High-performance Lithium-ion Batteries Research Articles

Well-Dispersed Manganese-Oxo Clusters as Anode Materials for High-Performance Lithium Ion Batteries.

Metal-oxo clusters show great promise in lithium ion battery applications as anode materials by virtue of their native nature of well-defined nanostructures and multielectron redox activities. However, their intrinsic unsatisfactory electrical conductivity and tendency to aggregation make them difficult to fully utilize. Herein, a well-dispersed Mn12O12(CH3COO)16(H2O)4 (denoted as Mn12) cluster is constructed by rationally adopting carbon dots (CDs) with nanosize and high conductivity as stabilizers. Thanks to the fully exposed redox sites of Mn12 clusters and additional interfacial energy storage mechanism, the optimized Mn12/CDs-1:20 anode delivers a high specific capacity of 1643 mAh g-1 at 0.2 A g-1 (0.25 C) and exhibits outstanding rate and cycling capabilities. This paper provides a green and efficient paradigm to synthesize well-dispersed manganese-oxo clusters for the first time and builds a new platform for cluster-based energy storage.

Towards practical Li-ion full batteries with glass anodes

Vanadium (V)-based glasses have recently garnered considerable attention as promising anode materials for lithium-ion batteries (LIBs) due to their abundance of Li+ storage sites, neglectable volume expansion upon lithiation/delithiation, and ease of preparation. However, the inherently low electrical conductivity and relatively low energy density of V-based glass anodes hinder its application in full LIBs. In this work, we tackled this challenge by optimizing the chemical composition of the V-based glass anode to achieve high-performance half and full batteries. We investigated the impact of partially substituting B2O3 for P2O5 in 50V2O5-(50-x)P2O5-xB2O3 (mol%) (VPB) glass series on its structure and electrochemical performances. The glass with 30mol% B2O3 (VPB30 glass) was found to deliver the highest electronic conductivity, an enhanced reversible capacity of 470mAh g−1 at 1Ag−1 after 500 cycles, and excellent rate capability. The optimized performances were ascribed to the boosted lithium-ion diffusivity and the increased lithium storage sites. We assembled a full cell by coupling a VPB30 glass anode with a LiCoO2 cathode to test its cycling performance. The VPB30//LiCoO2 cell exhibits the required power density, and hence, high practicality. Our work implied the practical application of glass anodes in high-performance LIBs.

Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries

Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries

Triazine-Based Large-Sized Single-Crystalline Two-Dimensional Covalent Organic Framework for High-Performance Lithium-ion Batteries.

A large-sized single crystalline 2D COFs with excellent crystallinity and stability was prepared through the traditional thermal solvent method. The electrochemical performance can be significantly enhanced using a straightforward hybrid approach that involves in-situ growth of the 2D COFs on multi-walled carbon nanotubes (MWCNTs). Both the advantages of COFs and CNTs are mutually enhanced. The single-crystalline feature of the obtained COFs improves the structural integrity and brings excellent chemical and electrochemical stabilities for lithium-ion battery applications. The resultant COF-CNT core-shell hybrids greatly improved the conductivity and demonstrated excellent lithium-ion storage performance with a high capacity of 228 mAh g-1 (0.2 A g-1).

Electrochemical-mechanical coupled lithium growth in fiber-structured electrodes

Lithium plating (stripping) on the electrode surface and embedding inside the electrode occur simultaneously in lithium-ion batteries during fast (dis)charging, which involves both deposition and diffusion mechanisms. The paper presents a developed finite-element procedure that accommodates these two mechanisms, facilitating the modeling of the (dis)charging process in electrodes. The framework, which integrates interface electrochemical reaction kinetics, electrochemical-mechanical coupling, comprehensive constitutive models for silicon/graphite/lithium, and a surface growth re-meshing algorithm, is capable of real-time simulation of the surface deposition and coupled diffusion-deformation processes on the electrode substrate. We examined the effects of charging rate, diffusion rate and volumetric expansion on the stress of the plated lithium layer in a fiber-structured electrode. By accounting for creep in lithium metal and subsequent stress relaxation, we obtained time-dependent stress profiles in the plated lithium layer. As an application, we quantified electroplating stresses in both fiber-structured graphite and silicon electrodes. Taking the silicon electrode as a model case, we demonstrate that hollow fiber structural electrodes can also alleviate the stress in the surface lithium-plating layer. The numerical framework may be further applied to explorations for the optimization of electrode structures in advanced high performance lithium-ion batteries.

