Rechargeable Lithium Batteries Research Articles

SEI-Coated Carbon Particles: Electrochemomechanical Fracture Mechanisms

By starting from fundamental physical principles, a generalized theoretical framework was developed to engineer the intercalation-induced mechanical degradation in SEI-coated carbon particles from the surrounding electrolyte in rechargeable lithium-ion batteries (LIBs). Six elemental regimes of fracture formation in spherical electrochemically active carbon particles of radius, r p , coated with an SEI layer of thickness, δ ≪ r p , have been identified: The pristine regime, the SEI debonding regime, the SEI surface flaw regime, the surface carbon flaw regime (delithiation), the internal circular carbon flaw regime (lithiation), and the carbon exfoliation regime (lithiation); as well as four combined regimes during delithiation and four combined regimes during lithiation. Results are summarized in terms of C-Rate versus particle size, degradation maps, to identify LIB operation conditions where the performance can be optimized, while suppressing the decrepitation of the SEI-coated carbon particle system. Improved porous electrode layers that deliver longer battery life are possible by selecting electrolytes that considering the design of SEI-coated carbon particles of tailored elastic stiffness and critical stress intensity factor, so that they are safe from developing a chemomechanically induced flaw, exfoliation, or carbon re-forming, during both lithiation or delithiation in the 1 to 10 μm size particle, and C-Rates < 1 C.

Hybrid Organosulfur Cathode Materials for Rechargeable Lithium Batteries

Hybrid Organosulfur Cathode Materials for Rechargeable Lithium Batteries

LiNO3 -Based Electrolytes via Electron-Donation Modulation for Sustainable Nonaqueous Lithium Rechargeable Batteries.

LiPF6 as a dominant lithium salt of electrolyte is widely used in commercial rechargeable lithium-ion batteries due to its well-balanced properties, including high solubility in organic solvents, good electrochemical stability, and high ionic conductivity. However, it suffers from several undesirable properties, such as high moisture sensitivity, thermal instability, and high cost. To address these issues, herein, we propose an electron-donation modulation (EDM) rule for the development of low-cost, sustainable, and electrochemically compatible LiNO3 -based electrolytes. We employ high donor-number solvents (HDNSs) with strong electron-donation ability to dissolve LiNO3 , while low donor-number solvents (LDNSs) with weak electron-donation ability are used to regulate the solvation structure to stabilize the electrolytes. As an example, we design the LiNO3 -DMSO@PC electrolyte, where DMSO acts as an HDNS and PC serves as an LDNS. This electrolyte exhibits excellent electrochemical compatibility with graphite anodes, as well as the LiFePO4 and LiCoO2 cathodes, leading to stable cycling over 200 cycles. Through spectroscopy analyses and theoretical calculation, we uncover the underlying mechanism responsible for the stabilization of these electrolytes. Our findings provide valuable insights into the preparation of LiNO3 -based electrolytes using the EDM rule, opening new avenues for the development of advanced electrolytes with versatile functions for sustainable rechargeable batteries.

Phenyl Tellurosulfides as Cathode Materials for Rechargeable Lithium Batteries.

Phenyl ditelluride (PDTe) as a cathode material for rechargeable batteries has a low specific capacity (130.9 mAh g-1) due to limited active sites (two). To increase its capacity, additional active species need to be added to the structure of PDTe, like sulfur. Here, phenyl tellurosulfide (PDTeS) and phenyl tellurodisulfide (PDTeS2) can be formed via addition reactions and have specific capacities of 242.8 and 339.6 mAh g-1, respectively. The products are characterized by mass spectrometry and Raman spectroscopy. The Li/PDTeSn (n = 1-2) cells exhibit high material utilization (>85%) and unique redox mechanism. They can be cycled stably for more than 1000 cycles at an areal mass loading of 1.1 mg cm-2 and maintain capacity retentions of >72% after 100 cycles with PDTeSn loading of ∼6 mg cm-2. Moreover, the Li/PDTeS2 cell achieves a specific energy of up to 695 Wh kg-1 even when the electrolyte/PDTeS2 ratio is as low as 2.5 μL mg-1. The successful synthesis and application of PDTeSn prove that they are promising cathode materials for rechargeable lithium batteries.

