Materials For Li-ion Batteries Research Articles

Design of Silicon-Based Anode Materials for High Energy Density Li-Ion Batteries

Compared to other types of batteries, lithium batteries have an extremely high energy density, which means they can store more energy while maintaining a smaller size and weight. The ideal electrode material must have a high lithium ion capacity to store many lithium ions. In addition, the electrode material must have good electronic conductivity to promote lithium ions' rapid entry and exit. However, traditional carbon materials have limited theoretical specific capacity, and the transmission of lithium-ion batteries in traditional materials is limited, resulting in a significant decrease in capacity. Silicon has a theoretical capacity of up to 4200mAh/g, more than ten times the capacity of commercial graphite negative electrodes. In addition, silicon and lithium can undergo alloying reactions to form Li Si alloys, which helps improve the material's specific capacity. This article first summarizes the advantages of electric vehicles and lithium-ion batteries. Then, the benefits and challenges of using silicon-based materials as negative electrodes for lithium-ion batteries were elaborated in detail, and finally, the prospects of silicon-based materials in lithium-ion battery applications were summarized. This article has reference significance in improving the energy density of lithium-ion batteries.

Research Progress in Strategies for Enhancing the Conductivity and Conductive Mechanism of LiFePO4 Cathode Materials

LiFePO4 is a cathode material for lithium (Li)-ion batteries known for its excellent performance. However, compared with layered oxides and other ternary Li-ion battery materials, LiFePO4 cathode material exhibits low electronic conductivity due to its structural limitations. This limitation significantly impacts the charge/discharge rates and practical applications of LiFePO4. This paper reviews recent advancements in strategies aimed at enhancing the electronic conductivity of LiFePO4. Efficient strategies with a sound theoretical basis, such as in-situ carbon coating, the establishment of multi-dimensional conductive networks, and ion doping, are discussed. Theoretical frameworks underlying the conductivity enhancement post-modification are summarized and analyzed. Finally, future development trends and research directions in carbon coating and doping are anticipated.

Electrochemical Performance of MoB/Si3N4 Heterojunction as a Potential Anode Material for Li Ion Batteries.

In response to the current policy of high storage capacity, two-dimensional (2D) materials have revealed promising prospects as high-performance electrode materials. MoB, as a type of such material, is widely regarded as an anode candidate for Li-ion batteries due to its large specific surface area and abundant ion diffusion channels; the long-term cycling stability, however, is poor owing to material pulverization during the cycle. Therefore, MoB/Si3N4 heterojunction in this work is proposed as an anode material, with Si3N4 acting as a skeleton, maintaining the stability of the structure, while retaining the high energy storage properties of MoB as well. In addition, a certain built-in electric field is formed between them, which can play a role in regulating charge transfer, improving the ion transport channel, and accelerating the migration rate. Herein, the structural, electronic, and electrochemical properties are systematically investigated by first-principles calculations; the final results indicate that the heterojunction anode material does indeed have built-in electric fields, which promote the anode material to possess excellent electrical conductivity and outstanding electrochemical property. Meanwhile, the introduction of vacancy defects can bolster the diffusion kinetic performance of ion transport and greatly reduce the diffusion energy barrier of Li ions, which is conducive to the realization of rapid charge and discharge for the Li ion battery. Based on the synergistic effect of two single-component materials, the synthesized anode material displays a high theoretical capacity of 461 mAh/g, and the calculated open-circuit voltage is 0.66 V, within the range of the negative electrode criterion of 0-1 V, which can effectively play a role in preventing the formation of Li dendrites; these properties are comparable to other 2D anode materials as well. Given these intriguing properties, the MoB/Si3N4 heterojunction is an exceptional candidate for advanced LIB high-performance anode materials.