CoO nanoparticles anchored on porous pinecone-derived activated carbon as anodes for high-performance lithium and sodium-ion batteries

In this work, a new nanocomposite system based on CoO nanoparticles (NPs) anchored on pinecone-derived activated carbon (PAC), denoted as CoO(x)@PAC, is synthesized by facile ball-milling and sonication processes followed by annealing. H3PO4 is employed as an activation agent to activate the porous carbon derived from pinecone. The loading amount of CoO is varied to obtain the optimum electrochemical performances. Among the nanocomposites, the CoO(20)@PAC delivers a discharge capacity of 886 mA h g−1 after 100 cycles at a current density of 100 mA g−1 when employed as an anode in lithium-ion batteries (LIBs). At higher current rate of 1000 mA g−1, the anode provides an enhanced discharge capacity of 456.6 mA h g−1 after 200 cycles with 99 % capacity retention compared to the 4th cycle capacity. In sodium-ion batteries (SIBs), the CoO(20)@PAC anode delivers a discharge capacity of 290 mA h g−1 at 50 mA g−1. The same nanocomposite anode provides a discharge capacity of 120 mA h g−1 after 900 cycles at a current density of 500 mA g−1. The CoO(20)@PAC nanocomposite shows a great potential as an anode for both LIBs and SIBs, due to its higher capacity, exceptional rate capability, longer cycle life, and a Coulombic efficiency exceeding 99 %.

One step for the construction of MnCO3-Mn3O4 composite for the high-performance lithium-ion batteries

In this work, MnCO3-Mn3O4 composite materials were prepared by one-step solvothermal method. The structure, morphology and chemical composition were characterized and analyzed. As the anode materials of lithium-ion batteries, the formed MnCO3-Mn3O4 composites on the basis of initial KMnO4/DMF weight ratio of 1:40 and 1:20 delivered the specific discharge capacities of 654.8 and 598.7 mA h g−1 after 100 cycles at a current density of 1.0 A g−1. The testing results indicate that MnCO3-Mn3O4 composite has significant advantage in electrochemical lithium storage capacity and can be utilized as one prospective anode material for the high performance lithium-ion batteries.

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

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

Synergistic effects of multi-dimensionality in an aerogel for lithium-ion battery anodes with an enhanced capacitive contribution

The rational design of anode materials is important when seeking to produce high-performance lithium-ion batteries (LIBs) that offer both a high-power density (P) and a high energy density (ε). In this study, a multi-dimensional aerogel composed of 1-dimensional (1D) and two-dimensional (2D) nanostructures was synthesized. To impart conductivity and dimensional diversity, reduced graphene oxide (rGO) nanoplates were introduced to a 1D Co-S aerogel using a metal coordination-assisted sol–gel method. As the anode material for an LIB, the resulting multi-dimensional rGO@Co-S aerogel with 1.4 wt% GO exhibited outstanding electrochemical performance, with a high specific capacity, high-rate capability, strong cycling stability (84 % at 0.5 A/g after 350 cycles), an excellent P (9,660 W/kg), and a high ε (1,566 Wh/kg). This was attributed to the shorter ion and electron diffusion paths arising from the multi-dimensional structure, coupled with the higher surface area and enhanced capacitive contribution due to the addition of the rGO nanoplates.

Grain Analysis of NCM Cathode Materials by ASTAR Technique and Its Effect on Battery Performance

Lithium-ion batteries (LIBs) are one of the most promising energy storage systems for portable electronic devices, electric vehicles, and renewable energy systems. Among the various cathode materials for LIBs, nickel cobalt manganese (NCM) oxide has attracted considerable attention due to its high specific capacity, good cycling stability, and appropriate cost for commercialization. However, Ni-rich NCM (Ni >80%) showed poor cyclability and huge gas evolution because of surface instability.Single crystal NCM has been suggested as a solution to these issues due to its excellent properties. However, it is difficult to quantify the degree of single crystallinity because it is so far subjective. In this study, we employed ASTAR technique (transmission electron microscopy combined with electron backscatter diffraction) to investigate the microstructural features of NCM cathode materials. Our ASTAR analysis showed that NCM cathode materials consist of complex grain and grain boundary structures with varying orientations and sizes. By analyzing the grain size and its morphology, we were able to define the single crystallinity of NCM cathode materials, including the poly NCM and single crystal NCM particles.Furthermore, we found that the grain size and its distribution significantly affects the battery performance and lifespan of NCM cathode materials. Specifically, the poly NCM particles exhibited a larger grain boundary and surface area compared to the single crystal NCM particles. The poly NCM particles also showed a faster DC-IR increase and a shorter lifespan than the single crystal NCM particles, indicating that the grain size has a critical influence on the battery performance and lifespan of NCM cathode materials.Our results provide insights into the design and optimization of NCM cathode materials for next-generation LIBs. By controlling the grain size and its distribution of NCM cathode materials, it is possible to enhance the battery performance and lifespan. Therefore, our study highlights the importance of understanding the microstructural features of NCM cathode materials for developing high-performance and stable LIBs.

