High-performance Lithium-ion Batteries Research Articles

Co-Assembly of Polyoxometalates and Porphyrins as Anode for High-Performance Lithium-Ion Batteries.

Polyoxometalates (POMs) have been considered one of the most promising anode candidates for lithium-ion batteries (LIBs) in virtue of their high theoretical capacity and reversible multielectron redox properties. However, the poor intrinsic electronic conductivity, low specific surface area, and high solubility in organic electrolytes hinder their widespread applications in LIBs. Herein, a novel hybrid nanomaterial is synthesized by co-assembling POMs and porphyrins (PMo12/CoTPyP) through a facile solvothermal method. The POM clusters are stabilized by porphyrin units through electrostatic interactions, which simultaneously realize the uniform dispersion of POMs and porphyrin units. Benefiting from the generated sub-1nm channels for fast ion transport and the synergistic effect between evenly distributed PMo12 clusters and high-conductive CoTPyP units, the LIB based on the optimized PMo12/CoTPyP anode exhibits significantly improved Li+ storage capability as well as superior rate and cycling performance. The results of density functional theory simulations further reveal that the co-assembly of PMo12 and CoTPyP can accelerate the mobility of Li+ and electrons, which in turn promotes the enhancement of LIBs performance. This work paves a strategy for synthesizing POMs-based anode materials with simultaneously high dispersibility, redox activity, and stability.

Multilayer Ti3C2Tx-loaded CoOHF composite structures for high-performance lithium-ion batteries

Research into new composites to enhance the performance of lithium-ion battery electrode materials has become a trendy area of study. Cobalt-based composites are particularly prominent due to their exceptional electrochemical performance and unique physicochemical properties. Additionally, Ti3C2Tx MXenes materials are anticipated to replace graphene and other carbonaceous materials since they possess an open structure and low lithium-ion diffusion barrier. In this work, we employed simple hydrothermal method to combine layered Ti3C2Tx with needle-shaped CoOHF. The resulting nanosheets showed an even dispersion of CoOHF in the surface, leading to a remarkable increase in specific capacity. Furthermore, Ti3C2Tx provided a higher number of lithium-ion active sites and improved the lithium-ion migration rate, while also ensuring the structure and stability of CoOHF. This composite material enables stable cycling for 1000 cycles at high current densities of 2 A g−1 and ultimately shows a large capacity of 802.4 mAh g−1 stably. Additionally, CoOHF/MXene composites display exceptional performance rate and cycling stability. This study highlights new feasible strategies for using multilayer Ti3C2Tx in lithium-ion batteries, along with metal hydroxyfluorides in new, highly efficient lithium-ion battery anode materials.

Electronic structure and delithiation mechanism of vanadium and nickel doped Li2MnPO4F cathode material for lithium-ion batteries

This study calculates the energy band structure and density of states of Lithium manganese fluorophosphate (Li2MnPO4F, a lithium transition metal phosphate compounds) using the first-principles plane-wave pseudopotential approach within the density-functional theory. The model of Li2M0.5Mn0.5PO4F (M = V, Ni) with transition metal doped Mn sites is constructed by using the CASTEP module. The calculation findings indicate that the transition metal doping can regulate the energy band structure of the intrinsic system, and Li2MnPO4F makes the band gap decrease, and the volume increase with the Li ions of being deintercalated, and the electrons can be readily stimulated from the valence band to the conduction band. The findings indicate that Li2MnPO4F is a favorable cathode material for high-voltage lithium ion batteries (LIBs). The introduction of vanadium (V) and nickel (Ni) doping reduces the band gap, facilitating an easier excitation of electrons from the valence band to the conduction band. This study provides a theoretical study of new cathode materials for high performance LIBs.