A Layered Organic Cathode for High-Energy, Fast-Charging, and Long-Lasting Li-Ion Batteries.

Eliminating the use of critical metals in cathode materials can accelerate global adoption of rechargeable lithium-ion batteries. Organic cathode materials, derived entirely from earth-abundant elements, are in principle ideal alternatives but have not yet challenged inorganic cathodes due to poor conductivity, low practical storage capacity, or poor cyclability. Here, we describe a layered organic electrode material whose high electrical conductivity, high storage capacity, and complete insolubility enable reversible intercalation of Li+ ions, allowing it to compete at the electrode level, in all relevant metrics, with inorganic-based lithium-ion battery cathodes. Our optimized cathode stores 306 mAh g-1cathode, delivers an energy density of 765 Wh kg-1cathode, higher than most cobalt-based cathodes, and can charge-discharge in as little as 6 min. These results demonstrate the operational competitiveness of sustainable organic electrode materials in practical batteries.

A dicarbonate solvent electrolyte for high performance 5 V-Class Lithium-based batteries

Rechargeable lithium batteries using 5 V positive electrode materials can deliver considerably higher energy density as compared to state-of-the-art lithium-ion batteries. However, their development remains plagued by the lack of electrolytes with concurrent anodic stability and Li metal compatibility. Here we report a new electrolyte based on dimethyl 2,5-dioxahexanedioate solvent for 5 V-class batteries. Benefiting from the particular chemical structure, weak interaction with lithium cation and resultant peculiar solvation structure, the resulting electrolyte not only enables stable, dendrite-free lithium plating-stripping, but also displays anodic stability up to 5.2 V (vs. Li/Li+), in additive or co-solvent-free formulation, and at low salt concentration of 1 M. Consequently, the Li | |LiNi0.5Mn1.5O4 cells using the 1 M LiPF6 in 2,5-dioxahexanedioate based electrolyte retain >97% of the initial capacity after 250 cycles, outperforming the conventional carbonate-based electrolyte formulations, making this, and potentially other dicarbonate solvents promising for future Lithium-based battery practical explorations.

Tuning the electrochemical performance of Cr2B2 MBene anodes for Li and Na-ion batteries through F and Cl-functionalization: A DFT and AIMD study

In an era in which sustainable energy sources and electric vehicles are prevalent, the development of efficient anode materials is paramount to address the pressing demand for improved energy storage technologies. After the graphene revolution, many other 2D materials such as graphene, MXene (atomically thin layer of Transition Metal Carbide/Nitride/Carbonitride), TMDC (Transition Metal Dichalcogenide), and MBene (atomically thin layer of Transition Metal Borides) have emerged as potential high-performance anode materials. A recent study demonstrated the possibility of synthesizing chromium-based MBenes for the first time, and the electrochemical performance of Cr2B2 as a potential anode material has also been studied theoretically. Inspired by this, the current study utilized density functional theory and ab initio molecular dynamics simulations to probe the role of Cl and F-functionalization of Cr2B2 MBenes as anode materials for rechargeable lithium-ion batteries (LIB) and sodium-ion batteries (NIB). The electronic structure, adsorption, diffusion, and storage capacity of Li (Lithium) and Na (Sodium) were systematically investigated. This study revealed that Cr2B2F2 and Cr2B2Cl2 exhibit excellent conductivity due to their intrinsic metallic properties. In addition, they have low diffusion energy barriers for Li and Na ions (0.13/0.14 and 0.20/0.20 eV for Cr2B2F2 and Cr2B2Cl2, respectively) facilitating rapid charge/discharge rates. The calculations further unveiled a notable Li-ion storage capacity of 818 mAh g-1 for 2D Cr2B2Cl2, accompanied by a moderate open-circuit voltage (OCV) range of 0.38 V to 0.98 V, illustrating its potential as a superior anodic material for LIBs. Similarly, Cr2B2F2 demonstrated a substantial Na-ion storage capacity of 655 mAh g-1, coupled with a reasonably ranged average OCV of 0.20 V to 0.71 V, positioning it as a compelling candidate for NIBs. In all, this investigation has identified two superior electrode materials for alkali-ion batteries, which can spark additional interest in exploring MBene as a promising candidate for advancing next-generation anode materials.