More about the BaO(BaCO3)–Lu2O3–CuO system

The phase diagram of the BaO(BaCO3)–Lu2O3–CuO system was built at 900°C. It comprises of 8 single-phase, 15 two-phase, and 8 three-phase regions. The boundary oxide systems Lu2O3–CuO and BaO–CuO contain the phases Lu2Cu2O5 (structure type Ho2Cu2O5, Pearson symbol oP36, space group Pna21, a = 10.702(1), b = 3.412(1), c = 12.360(1) Å, RB = 0.076) and Ba44Cu45O90 (own structure type, cI400, Im-3m, a = 18.294(3) Å, RB = 0.114), whereas in the Lu2O3–BaO(BaCO3) system the oxide-carbonate Ba3Lu2[CO3]O5 (Ba3Yb2[CO3]O5, tP26, P4/mmm, a = 4.322(1), c = 11.862(2) Å, RB = 0.107) was identified under the conditions of the experiment. Two quaternary oxides were observed. The structure of BaLu2CuO5 was confirmed (BaY2CuO5, oP36, Pnma), whereas the structure of the phase with approximate composition Ba3LuCu2O6.5 still needs to be established. The electrochemical properties of BaLu2CuO5 as cathode material in Li-ion batteries were investigated. The existence of a (in part) substitutional solid solution BaLu2CuO5:Li was confirmed by the decrease of the unit-cell volume (–0.11 %). No traces of the formation of a phase with YBCO-type structure were detected at 900°C.

The reduced graphene oxide conductive additives with a certain defect concentration enabling rate-capability of lithium-ion batteries

Graphene as conductive additives for enhancing the electrochemical performance of commercial cathode materials (e.g., LiFePO4, LiCoO2, and LiMn2O4) in advanced Li-ion batteries (LIBs) has attracted great attention in recent years. However, the LiFePO4 and LiCoO2 electrodes usually show a poor rate capability when using graphene as the conductive additive, since its planar structure hinders ion transmission. Herein, a variety of reduced graphene oxides (rGO-x) have been successfully prepared using the modified Hummer's method followed by calcination. The results show that due to a large specific area and moderate defect density, rGO-5 can ensure good enough interfacial contact between active material particles and collector, thus maintaining fast electron/ion transportation. It has been found that LiFePO4 and LiCoO2 electrodes exhibit good lithium storage properties of 160.95 and 139.41 mA h g-1 at a rate of 0.1 C when rGO-5 is utilized as a conductivity additive. Meanwhile, combined with the electrochemical impedance and kinetic exploration, it can be seen that the LiFePO4 and LiCoO2 electrodes demonstrate a high Li+ diffusion coefficient (DLi+) of 6.7 × 10-14 cm2 s-1 and 4.3 × 10-13 cm2 s-1, respectively. Therefore, this research sheds new light on the practical utilization of rGO additives in high-performance lithium-ion batteries.

Pushing the Energy-Lifetime Frontier of Li-Ion Batteries: Study of Ni-Rich, Co-Free NMAW Cathode Material

Abstract Dopants and coatings have been widely used to improve the performance of Ni-rich positive electrode active materials. Previous studies have aimed to elucidate the mechanism by which Al and W improve lithium metal oxides, providing valuable insight on the design of enhanced electrode materials for Li-ion batteries. In this work, Al and W are compared as individual dopants as well as co-dopants in order to design an optimal Ni-rich, Co-free material. This involved studying the effect of synthesis temperature in the presence of Al and/or W as well as the effect that these metals have on the morphology of the resultant polycrystalline materials. In addition, structural analysis by X-ray diffraction, electrochemical analysis, and characterization of the mechanical strength of the materials were also conducted. The change in performance with the addition of Al and W depends greatly on particle size and chemical composition. Small sized Ni-rich polycrystalline particles (Ni content of 94%) with low contents of Al (3%) and W (1%) showed the greatest enhancement in energy density with good cycle life.