Enhanced mechanical and surface chemical stability in cobalt-free, high-nickel cathode materials for lithium-ion batteries

Cobalt-free, high-nickel cathode materials are essential for the sustainable evolution of energy storage technologies, reducing the dependence on resources with significant environmental and social implications and simultaneously improving the efficiency and cost effectiveness of batteries. This paper introduces a cobalt-free, high-nickel cathode material called 0.01B-LiNi0.98Mg0.01Zr0.01O2 (NMZB) developed using a novel blend of elements to enhance mechanical and surface chemical stability. Detailed evaluations confirmed the successful integration of Mg, Zr, and B into the particles, with Mg and Zr primarily located within the particle interior and B predominantly on the surface. This unique elemental configuration significantly improves the stability of the bulk phase and surface structure of the material. In addition, the refinement of primary particles within NMZB further enhances its mechanical stability. As a result, NMZB exhibits exceptional electrochemical stability, achieving 90.5 % capacity retention after 200 cycles at a 1C rate. This compositional strategy incorporates a high nickel content into layered materials while eliminating cobalt, which is crucial for advancing the development of cost effective and high-performance lithium-ion battery technology.

Insight into graphene/boron arsenide heterostructure used for high-performance lithium-ion battery anode materials: The first principles study

Two-dimensional (2D) van der Waals (vdW) heterostructures demonstrate potential applications in Lithium-ion batteries (LIBs) characterized by their elevated energy storage capacity and extended operational longevity as anode materials. The structures and electronic properties of graphene/boron arsenide (Gr/BAs) heterostructures, along with the adsorption and migration of lithium (Li) atoms within the structures, are methodically analyzed through first-principles studies underpinned by density functional theory. Our calculations indicate the metallic Gr/BAs heterostructures have the structural stability, where their mechanical strength is confirmed from the elastic constant. Its diffusion barrier of Li atoms (0.25 eV) is superior among similar anode materials. The Li atoms' diffusion coefficient within the Gr/BAs heterostructure at 300 K (1.27 × 10−10 m2/s) exceeds that observed in Gr (2.0×10−11 m2/s). Besides, the presence of Gr assists in maintaining the open-circuit voltage (OCV) of Gr/BAs heterostructures in the range of 0-1 V. The theoretical specific capacity of proposed heterostructure reaches 920 mAh/g. The present calculations suggest that the Gr/BAs heterostructure could serve effectively as an anode in LIBs due to its excellent electrical conductivity, small diffusion barriers and appropriate open-circuit voltage.

A novel embedded KVO3/NC anode for high-performance lithium-ion batteries

Vanadium-based metallic salts, characterized by their intrinsic low electronic conductivity, are impeding their advancement as anode materials in the realm of lithium-ion battery technology. This study presents a novel embedded anode material KVO3/NC (KVO/NC) synthesized via a sol–gel method, with KVO3 (KVO) particles in situ growing on N-doped carbon, thereby ameliorating conductivity and electrochemical performance. The findings reveal that KVO/NC composite has three lithium-ion storage sites, ultra-high cycling stability (289 mA h/g@5000 cycles@10 C@100 %), and superior rate performance (249 mA h/g@15 C; 221 mA h/g@20 C). Coupled with LiFePO4 cathode, it achieves a competitive energy density (391 W h kg−1@0.1 C; 1–3.9 V). This work reveals the practical potential of KVO/NC as a new type of lithium-ion battery anode material with high energy density and long cycle life through a series of ex situ/in situ characterizations.

Fabrication of single-ion conductive quasi-solid-state electrolyte membrane for high-performance lithium-ion batteries

The aim of this work is to develop new quasi-solid-state electrolyte materials for lithium-ion batteries (LIBs) to improve their safety and comprehensive electrochemical performance. Herein, helical mesoporous silica nanofibers were synthesized by a sol–gel method. After grafting lithium salt onto their surfaces, a single-ion conductor (SL) was obtained. Then, using poly(vinylidene fluoride-co-hexafluoropropylene) as the polymer matrix, SL as the filler, a porous composite film was prepared by solution casting method. After soaking organic electrolyte with low concentration Li salt till saturation, one quasi-solid-state electrolyte membrane (PSLE) was achieved. It showed high electrolyte adsorption rate of 660 % and good thermal stability. A high lithium-ion transfer number of 0.85 indicated typical single-ion conductivity. Moreover, a high electrochemical stability window of up to 5.5 V and an ionic conductivity of 2.5 × 10−3 S·cm−1 at 25 °C were gained. The assembled LFP|PSLE|Li battery exhibited excellent rate performance and cycle stability, indicating that the PSLE has great application prospect in solid-state LIBs.