A protocol and training guidelines for mosquito sampling in remote areas with limited power supply

Mosquito-borne diseases pose a significant threat in many Southeast Asian countries, particularly through the sylvatic cycle, which has a wildlife reservoir in forests and rural areas. Studying the composition and diversity of vectors and pathogen transmission is especially challenging in forests and rural areas due to their remoteness, limited accessibility, lack of power, and underdeveloped infrastructure. This study is based on the WHO mosquito sampling protocol, modifies technical details to support mosquito collection in difficult-to-access and resource-limited areas. Specifically, we describe the procedure for using rechargeable lithium batteries and solar panels to power the mosquito traps, demonstrate a workflow for processing and storing the mosquitoes in a -20 °C freezer, data management tools including microclimate data, and quality assurance processes to ensure the validity and reliability of the results. A pre- and post-test was utilized to measure participant knowledge levels. Additional research is needed to validate this protocol for monitoring vector-borne diseases in hard-to-reach areas within other countries and settings.

Three-dimensional copper current collector as an anode for rechargeable anode-less lithium-ion batteries

The formation of dendrites presents a significant challenge that hampers the performance of lithium metal batteries, leading to rapid capacity degradation, low coulombic efficiency, and potential short circuits. In this regard we have engineered a rechargeable lithium metal battery without a conventional anode – lithium, employing commercially available LiNi1/3Co1/3Mn1/3O2 as a cathode and enhanced three-dimensional copper foam current collector as an anode. The modification of the three-dimensional copper foam current collector with gold effectively reduced the local current density while providing a substantial surface area for lithium deposition. Moreover, our approach incorporates a blend of salts, namely lithium bis(trifluoromethanesulfonyl)imide and lithium difluoro(oxalato)borat, resulting in an impressive reversible capacity of 100 mAh g−1 with an outstanding coulombic efficiency of 99.9% after 50 cycles. These discoveries hold particular significance in the advancement of next-generation energy storage systems characterized by high energy density and immunity to dendrite formation.

Compositionally complex ball-in-ball type metal oxide anode via laser-induced fast fabrication for binder-free high-capacity Li-ion batteries

This study focuses on addressing the limited cycleability challenge of conversion-type anodes in rechargeable lithium-ion batteries (LIBs) by utilizing new high entropy materials with innovative fabrication techniques. This is the inaugural exploration of first-row transition metals (Fe, Co, Ni, Mn, Cr) composed in an entropically stabilized glycerate form (HEG) as an efficient LIB anode with a high reversible capacity exceeding 500 mAh/g (0.1 A/g) over 270 cycles. Further, we demonstrate an innovative rapid conversion of the HEG to a spinel phase high entropy oxide (HEO) via a CO2 laser treatment and demonstrate the fabrication of a binder-free anode comprising laser-induced reduced graphene oxide (rGO) and HEO ((Fe0.45Co0.14Ni0.2Cr0.13Mn0.08)3O4) composites. The composite (HEO@rGO) showed a high specific capacity of ~794 mAh/g (0.1 A/g) after 100 cycles and a specific capacity of ~530 mAh/g (0.5 A/g) after 200 cycles. These results surpass the performance of many previous reports on high entropy materials. The charge storage mechanism demonstrated the persistence of the spinel structure within HEO, accompanied by a partial transformation towards a rock salt configuration. The undulating nature of the cycling stability profile was found to be linked with a variation in charge transfer resistance and lithium diffusion with cycling.