Synthesis and characterization of MoS2-carbon based materials for enhanced energy storage applications

The article delves into the synthesis and characterization of MoS2-carbon-based materials, holding promise for applications in supercapacitors and ion batteries. The synthesis process entails the preparation of MoS2 and its carbon hybrids through exfoliation, hydrothermal treatment, and subsequent pyrolysis. Various analytical techniques were employed to comprehensively examine the structural, compositional, and morphological properties of the resulting materials. The article explores the electrochemical performance of these electrode materials in supercapacitors and ion batteries (LiB, SiB, KiB). Electrochemical measurements were conducted in aqueous electrolyte for supercapacitors and various aprotic electrolytes for ion batteries. Results highlight the impact of the synthesis process on electrochemical performance, emphasizing factors such as capacitance, rate capability, and charge/discharge cycle performance. Hydrothermally treated MoS2-carbon exhibited a specific capacitance of approximately 150 F g-1 in supercapacitors, attributed to its high surface area and efficient charge storage mechanisms. Additionally, for Li-ion battery materials without hydrothermal treatment showed impressive capacity retention of around 88% after 500 charge-discharge cycles, starting with an initial specific capacity of about 920 mAh/g. Long-term stability was demonstrated in both supercapacitors and lithium-ion batteries, with minimal capacitance degradation even after extensive charge-discharge cycles. This research underscores the potential of MoS2-based materials as effective energy storage solutions.

Unveiling BaTiO3-SrTiO3 as Anodes for Highly Efficient and Stable Lithium-Ion Batteries.

Amidst the swift expansion of the electric vehicle industry, the imperative for alternative battery technologies that balance economic feasibility with sustainability has reached unprecedented importance. Herein, we utilized Perovskite-based oxide compounds barium titanate (BaTiO3) and strontium titanate (SrTiO3) nanoparticles as anode materials for lithium-ion batteries from straightforward and standard carbonate-based electrolyte with 10% fluoroethylene carbonate (FEC) additive [1M LiPF6 (1:1 EC: DEC) + 10% FEC]. SrTiO3 and BaTiO3 electrodes can deliver a high specific capacity of 80 mA h g-1 at a safe and low average working potential of ≈0.6 V vs. Li/Li+ with excellent high-rate performance with specific capacity of ~90 mA h g-1 at low current density of 20 mA g-1 and specific capacity of ~80 mA h g-1 for over 500 cycles at high current density of 100 mA g-1. Our findings pave the way for the direct utilization of perovskite-type materials as anode materials in Li-ion batteries due to their promising potential for Li+ ion storage. This investigation addresses the escalating market demands in a sustainable manner and opens avenues for the investigation of diverse perovskite oxides as advanced anodes for next-generation metal-ion batteries.

Mitigating the Kinetic Hysteresis of Co-Free Ni-Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon.

Co-free Ni-rich layered oxides are considered a promising cathode material for next-generation Li-ion batteries due to their cost-effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li-ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si-O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co-free Ni-rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li-ion diffusion kinetics in atomic and electrode particle scales, the as-obtained cathodes (LiNixMn1-xSi0.01O2, 0.6≤x≤0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li-ion transport properties, and the concept will inspire more researchers to conduct an intensive study.

Analysis of the interfacial reaction between Si-based anodes and electrolytes in Li-ion batteries.

To ensure optimal operation of electrochemical energy storage devices, a precise design of the interfaces formed between the electrodes and the electrolyte is essential. Si is a promising anode active material for Li-ion batteries owing to its high theoretical capacity; however, the large volume change associated with Li absorption and release hinders its practical applications. The development of high-performance storage batteries depends on the construction of an electrode-electrolyte interface that facilitates Li+ movement. To this aim, the authors have developed Si-specific interface observation methods. In this feature article, we review and discuss recent advances in the reaction behavior of Si-based anodes, particularly at the Si electrode-electrolyte interface.

Unraveling the contribution of nucleation to the intercalation energy barrier for phase-transforming Li-ion battery materials

Phase-transforming intercalation compounds, such as LiFePO4 (LFP) and Li4Ti5O12 (LTO), are widely utilized in Li-ion batteries, particularly for applications requiring high power and operation at low temperatures. However, the impact of phase transformation kinetics on energy density losses under extreme conditions has been largely unexplored. Specifically, the role of nucleation, the initial stage of phase transformation, in contributing to battery performance losses has not been previously investigated. In this study, we not only quantified the significance of material-level factors, such as interfacial charge transfer, in the low-temperature and high-rate performance of LFP and LTO materials, but also provided the first estimates of the apparent activation energies of nucleation. Our findings revealed that nucleation, particularly in the case of LFP, contributes significantly to overpotential, highlighting its pivotal role among material-level factors. Furthermore, our analysis allowed us to differentiate between material-level and particle-level limitations for the LTO/LFP cell, emphasizing the paramount importance of controlling the porosity of secondary particles to ensure high tolerance towards high-rate/low-temperature discharge.