Research Trends of Transition Metal Carbonate for Lithium-Ion Batteries

Transition Metal Carbonates (TMCs) have emerged as promising candidates for advancing the performance of lithium-ion batteries (LIBs), driven by the increasing demand for high energy and power density in applications such as electric vehicles. This review paper provides a comprehensive overview of the potential of TMCs as anode materials for LIBs, focusing on their unique electrochemical properties and mechanisms. TMCs offer advantages such as eco-friendliness, low cost, and high capacity compared to traditional graphite anodes. Their electrochemical stability, achieved through redox reactions of transition metals, enables capacities exceeding theoretical limits. However, challenges including volumetric expansion and low electrical conductivity during cycling hinder their rate performance and cycling stability. This paper discusses ongoing research efforts to address these challenges, including strategies to mitigate volumetric expansion and enhance electrical conductivity. Furthermore, the lithiophilic nature of TMCs’ transition metals is explored for its role in stabilizing lithium metal surfaces and interfaces within lithium metal batteries, contributing to improved battery performance and safety. Moreover, integrating carbon capture, utilization, and storage (CCUS) technologies into TMC synthesis offers environmentally friendly synthesis methods, aligning with sustainability goals and reducing the carbon footprint of battery manufacturing processes. Overall, this review highlights the potential of TMCs as anode materials for high-performance LIBs, while also addressing challenges and opportunities for further research and development in this promising field.

Modulating porous silicon-carbon anode stability: Carbon/silicon carbide semipermeable layer mitigates silicon-fluorine reaction and enhances lithium-ion transport

Silicon-based material is regarded as one of the most promising anodes for next-generation high-performance lithium-ion batteries (LIBs) due to its high theoretical capacity and low cost. Harnessing silicon carbide's robustness, we designed a novel porous silicon with a sandwich structure of carbon/silicon carbide/Ag-modified porous silicon (Ag-PSi@SiC@C). Different from the conventional SiC interface characterized by a frail connection, a robust dual covalent bond configuration, dependent on SiC and SiOC, has been successfully established. Moreover, the innovative sandwich structure effectively reduces detrimental side reactions on the surface, eases volume expansion, and bolsters the structural integrity of the silicon anode. The incorporation of silver nanoparticles contributes to an improvement in overall electron transport capacity and enhances the kinetics of the overall reaction. Consequently, the Ag-PSi@SiC@C electrode, benefiting from the aforementioned advantages, demonstrates a notably elevated lithium-ion mobility (2.4 * 10−9 cm2·s−1), surpassing that of silicon (5.1 * 10−12 cm2·s−1). The half-cell featuring Ag-PSi@SiC@C as the anode demonstrated robust rate cycling stability at 2.0 A/g, maintaining a capacity of 1321.7 mAh/g, and after 200 cycles, it retained 962.6 mAh/g. Additionally, the full-cell, featuring an Ag-PSi@SiC@C anode and a LiFePO4 (LFP) cathode, exhibits outstanding longevity. Hence, the proposed approach has the potential to unearth novel avenues for the extended exploration of high-performance silicon-carbon anodes for LIBs.

Tri-monomer polyamide acid nanofiber separator for safe and high performance lithium-ion batteries

The separators play a crucial role in ensuring the safety of lithium batteries and greatly affect the electrochemical performance of the battery. However, the weak thermal stability and non-polar surface of commercial polyolefin separators severely restrict the development of the high-performance lithium batteries. In this work, we initially proposed polyamide acid (PAA) nanofiber separator with three monomers through a two-step synthesis method, which was prepared by electrospinning. By controlling different processing temperatures, PAA separators containing different amount of carboxyl groups were obtained. PAA separator had better wettability and thermal stability than PE separator. Meanwhile, the electrospinning method brings ultra-high porosity (95.3 %) to the membrane, resulting a much higher electrolyte absorption and retention rate of PAA (initially 3214 %, 240 % at 50 min) compared to PE separator. In particular, carboxyl groups serve as functional groups to provide an electronegative atmosphere, promoting the transport of lithium ion between the anode and cathode, and playing an important role in improving ionic conductivity. Consequently, batteries with PAA-SOH-50 separator showed the best rate charging/discharging performance, maintaining 87.7 % and 73.6 % of its initial capacity at 2.0 C. Moreover, cells with PAA separator exhibited much higher initial discharge capacity (164.3 mAh g−1) than that with PE separator (126.8 mAh g−1). After 100 cycles at 0.5 C, the PAA nanofiber separator achieved an ultralow attenuation rate of only 0.04 % per cycle, which was less than half of the commercial PE separator (0.10 % per cycle). This work provides a new vision for the development of separator materials, revealing the great influence of functional groups, such as carboxyl groups, on the performance of separators, which provides a strong basis for the further research of high-performance separators.