Trilithium salt of tetrahydroxyanthraquinone: A high-voltage and stable organic cathode material for rechargeable lithium metal and lithium-ion batteries

Organic cathode materials (OCMs) have drawn considerable attention for lithium batteries but suffer from unfavorable dissolution problem and thus inferior cycling performance. Salification is a simple approach to restrain the dissolution but most reported lithium-salt-type OCMs are still unable to achieve good cycling stability due to poorly conjugated and/or asymmetric structure. Herein, we report a novel air-stable, largely conjugated, and symmetric organic lithium salt synthesized from 1,4,5,8-tetrahydroxyanthraquinone (THAQ), namely Li3THAQ. It possesses a layered crystalline structure with large interlayer spacings, which is relatively stable in the reversible conversion between Li4THAQ and Li2THAQ. Benefiting from this, Li3THAQ exhibits exceptional electrochemical performance within 2.0–3.6 V, including high reversible capacity (192 mAh g−1), high discharge potential (2.93 V vs. Li+/Li), high rate capability (75 % capacity retention at 5000 mAh g−1 vs. 50 mAh g−1), and high cycling stability (95 % capacity retention after 500 cycles). Additionally, it can be also matched with natural graphite anode to construct a Li-ion full-cell, which was rarely reported for OCMs. In brief, Li3THAQ shows great advantages in structure stability, electrochemical performance, and practicability compared to its counterparts, and the in-depth mechanism understanding provides important insights into the development of lithium-salt-type OCMs.

A high-current initiated formation strategy for improved cycling stability of anode-free lithium metal batteries

Anode-free lithium metal batteries (AFLMBs) are considered as one of the most promising candidates for next-generation high-energy-density rechargeable lithium batteries. An efficient high-current initiated formation strategy is developed for AFLMBs.

Design of a new Li-rich Mn-based ternary cathode material based on the Ni, Co, and Mn action mechanism.

Rechargeable lithium-ion batteries, as the most advanced energy storage devices currently available, urgently require the development of cathode materials with high capacity, large specific energy, and fast charge/discharge performance to satisfy the continuous technological innovation. Here, a Li-rich Mn-based ternary cathode material Li7/6Nil/6Co1/6Mn1/2O2 is designed, and the geometrical structure, electronic properties, and thermodynamic properties of this material are investigated employing the first-principles method. Six layered structure models are established by adjusting the ratio of Ni, Co, and Mn elements, and the effects of various elements on the material properties are evaluated. Based on the performance of Ni, Co, and Mn in the structure, Li1.2Ni0.15Co0.1Mn0.55O2 features favorable electrical conductivity, thermal conductivity, and excellent stability. This material obtained through co-precipitation using a high temperature solid phase synthesis presents a high actual capacity (245 mA h g-1) and superior cycling performance (the capacity retention rate of the material is 84% after 60 cycles at 0.2C). This effort discusses the Li-rich Mn-based cathode materials in terms of the structural basis, reaction mechanism, and application exploration, which are valuable for guiding their theoretical design, optimization modification, and industrial application.

Theoretical study of two-dimensional BeB&lt;sub&gt;2&lt;/sub&gt; monolayer as anode material for magnesium ion batteries