Entropy-Stabilized Multication Fluorides as a Conversion-Type Cathode for Li-Ion Batteries-Impact of Element Selection.

Metal fluorides (e.g., FeF2 and FeF3) have received attention as conversion-type cathode materials for Li-ion batteries due to their higher theoretical capacity compared to that of common intercalation materials. However, their practical use has been hindered by low round-trip efficiency, voltage hysteresis, and capacity fading. Cation substitution has been proposed to address these challenges, and recent advancements in battery performance involve the introduction of entropy stabilization in an attempt to facilitate reversible conversion reactions by increasing configurational entropy. Building on this concept, high entropy fluorides with five cations were synthesized by using a simple mechanochemical route. In order to examine the impact of element selection, Co0.2Cu0.2Ni0.2Zn0.2Fe0.2F2 (HEF-Fe) was compared with Co0.2Cu0.2Ni0.2Zn0.2Mg0.2F2 (HEF-Mg), replacing electrochemically inactive Mg with Fe as an active participant in the conversion reaction. Combining electrochemical measurements with first-principles calculations, high-resolution electron microscopy, and synchrotron X-ray analysis, HEFs' battery performances and conversion reaction mechanisms were investigated in detail. The results highlighted that replacement of Mg with Fe was beneficial, with enhanced capacity, rate capability, and surface stability. In addition, it was found that HEF-Fe showed similar cycle stability without an electrochemically inactive element. These findings provide valuable insights for the design of high entropy multielement fluorides for improved Li-ion battery performance.

Enhanced Electrochemical Performance of Surface-Nitrided MnO Negative Electrode Materials in Li-Ion Batteries

Enhanced Electrochemical Performance of Surface-Nitrided MnO Negative Electrode Materials in Li-Ion Batteries

3-Electrode Setup for the Operando Detection of Side Reactions in Li-Ion Batteries: The Quantification of Released Lattice Oxygen and Transition Metal Ions from NCA

Detecting parasitic side reactions is paramount for developing stable cathode active materials (CAMs) for Li-ion batteries. This study presents a method for the quantification of released lattice oxygen and transition metal ions (TMII+ ions). It is based on a 3-electrode cell design employing a Vulcan carbon-based sense electrode (SE) that is held at a controlled voltage against a partially delithiated lithium iron phosphate (LFP) counter electrode (CE). At this SE, reductive currents can be measured while polarizing a CAM working electrode (WE), here a LiNi0.80Co0.15Al0.05O2 (NCA), against the same LFP CE. In voltammetric scans, we show how the SE potential can be selected to specifically detect a given side reaction during CAM charge/discharge, allowing, e.g., to discriminate between lattice oxygen and dissolved TMs. Furthermore, it is shown via online electrochemical mass spectrometry (OEMS) that O2 reduction in the here-used LP47 electrolyte consumes ∼2.3 electrons/O2. Using this value, the lattice oxygen release deduced from the 3-electrode setup upon charging of the NCA WE is in good agreement with OEMS measurements up to NCA potentials >4.65 VLi. At higher potentials, the contributions from the reduction of TMII+ ions can be quantified by comparing the integrated SE current with the O2 evolution from OEMS.