In situ formation of polymer electrolytes using a phosphazene cross-linker for high-performance lithium-ion batteries

Polymer electrolytes (PEs) have been intensively studied in lithium-ion batteries and the studies have recently focused on improving their electrochemical performances. In this study, an in situ thermal curing method is proposed to prepare polyethylene glycol-based electrolytes using a cyclic phosphazene cross-linker directly onto the lithium anode, endowing the preparation of PEs with improved ion transport across the interfaces and better electrochemical performances than those using free-standing polymer electrolytes. The buildup of the cross-linked electrolyte network by incorporating the phosphazene cross-linker endows the as-prepared PEs exhibiting excellent deformation and thermal stability, a wide electrochemical window, high ionic conductivity (3.07 × 10−3 S cm−1) at room temperature. The in situ-formed, cross-linked electrolyte network with good elasticity and conformal attachment at the electrolyte/electrode interface achieves a high capacity (>160 mAh g−1 at 0.1C rate) and a long cycle life at room temperature (0.2C rate, 93.8% at 250 cycles) in the equipped Li|LiFePO4 cell, making this strategy a promising approach for developing the next-generation lithium-ion batteries.

Design of two-dimensional coordination polymer with multiple redox-active sites for high-performance lithium-ion batteries anode material

Design of two-dimensional coordination polymer with multiple redox-active sites for high-performance lithium-ion batteries anode material

Synthesizing Si/SiOC composites through different sol-gel reaction routes for lithium-ion battery anode materials

Silicon oxycarbide (SiOC) exhibits good retention and a reasonable specific capacity and is an alternative to silicon used as an anode material for high-performance lithium-ion batteries. However, SiOC generally shows a low Initial Coulombic Efficiency (ICE), wasting the lithium from the cathode. This work explores different sol-gel routes to synthesize SiOC from silanes and compares their performance. We found that the crushed bulk acid-catalyzed SiOC is simple and cost-effective but with excellent performance. Adding dimethyldimethoxysilane (DMDMS) by decreasing the oxygen content further enhances the battery performance. Building upon the excellent performance of SiOC, we further embed nano-silicon into SiOC. The Si/SiOC composites achieved a significantly higher specific capacity of 2185 mAhg−1 and an impressive ICE of 77 % with acceptable battery retention.

Application of Li6.4La3Zr1.45Ta0.5Mo0.05O12/PEO Composite Solid Electrolyte in High-Performance Lithium Batteries.

Replacing the flammable liquid electrolytes with solid ones has been considered to be the most effective way to improve the safety of the lithium batteries. However, the solid electrolytes often suffer from low ionic conductivity and poor rate capability due to their relatively stable molecular/atomic architectures. In this study, we report a composite solid electrolyte, in which polyethylene oxide (PEO) is the matrix and Li6.4La3Zr1.45Ta0.5Mo0.05O12 (LLZTMO) and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) are the fillers. Ta/Mo co-doping can further promote the ion transport capacity in the electrolyte. The synthesized composite electrolytes exhibit high thermal stability (up to 413 °C) and good ionic conductivity (LLZTMO-PEO 2.00 × 10-4 S·cm-1, LLZTO-PEO 1.53 × 10-4 S·cm-1) at 35 °C. Compared with a pure PEO electrolyte, whose ionic conductivity is in the range of 10-7~10-6 S·cm-1, the ionic conductivity of composite solid electrolytes is greatly improved. The full cell assembled with LiFePO4 as the positive electrode exhibits excellent rate performance and good cycling stability, indicating that prepared solid electrolytes have great potential applications in lithium batteries.