(Invited) A Study of the SEI Layer Cross-Talk in Si/C Composite Li-Ion Anodes

Composite electrodes, especially silicon/carbon (Si/C) anodes, present significant opportunities for advancing the energy density of lithium-ion batteries (LIBs). However, challenges emerge, particularly in performance metrics when a high weight percentage of Si beyond 8-10 wt.% is employed 1. A nuanced understanding of the solid electrolyte interphase (SEI) in Si/C composites is imperative to overcome these limitations and enhance energy density. Conventional techniques such as ex-situ X-ray photoelectron spectroscopy and cryogenic electron microscopy face inherent drawbacks, including exposure to ultrahigh vacuum and the need for solvent washing, potentially altering the SEI layer 2. In contrast, nano-FTIR, utilizing Fourier transform infrared near-field spectroscopy, overcomes these challenges, enabling non-destructive probing of the SEI layer's chemistry and structure at room temperature within an inert atmosphere 3–5.In this study, we engineer custom-patterned electrodes featuring amorphous Si on atomically flat highly ordered pyrolytic graphite (HOPG) to emulate model composite electrodes. Leveraging nano-FTIR spectroscopy, near-field nanoscale white-light imaging, and atomic force microscopy measurements, our investigation reveals that the SEI on HOPG is enriched in organic lithium ethylene decarbonate (LiEDC), while the SEI on lithiated silicon unveils the presence of inorganic Li2CO3. Notably, we unveil a unique "mixed" SEI layer zone at the Si/HOPG interface, comprising a mixture of dominant SEI species from the surfaces of both the lithiated Si and the HOPG. The coexistence of these species suggests the formation of an SEI layer with presumably unique physicochemical properties, forming along Si-C interfaces in Si/C composite electrodes. These findings provide a comprehensive approach to studying model composite electrodes and offer valuable insights into optimizing the surface passivation of Si/C composite electrodes for high-performance LIBs. Acknowledgments This research was supported by the US Department of Energy (DOE)’s Vehicle Technologies Office under the Silicon Consortium Project directed by Brian Cunningham and managed by Anthony Burrell. References V. G. Khomenko and V. Z. Barsukov, Electrochim Acta, 52, 2829–2840 (2007).J. Wu, M. Ihsan-Ul-Haq, Y. Chen, and J. K. Kim, Nano Energy, 89, 106489 (2021).X. He, J. M. Larson, H. A. Bechtel, and R. Kostecki, Nat Commun, 13, 1398 (2022).I. Yoon, J. M. Larson, and R. Kostecki, ACS Nano, 17, 6943–6954 (2023).A. Dopilka, Y. Gu, J. M. Larson, V. Zorba, and R. Kostecki, ACS Appl Mater Interfaces, 15, 6755–6767 (2023).

Thermodynamic and Kinetic Behaviors of Electrolytes Mediated by Intermolecular Interactions Enabling High-Performance Lithium-Ion Batteries.

Electrolyte solvation chemistry regulated by lithium salts, solvents, and additives has garnered significant attention since it is the most effective strategy for designing high-performance electrolytes in lithium-ion batteries (LIBs). However, achieving a delicate balance is a persistent challenge, given that excessively strong or weak Li+-solvent coordination markedly undermines electrolyte properties, including thermodynamic redox stability and Li+-desolvation kinetics, limiting the practical applications. Herein, we elucidate the crucial influence of solvent-solvent interactions in modulating the Li+-solvation structure to enhance electrolyte thermodynamic and kinetic properties. As a paradigm, by combining strongly coordinated propylene carbonate (PC) with weakly coordinated cyclopentylmethyl ether (CPME), we identified intermolecular interactions between PC and CPME using 1H-1H correlation spectroscopy. Experimental and computational findings underscore the crucial role of solvent-solvent interactions in regulating Li+-solvent/anion interactions, which can enhance both the thermodynamic (i.e., antireduction capability) and kinetic (i.e., Li+-desolvation process) aspects of electrolytes. Additionally, we introduced an interfacial model to reveal the intricate relationship between solvent-solvent interactions, electrolyte properties, and electrode interfacial behaviors at a molecular scale. This study provides valuable insights into the critical impact of solvent-solvent interactions on electrolyte properties, which are pivotal for guiding future efforts in functionalized electrolyte engineering for metal-ion batteries.