Fly-ash derived crystalline Si (cSi) Improves the capacity and energy density of LiNi0.8Co0.1Mn0.1O2 battery: Synthesis and performance

For decades, graphite has been the key ingredient in the anode of Li-ion batteries (LIBs). The search for high-capacity anode materials for Li-ion batteries (LIBs) has led to increasing interest in silicon (Si) as a potential replacement for graphite. This study presents an innovative approach to synthesizing crystalline Si (cSi) from type C fly ash, addressing both the need for improved LIB anodes and the challenge of industrial waste management. Our novel process involves a stepwise method of extraction, gelation using various mineral acids (HCl, H2SO4, and HNO3), magnesiothermic reduction, and purification. X-ray diffraction and energy-dispersive X-ray spectroscopy confirmed the production of high-purity SiO2 and cSi. Notably, a cSi-doped graphite anode (5 % Si) paired with LiNi0.8Mn0.1Co0.1O2 (NMC811) in a cylindrical cell achieved a minimum specific discharge capacity of 388 mAh/ganode after formation, surpassing the theoretical capacity of graphite (372 mAh/g). This demonstrates that even a small amount of cSi can significantly enhance anode performance. Our scalable, simple, and economical process offers a dual benefit: improving battery characteristics while providing an efficient method for fly ash waste utilization. This approach paves the way for sustainable production of high-performance LIB anodes while addressing critical waste management challenges.

Enhanced structural stability of Si electrode employing TiNi/Si pillars with oriented Li diffusion pathway

As the anode materials of Li-ion batteries, pillar-shaped TiNi/Si particles fabricated by employing electrochemical etching of (100) Si wafers and TiNi alloy coating, were investigated for their structural and electrochemical properties. The most suitable porous wafer for producing Si pillars was obtained at a current density of 2.5 mA/cm2 during etching. The deposited TiNi alloy film consisted of a crystallized austenitic (B2) phase capable of inducing phase transformation through annealing at 500°C. Particularly, by coating with the inactive materials, only the (100) plane of single crystalline Si was exposed during the initial charging process to restrict Li ion movement exclusively along the <100>Si direction. The TiNi/Si electrode exhibited a lower capacity compared to the Si electrode but demonstrated improved cycling performance. It showed a charge capacity of 1110 mAh/g at 0.1 C with an initial efficiency of 77 % and maintained a capacity retention of 49 % (543 mAh/g) up to 100 cycles. After the initial cycle, Si electrodes exposed to various lithium insertion directions exhibited severe structural damage such as cracking and particle pulverization, whereas TiNi/Si electrodes demonstrated enhanced structural stability due to surface coating and restricted reaction pathway.

Aspects of Spodumene Lithium Extraction Techniques

Lithium (Li), a leading cathode material in rechargeable Li-ion batteries, is vital to modern energy storage technology, establishing it as one of the most impactful and strategical elements. Given the surge in the electric car market, it is crucial to improve lithium recovery from its rich mineral deposits using the most effective extraction technique. In recent years, both industry and academia have shown significant interest in Li recovery from various Li-bearing minerals. Of these, only extraction from spodumene has established a reliable industrial production of Li salts. The current approaches for cracking of the naturally occurring, stable α-spodumene structure into a more open structure—β-spodumene—involve the so-called decrepitation process that takes place at extreme temperatures of ~1100 °C. This conversion is necessary, as β-spodumene is more susceptible to chemical attacks facilitating Li extraction. In the last several decades, many techniques have been demonstrated and patented to process hard-rock mineral spodumene. The objective of this review is to present a thorough analysis of significant findings and the enhancement of process flowsheets over time that can be useful for both research endeavors and industrial process improvements. The review focuses on the following techniques: acid methods, alkali methods, carbonate roasting/autoclaving methods, sulfuric acid roasting/autoclaving methods, chlorinating methods, and mechanochemical activation. Recently, microwaves (MWs), as an energy source, have been employed to transform α-spodumene into β-spodumene. Considering its energy-efficient and short-duration aspects, the review discusses the interaction mechanism of MWs with solids, MW-assisted decrepitation, and Li extraction efficiencies. Finally, the merits and/or disadvantages, challenges, and prospects of the processes are summarized.