Tailoring cathode materials: A comprehensive study on LNMO/LFP blending for next generation lithium-ion batteries

Lithium-ion batteries (LIBs) play a crucial role in diverse applications, including electric vehicles, portable electronics, and grid energy storage, owing to their commendable features, such as high energy density, extended cycle life, and low self-discharge rates. Despite their widespread use, the growing market demands continuous efforts to enhance LIBs performance, particularly in terms of energy density and cycling stability. This paper details the development of a lithium nickel manganese oxide (LNMO - LiNi0·5Mn1·5O4)/lithium iron phosphate (LFP - LiFePO4) blended cathode for high-performance LIBs. The study investigates the impact of blending LFP and LNMO, examining morphological and electrochemical aspects. The usage of resonant acoustic mixing (RAM) technology is demonstrated to be a promising approach to improve the distribution of LFP and LNMO particles, leading to increased electrochemical performance. The blended LNMO/LFP cathode exhibits a specific capacity exceeding 125 mAh g−1 at C/10 and a capacity retention exceeding 80 % after 1000 cycles at 1C versus lithium. Moreover, in a full-cell configuration, the blended electrode displays a capacity retention close to 74 % after 100 cycles, showcasing a nearly 30 % improvement compared to the pure LNMO cathode. This research highlights the potential of blended cathode materials in advancing the capabilities of LIBs.

Tailoring nanoscale primary silicon in laser powder bed fusion for high-performance lithium-ion battery anodes

Silicon-based anodes, utilizing nanosized silicon materials, hold great promise for the next-generation of lithium-ion batteries due to their high capacity and stable expansion. This study aims to address challenges in traditional slurry-coated anodes, such as agglomeration and low adhesive strength, through the application of laser powder bed fusion (LPBF). The process involves fabricating an Al-Si-Cu alloy layer on a Cu foil current collector, followed by dealloying to create a porous Si-Cu anode. Simulated and experimental results demonstrate successful alloy layer formation through optimized laser spot (55 μm) and powder sizes (1–5 μm). Controlled cooling produces primary Si particles ranging from 150 nm to 1 μm. The resulting microstructure enhances electrochemical performance, particularly by tailoring the size of primary Si. The resultant porous Si-Cu anode, featuring uniformly distributed primary Si (200 nm) metallurgically bonded with Cu networks, exhibits an initial coulombic efficiency of 83% and a remarkable capacity retention of 80% after 300 cycles at 2 C. In-situ and ex-situ observations confirm the crucial role of anode architecture in performance enhancement. This study elucidates the influence of the LPBF microstructure on anode performance and broadens the potential application of laser powder bed fusion in battery manufacturing.

Elucidating the role of embedding dispersed cobalt sites in nitrogen-doped carbon frameworks in Si-based anodes for stable and superior storage

Unsatisfactory conductivity and volume effects have hindered the commercial application of silicon-based materials as advanced anode materials for high-performance lithium-ion batteries. Herein, nitrogen doped carbon silicon matrix composite with atomically dispersed Co sites (Si/Co-N-C) is obtained via the design of the frame structure loaded with nano-components and the multi-element hybrid strategy. Co atoms are uniformly fixed to the N-C frame and tightly packed with nanoscale silicon particles as an activation and protection building block. The mechanism of the N-C framework of loaded metal Co in the Si alloying process is revealed by electrochemical kinetic analysis and ex situ characterization tests. Impressively, the nitrogen-doped Co site activates the intercalation of the outer carbon matrix to supplement the additional capacity. The Co nanoparticles with high conductivity and support enhance the conductivity and structural stability of the composite, accelerating the Li+/Na+ diffusion kinetics. Density functional theory (DFT) calculation confirms that the hetero-structure Si/Co-N-C adjusts the electronic structure to obtain good lithium-ion adsorption energy, reduces the Li+/Na+ migration energy barrier. This work provides meaningful guidance for the development of high-performance metal/non-metal modified anode materials.

Extended Plateau Capacity of Hard Carbon Anode for High Energy Lithium-Ion Batteries.