&lt;sec&gt;Rechargeable lithium-ion batteries as the main energy storage equipment should possess high power density, excellent reversible capacity, and long cycle life. However, due to the high cost and dendrite growth of Li, searching for non-Li-ion batteries is urgent. Compared with lithium, magnesium has abundant resources, small ionic radius, and high energy density. Therefore, magnesium-ion batteries (MIBs) can serve as the next generation metal-ion batteries. Two-dimensional materials based on Be or B element acting as the anode of metal-ion batteries always exhibit high theoretical storage capacity. Using first-principles calculations, we systematically explore the potential of BeB&lt;sub&gt;2&lt;/sub&gt; as MIBs anode. The optimized BeB&lt;sub&gt;2&lt;/sub&gt; monolayer structure shown in Fig. (a) consists of two atomic layers, where each Be atom is coordinated with six B atoms, and each B atom is coordinated with three Be atoms.&lt;/sec&gt;&lt;sec&gt;The lattice constants are &lt;i&gt;a&lt;/i&gt; = &lt;i&gt;b&lt;/i&gt; = 3.037 Å with a thickness of 0.554 Å. From the phonon spectrum calculations, the absence of imaginary modes indicates the dynamic stability of BeB&lt;sub&gt;2&lt;/sub&gt; monolayer. The presence of a Dirac cone further suggests the excellent conductivity (Fig.(b)). Three stable adsorption sites (Be&lt;sub&gt;1&lt;/sub&gt;: top of Be atoms; Be&lt;sub&gt;2&lt;/sub&gt; and B&lt;sub&gt;2&lt;/sub&gt;: bottom of Be and B atoms) are labeled in Fig. (a). Taking symmetry into account, we consider three pathways to evaluate the migration of Mg atom on BeB&lt;sub&gt;2&lt;/sub&gt; monolayer (Fig.(c)). The corresponding lowest diffusion energy barrier is 0.04 eV along Path III. The stable configuration with the maximum adsorption Mg concentration is shown in Fig.(d), which generates a theoretical capacity of 5696 mA·h·g&lt;sup&gt;–1&lt;/sup&gt;. The calculated average open-circuit voltage is 0.33 V. Based on &lt;i&gt;ab initio&lt;/i&gt; molecular dynamics simulations, the total energy of BeB&lt;sub&gt;2,&lt;/sub&gt; with Mg adsorbed, fluctuates within a narrow range, suggesting that BeB&lt;sub&gt;2&lt;/sub&gt; can sustain structural stability after storing Mg at room temperature (Fig.(e)). Finally, for practical application, we investigate the adsorption and diffusion behavior of Mg on bilayer BeB&lt;sub&gt;2&lt;/sub&gt;. Three configurations are considered: &lt;i&gt;AA&lt;/i&gt; stacking (overlapping of Be atoms in upper layer with Be atoms in lower layer), &lt;i&gt;AB&lt;/i&gt; stacking (overlapping of Be atoms in upper layer with B atoms in lower layer), and &lt;i&gt;AC&lt;/i&gt; stacking (overlapping of Be atoms in upper layer with B—B bonds in lower layer). The most stable configuration is &lt;i&gt;AB&lt;/i&gt; stacking (shown in Fig.(f)) with the interlayer spacing of 3.12 Å and the binding energy of –120.97 meV/atom. Comparing with the BeB&lt;sub&gt;2&lt;/sub&gt; monolayer structure, the adsorption energy of Mg is –2.24 eV for Be&lt;sub&gt;1&lt;/sub&gt;, –1.38 eV for B&lt;sub&gt;5&lt;/sub&gt; site, and –1.90 eV for B&lt;sub&gt;4&lt;/sub&gt; site, while the lowest diffusion energy barrier is 0.13 eV along the path of B&lt;sub&gt;5&lt;/sub&gt;-Be&lt;sub&gt;3&lt;/sub&gt;-B&lt;sub&gt;5&lt;/sub&gt;. Therefore, according to the above-mentioned properties, we believe that BeB&lt;sub&gt;2&lt;/sub&gt; monolayer can serve as an excellent MIBs anode material.&lt;/sec&gt;

Tuning wettability of gallium-based liquid metal anode for lithium-ion battery via a metal mixing strategy

Exploring highly stable alloy-type anodes for rechargeable lithium batteries is urgent with the ever-increasing demands for high energy density batteries. The liquid metal (LM)-based anodes demonstrate great potential in advanced lithium-ion batteries due to their high energy densities and self-healing performance. However, its high surface tension leads to poor wettability towards the current collector and higher interfacial contact resistance. In this study, we developed a new free-standing LM-based anode LM-W10/Cu foil with good wettability and machinability by mixing high-melting-point tungsten (W) nanoparticles. It greatly improves the inherent defects of poor interfacial contact and lithium diffusion kinetics between the LM and current collectors, reduces the tedious and costly electrode manufacturing process, and regulates lithium deposition behaviors. And this metal mixing strategy has a negligible effect on the self-healing nature of LM. Symmetric cells of LM-W10/Cu foil anodes displayed a low overpotential (~13 mV) and cycled stably for more than 8,000 h (4,000 cycles) at 0.5 or 1 mA/cm2; full cells coupled with LiFePO4 cathode showed a high capacity retention of 95.15% after 150 cycles.