Li3V2(PO4)3 sintering atmosphere optimisation for its integration in all-solid-state batteries

Integration of active materials into the architecture of all-solid-state batteries represents a significant scientific inquiry. Li3V2(PO4)3 (LVP), a positive and negative electrode active material for Li-ion batteries, has been subject to extensive research to elucidate its electrochemical behaviour during cycling processes. However, the comprehensive analysis of its thermal behaviour under different sintering atmosphere conditions has remained underexplored, particularly in the context of its compatibility with solid electrolytes. This study presents a meticulous study of sintering process under different atmospheres with precise control over oxygen partial pressure. Interestingly, we were able to sinter LVP and obtain dense, pure ceramic phase under slightly oxidising atmosphere, characterized by conductivity properties analogous to those observed in samples sintered under Ar/H2 conditions. The findings of this investigation contribute to the understanding of the optimal conditions required for the sintering of LVP, paving the way for the co-sintering of this material with inorganic solid electrolyte unstable under reducing atmosphere, such as LATP.

Functionalized MBene, Ti[formula omitted]BX[formula omitted] (X=Si, Ge, P, As) as potential excellent anode materials for lithium and sodium-ion batteries: A first-principles study

In the search for next-generation energy storage devices, superior-performance alternative electrode materials based on two-dimensional materials for rechargeable metal-ion batteries are essential. Here, we explored group III and IV functionalization of 2D Ti2B, Ti2BX2 (X=Si, Ge, P, As) as anode materials for Li and Na ion batteries using first-principles calculations. The structures had excellent metallic properties and demonstrated energetically favorable adsorptions for metal ions. Analyzing charge transfer and electronic band structures, silicon and phosphorous-functionalized Ti2B (Ti2BSi2 and Ti2BP2) showed the most potential. The energy band diagrams showed that both Ti2BSi2 and Ti2BP2 had metallic characteristics after Li and Na-ion adsorption, which offered considerable advantage for rechargeable-ion batteries. The structures exhibited low energy barriers for Li and Na-ion migration. The minimum energy barriers calculated for Na were 0.08 eV for Ti2BSi2 and 0.24 eV for Ti2BP2. Theoretical specific capacity and open circuit voltage were calculated using maximum layer adsorption. For both Li and Na, high values of specific capacity and low values of open circuit voltage (¡ 1 V) were found. Ti2BSi2 had the best performance, with a theoretical specific capacity of 1647.10 and 1317.68 mA h/g for Li and Na, respectively. Its open circuit voltages for Li and Na were 0.65 and 0.38 V. The insights of this study will be beneficial in fabricating high-performing Ti2BX2-based anodes for rechargeable Li and Na ion batteries.

Conducting LixPOy Interface Generated From Insulating Residual Lithium Compounds on LiNi0.8Mn0.1Co0.1O2 Surface Improves Cycle Life and Assists in Fast Cycling.

LiNi0.8Mn0.1Co0.1O2 (NMC811) is the most promising cathode material for future Li-ion batteries (LIBs). However, the bulk and surface structural instabilities retard its commercial success. Surface chemical instability toward exposure to moisture (H2O and CO2) leads to the formation of residual lithium compounds (RLCs: Li2CO3, LiOH) on the surface. The alkaline RLCs form a resistive layer on the surface of NMC811 by undergoing parasitic side reactions with electrolytes. Herein, an "Adverse-to-Beneficial" approach is proposed to eliminate RLCs by chemically transforming them into a LixPOy (Li3PO4 and LiPO3) interface. The interface protects the NMC811 surface from moisture attack and unwanted side reactions with electrolytes. It enhances the cycle life by retaining 70% of the initial capacity after 300 cycles at a 0.5C rate and 60% after 500 cycles, even at a 5C rate in a voltage window of 3.0-4.3V versus Li+/Li. The coexistence of two Li-conducting phases lowers the voltage polarization of the kinetically sluggish H1 → M phase transition to unlock fast cycling, reduces cationic disorder, improves coulombic efficiency, enhances ion diffusion kinetics, and minimizes particle crack formation after long-term cycling. Hence, the LixPOy interface yields multifaceted benefits in the storage, processing, and electrochemistry of NMC811.