electrolyte without Sintering Process.

Solid-state batteries (SSBs) have been widely studied as next-generation lithium-ion batteries (LiBs) for many electronic devices due to their high energy density, stability, nonflammability, and chemical stability compared to LiBs which consist of liquid electrolytes. However, solid electrolytes exhibit poor electrochemical characteristics due to their interfacial properties, and the sintering process, which necessitates high temperatures, is an obstacle to the commercialization of SSBs. Hence, the aim of this study was to improve the interfacial properties of the lithium tantalum phosphate (LTPO) solid electrolyte by adding succinonitrile (SN) on the interface of the LTPO particle to enhance ionic conductivity without the sintering process. Electrochemical impedance spectroscopy (EIS), the Li symmetric cell test, and the galvanostatic cycle test were performed to verify the performance of the SN-containing LTPO composite electrolyte. The LTPO composite solid electrolyte exhibited a high ionic conductivity of 1.93 × 10-4 S/cm at room temperature (RT) compared to the conventional LTPO. Also, it showed good cycle stability, and low interfacial resistance with Li metal, ensuring electrochemical stability. On the basis of our experimental results, the performance of solid electrolytes could be improved by adding SN and lithium salt. In addition, the SN can be used to fabricate the solid electrolytes without the sintering process at high temperatures.

Exploring the Mechanisms of LiNiO2 Cathode Degradation by the Electrolyte Interfacial Deprotonation Reaction.

Nickel-rich layered oxides stand as ideal cathode candidates for high specific capacity and energy density next-generation lithium-ion batteries. However, increasing the Ni content significantly exacerbates structural degradation under high operating voltage, which greatly restricts large-scale commercialization. While strategies are being developed to improve cathode material stability, little is known about the effects of electrolyte-electrode interaction on the structural changes of cathode materials. Here, using LiNiO2 in contact with electrolytes with different proton-generating levels as model systems, we present a holistic picture of proton-induced structural degradation of LiNiO2. Through ab initio molecular dynamics calculations based on density functional theory, we investigated the mechanisms of electrolyte deprotonation, protonation-induced Ni dissolution, and cathode degradation and the impacts of dissolved Ni on the Li metal anode surfaces. We show that the proton-transfer reaction from electrolytes to cathode surfaces leads to dissolution of Ni cations in the form of NiOOHx, which stimulates cation mixing and oxygen loss in the lattice accelerating its layered-spinel-rock-salt phase transition. Migration of dissolved Ni2+ ions to the anode side causes their reduction into the metallic state and surface deposition. This work reveals that interactions between the electrolyte and cathode that result in protonation can be a dominant factor for the structural stability of Ni-rich cathodes. Considering this factor in electrolyte design should be of benefit for the development of future batteries.

Polyacrylonitrile and aluminum metal dual functionalization interconnected network for superior lithium storage in silicon anode

Currently, silicon-based anode is one of the most promising anode materials that can be applied in next-generation lithium-ion batteries. However, the high activity of the electrode–electrolyte interface and low electronic conductivity of Si anode during the cycling process greatly limits its large-scale application. Aluminum (Al) is the metallic current collector known to promote electronic conductivity and lithium-ion transfer at low cost. However, to our knowledge, scalable interface engineering incorporating Al with carbonized polymer has not been reported. Herein, a polyacrylonitrile (PAN) and aluminum metal dual functionalization interconnected network is achieved via a simple sol-gel method followed by high-temperature calcination to obtain a stable solid electrolyte interphase (SEI) while allowing fast Li+ transmission. The calculated diffusion energy barrier for lithium ions in Al is 0.2198 eV, significantly lower than that in Cu and Fe. Benefiting from the enhanced interfacial protection and kinetics of Si with polyacrylonitrile/Al, the prepared Si@Al@CPAN anode exhibits high lithium storage capacity (2034.90 mAh/g after 150 cycles at 0.84 A/g). At the same time, the prepared Si@Al@CPAN anode outperforms the pure Si anode in rate performance at 12.6 A/g (1116.75 mAh/g vs. 2.84 mAh/g). The present work delivers new design ideas for high-performance Si anode with a multi-functionalization interface.

Tailoring the Li+ Intercalation Energy of Carbon Nanocage Anodes Via Atomic Al-Doping for High-Performance Lithium-Ion Batteries.

Graphitic carbon materials are widely used in lithium-ion batteries (LIBs) due to their stability and high conductivity. However, graphite anodes have low specific capacity and degrade over time, limiting their application. To meet advanced energy storage needs, high-performance graphitic carbon materials are required. Enhancing the electrochemical performance of carbon materials can be achieved through boron and nitrogen doping and incorporating 3D structures such as carbon nanocages (CNCs). In this study, aluminum (Al) is introduced into CNC lattices via chemical vapor deposition (CVD). The hollow structure of CNCs enables fast electrolyte penetration. Density functional theory (DFT) calculations show that Al doping lowers the intercalation energy of Li+. The Al-boron (B)-nitrogen (N-doped CNC (AlBN-CNC) anode demonstrates an ultrahigh rate capacity (≈300 mAhg-1 at 10 Ag-1) and a prolonged fast-charging lifespan (862.82 mAhg-1 at 5 Ag-1 after 1000 cycles), surpassing the N-doped or BN-doped CNCs. Al doping improves charging kinetics and structural stability. Surprisingly, AlBN-CNCs exhibit increased capacity upon cycling due to enlarged graphitic interlayer spacing. Characterization of graphitic nanostructures confirms that Al doping effectively tailors and enhances their electrochemical properties, providing a new strategy for high-capacity, fast-charging graphitic carbon anode materials for next-generation LIBs.