Hard carbon materials have shown promising potential for sodium-ion storage due to accommodating larger sodium ions. However, as for lithium-ion storage, the challenge lies in tuning the high lithiation plateau capacities, which impacts the overall energy density. Here, hard carbon microspheres (HCM) are prepared by tailoring the cross-linked polysaccharide, establishing a comprehensive methodology to obtain high-performance lithium-ion batteries (LIBs) with long plateau capacities. The "adsorption-intercalation mechanism" for lithium storage is revealed combining in situ Raman characterization and ex situ nuclear magnetic resonance spectroscopy. The optimized HCM possesses reduced defect content, enriched graphitic microcrystalline, and low specific surface area, which is beneficial for fast lithium storage. Therefore, HCM demonstrates a high reversible capacity of 537mAhg-1 with a significant low-voltage plateau capacity ratio of 55%, high initial Coulombic efficiency, and outstanding rate performance (152mAhg-1 at 10Ag-1). Moreover, the full cell (HCM||LiCoO2) delivers outstanding fast-charging capability (4min charge to 80% at 10C) and impressive energy density of 393Whkg-1. Additionally, 80% reversible capacity can be delivered under -40°C with competitive cycling stability. This work provides in-depth insights into the rational design of hard carbon structures with extended low-voltage plateau capacity for high energy LIBs.

Theoretical evaluation of newly predicted VC4 monolayer for Li-ion batteries

Carbon-rich materials could increase the capacity and improve stability by decreasing the Li+-metal repulsive interactions. Herein, a new two-dimensional (2D) vanadium tetra carbide (VC4) was predicted using the first-principles calculations. The electrical characteristics, Li-anodic applications, and structural stability of VC4 were evaluated. With a comparatively less band gap, the bare VC4 displayed a semiconductor, while the Li+-loaded VC4 possessed a metallic nature. Using a multilayer Li top/bottom adsorption technique, a high Li storage capacity of 1353 mA h g−1 was observed in the VC4 monolayer. Notably, Bader's charge scheme confirmed a favorable and reversible electrochemical reaction between Li5VC4 and VC4. Significantly, VC4 serves as a host for high-performance lithium-ion batteries (LIBs), featuring a low barrier energy of 0.18 eV and an average open circuit voltage (OCV) of 0.52 V. Impressively, the variations of the structural parameters are within 10 % for a maximum Li+ intercalation, indicating high structural stability. These enthralling findings indicate that the monolayer VC4 sheet can be realized as an efficient Li host material for rechargeable LIBs.

’Jelly to Joule’: Direct laser writing of sustainable jellyfish-based ’graphenic silicon’ anodes for environmentally remediating high-performance lithium-ion batteries

The ramifications of global climate change and resource scarcities have made it imperative to re-examine the definition of sustainable energy-storage systems. It is crucial to recognize that not all renewable resources are inherently sustainable, and their full impact on the environment must be assessed. With the proliferation of invasive jellyfish species wreaking havoc on marine ecosystems and economies worldwide, utilizing overabundant jellyfish as a carbon source presents an opportunity to create energy-storage systems that are both financially beneficial and environmentally remediating. Accordingly, a comprehensive approach to sustainability also requires eco-friendly solutions throughout the entire lifecycle, from material sourcing to battery production, without compromising high-performance requirements. Currently, most electrode syntheses for lithium-ion batteries (LIBs) employed are energy-intensive, multiple-steps, complex, and additive-heavy. In response, this work pioneers the straightforward use of low-energy laser irradiation of a jellyfish biomass/silicon nanoparticle blend to encapsulate the silicon nanoparticles in-situ within the as-forming conductive carbonized matrix, creating sustainable and additive-free composite anodes. The self-standing anode is directly synthesized under ambient conditions and requires no post-processing. Here, a laser-synthesized conductive three-dimensional porous carbon/silicon composite anode from raw jellyfish biomass for LIBs is presented, displaying outstanding cyclic stability (>1000 cycles), excellent capacity retention (>50% retention after 1000 cycles), exceptional coulombic efficiency (>99%), superb reversible gravimetric capacity (>2000 mAh/g), and high rate performance capability (>1.6 A/g), paving a new path to future sustainable energy production.