Towards separator safety of lithium-ion batteries: a review

The recent advance of high-safety separators with high mechanical strength, high thermal stability and good lithium dendritic resistance is the main focus in this review. The future challenges and perspectives of separators are provided for building high safety rechargeable lithium batteries.

Kinetically controlled synthesis of low-strain disordered micro-nano high voltage spinel cathodes with exposed {111} facets.

High-voltage LiNi0.5Mn1.5O4 (LNMO) is one of the most promising cathode candidates for rechargeable lithium-ion batteries (LIBs) but suffers from deteriorated cycling stability due to severe interfacial side reactions and manganese dissolution. Herein, a micro-nano porous spherical LNMO cathode was designed for high-performance LIBs. The disordered structure and the preferred exposure of the {111} facets can be controlled by the release of lattice oxygen in the high-temperature calcination process. The unique configuration of this material could enhance the structural stability and play a crucial role in inhibiting manganese dissolution, promoting the rapid transport of Li+, and reducing the volume strain during the charge/discharge process. The designed cathode exhibits a remarkable discharge capacity of 136.7 mA h g-1 at 0.5C, corresponding to an energy density of up to 636.4 W h kg-1, unprecedented cycling stability (capacity retention of 90.6% after 500 cycles) and superior rate capability (78.9% of initial capacity at 10C). The structurally controllable preparation strategy demonstrated in this work provides new insights into the structural design of cathode materials for LIBs.

Nickel-doped Li2MoO4 as a high-performance anode material for rechargeable lithium-ion batteries

Transition metal oxides represent a promising anode material for rechargeable lithium-ion batteries (LIBs) because of their high theoretical specific capacity. Li2MoO4 (LMO) has a high specific capacity due to its...

Low-cost p-benzoquinone-formaldehyde polymer/reduced graphene oxide composite films as a cathode material for rechargeable lithium-ion batteries

Due to the favorable chemical structure of FQ and the high electrical conductivity of rGO, FQ/rGO composite films demonstrate a high practical capacity at large current densities, while maintaining excellent cycling stability.

Fast discharging mitigates cathode-electrolyte interface degradation of LiNi0.6Mn0.2Co0.2O2 in rechargeable lithium batteries

The rapid deterioration of lithium-ion batteries in fast-charging and discharging conditions poses a major challenge for future mobility technologies. Accelerated failure is attributed to the non-equilibrium de/lithiation reaction at inter- and intra-particle levels in electrodes induced by high current densities. However, the correlation between the reaction heterogeneity and degradation rate remains elusive. Here, we unambiguously decouple the effects of fast charging and discharging on battery degradation by applying asymmetric charging–discharging protocols. Our findings reveal that fast charging stimulates the electrolyte decomposition and surface reconstruction and, surprisingly, fast discharging mitigates these detrimental effects. The improved cyclability originates from the kinetically lowered depth of discharge (DOD) upon fast discharging, enabling a homogeneous electrochemical reaction by evading the slow-kinetics state-of-charge regime. Proving the beneficial effect of limiting DOD, we demonstrate a protocol that effectively suppresses degradation under fast charging conditions, resulting in negligible capacity decay while delivering an accumulated capacity of 30 Ah g−1. In contrast, conventional protocols show drastic capacity decay (13.8% retention). This study establishes a causal coupling between cathode degradation, reaction heterogeneity, and current density and direction at multiple length scales, providing valuable guidance for designing advanced battery cycling protocols that promote stable long-term battery operation, particularly under fast-charging conditions.