Selective Methylation of Cyclic Ether Towards Highly Elastic Solid Electrolyte Interphase for Silicon-based Anodes.

Silicon (Si)-based anodes offer high theoretical capacity for lithium-ion batteries but suffer from severe volume changes and continuous solid electrolyte interphase (SEI) degradation. Here, we address these challenges by selective methylation of 1,3-dioxolane (DOL), thus shifting the unstable bulk polymerization to controlled interfacial reactions and resulting in a highly elastic SEI. Comparative studies of 2-methyl-1,3-dioxolane (2MDOL) and 4-methyl-1,3-dioxolane (4MDOL) reveal that 4MDOL, with its larger ring strain and more stable radical intermediates due to hyperconjugation effect, promotes the formation of high-molecular-weight polymeric species at the electrode-electrolyte interface. This elastic, polymer-rich SEI effectively accommodates volume changes of Si and inhibits continuous side reactions. Our designed electrolyte enables Si-based anode to achieve 85.4% capacity retention after 400 cycles at 0.5 C without additives, significantly outperforming conventional carbonate-based electrolytes. Full cells also demonstrate stable long-term cycling. This work provides new insights into molecular-level electrolyte design for high-performance Si anodes, offering a promising pathway toward next-generation lithium-ion batteries with enhanced energy density and longevity.

In situ anchoring of FeNi nanoparticles into three-dimensional nitrogen-doped carbon framework as a self-supporting electrode for high-performance lithium storage

Constructing free-standing electrodes with superior lithium storage capacity and good mechanical performance are fascinating for next-generation lithium-ion batteries (LIBs). Nevertheless, their practical application is hindered by complicated synthesis procedures and high cost. Herein, a highly stable, self-supporting and flexible electrode material for LIBs was constructed by encapsulating spherical FeNi nanoparticles into one-dimensional N-doped carbon fiber film (FeNi/N- CFM) using the electrospinning technique and subsequent heat treatment. The FeNi/N-CFM can be directly used as anode materials for LIBs without conductive additive, current collector and binder. The synergistic effect of uniformly dispersed small FeNi nanoparticles and three-dimensional (3D) conductive network constructed by CF framework effectively improves the utilization rate of active materials, enhances the transport of both electrons and lithium ions, facilitates the electrolyte penetration, and promotes the lithium-ion storage kinetics and stability, thus leading to a greatly enhanced electrochemical performance. Benefiting from the unique architectural feature and flexibility, the FeNi/N-CFM composites employed as binder-free electrodes for LIBs exhibit good lithium storage performance (an initial discharge capacity of 1031.5 mA h g−1 and a reversible capacity of 481.3 mA h g−1 at 100 mA g−1 after 100 cycles), rate capacity (305.1 mA h g−1 at 1000 mA g−1) and outstanding reversibility (coulombic efficiency of around 100 % after 100 cycles). Furthermore, this work also provides a facile and effective pathway to design and fabricate free-standing electrodes.

Controllable Synthesis of Hollow Dodecahedral Si@C Core-Shell Structures for Ultrastable Lithium-Ion Batteries.

Silicon (Si) has attracted considerable attention as a promising alternative to graphite in lithium-ion batteries (LIBs) because of its high theoretical capacity and voltage. However, the durability and cycling stability of Si-based composites have emerged as major obstacles to their widespread adoption as LIBs anode materials. To tackle these challenges, a hollow core-shell dodecahedra structure of a Si-based composite (HD-Si@C) is developed through a novel double-layer in situ growth approach. This innovative design ensures that the nano-sized Si particles are evenly distributed within a hollow carbon shell, effectively addressing issues like Si fragmentation, volume expansion, and detachment from the carbon layer during cycles. The HD-Si@C composite demonstrates remarkable structural integrity as a LIBs anode, resulting in exceptional electrochemical performance and promising practical applications, as evidenced by tests in pouch-type full cells. Notably, the composite shows outstanding cycling stability, retaining 85% of its initial capacity (713 mAh g-1) even after 3000 cycles at a high current rate of 5000mA g-1. Additionally, the material achieves a gravimetric energy density of 369Wh kg-1, showcasing its potential for efficient energy storage solutions. This research signifies a significant step toward realizing the practical utilization of Si-based materials in the next generation of LIBs.

Impact of Mn/Ni and Li/(Mn+Ni) ratios on phase equilibrium and electrochemical performance of the high voltage spinel LiNi0.5Mn1.5O4

LiNi0.5Mn1.5O4 (LNMO) emerges as a promising spinel-type positive electrode material for lithium-ion batteries (LIBs) due to its low cost and high operating voltage (4.8 V vs. Li+/Li), attributed to the Ni4+/Ni3+/Ni2+ redox couples, which contribute to high energy density, a crucial requirement for next-generation LIBs. In this study, we investigate the influence of Mn/Ni and Li/(Mn + Ni) ratios on the phase equilibrium and electrochemical performance of LNMO positive electrode materials. A series of 18 samples were synthesized using a two-stage solid-state method with varying Mn/Ni and Li/(Mn + Ni) ratios and annealing under different atmospheres. These synthesis conditions have major impact on the composition and level of purity of LNMO phases, as well as on the nature of the impurities themselves. Mn excess significantly enhances the electrochemical performance, with superior discharge capacity, coulombic efficiency, and capacity retention for the Mn-rich sample with Li/(Mn + Ni) = 0.50. A comprehensive structural analysis combining synchrotron X-ray and neutron powder diffraction gives an in-depth characterization of these samples with a clear differentiation between the global Mn content within samples and that within the LNMO phase.