Electrospinning synthesis of hollow V0.95Mo0.97O5 nanofibers for high-performance lithium-ion batteries

We report the facile electrospinning fabrication of hollow V0.95Mo0.97O5 nanofibers via controlling oxidization of the V/Mo/polymer precursor, whose structural evolution upon increasing the annealing temperature are revealed. When examined as anode of lithium-ion batteries, the hollow V0.95Mo0.97O5 nanofibers display superior electrochemical properties with high cycle and rate capability, delivering high reversible capacities of 746.7/583.8 mAh/g at 500/1000 mA/g after 300 cycles, and a high-rate capacity of 614 mAh/g at 2000 mA/g.

Batch-Scale Synthesis and Interfacially Enhanced Stability of Silicon Suboxide-Based Anodes toward High-Performance Lithium-Ion Batteries.

SiOx anode materials are among the most promising candidates for next-generation high-energy-density lithium-ion batteries (LIBs). However, their commercial application is hindered by poor conductivity, low initial Coulombic efficiency (ICE), and an unstable solid electrolyte interface. Developing cost-effective SiOx anodes with high electrochemical performance is crucial for advanced LIBs. To tackle these issues, this study utilized APTES as a silicon source and carbon nanotubes (CNTs) as additives to prepare a T-SiOx/C/CNTs composite material with N doping and in situ carbon coating using a "molecular assembly combined with controlled pyrolysis" strategy under mild conditions. The in situ carbon coating, formed by the pyrolysis of organic groups on the molecular precursor, effectively protects the inner SiOx active material. The introduced CNTs enhance electron migration and improve the rigidity of the carbon coating layer. The prelithiated T-SiOx@C/CNTs electrode achieves an ICE of 91.6%, with a specific capacity of 622 mAh g-1 after 400 cycles at 1 A g-1 and 475.8 mAh g-1 after 800 cycles. Full cell tests with commercial NCM811 cathodes further demonstrate the potential of T-SiOx@C/CNTs as a highly promising anode material. This work provides some insights into the rational design of advanced anode materials for LIBs, paving the way for their future development and application.

Controllable preparation of carbon coating Ge nanospheres with a cubic hollow structure for high-performance lithium ion batteries

Germanium based nanomaterials are very promising as the anodes for the lithium ion batteries since their large specific capacity, excellent lithium diffusivity and high conductivity. However, their controllable preparation is still very difficult to achieve. Herein, we facilely prepare a unique carbon coating Ge nanospheres with a cubic hollow structure (Ge@C) via a hydrothermal synthesis and subsequent pyrolysis using low-cost GeO2 as precursors. The hollow Ge@C nanostructure not only provides abundant interior space to alleviate the huge volumetric expansion of Ge upon lithiation, but also facilitates the transmission of lithium ions and electrons. Moreover, experiment analyses and density functional theory (DFT) calculations unveil the excellent lithium adsorption ability, high exchange current density, low activation energy for lithium diffusion of the hollow Ge@C electrode, thus exhibiting significant lithium storage advantages with a large charge capacity (1483 mAh/g under 200 mA g−1), distinguished rate ability (710 mAh/g under 8000 mA g−1) as well as long-term cycling stability (1130 mAh/g after 900 cycles under 1000 mA g−1). Therefore, this work offers new paths for controllable synthesis and fabrication of high-performance Ge based lithium storage nanomaterials.

Defect-driven ion storage on hexagonal boron nitride for fire-safe and high-performance lithium-ion batteries

The mass market adoption of electric vehicles has increased the risk of safety concerns, such as overheating and flammability. Rational design of fire-safe and high-capacity anodes with thermal tolerance, capable of fast-charging and long cycle-life, is crucial for the development of next generation Li-ion batteries operating under extreme conditions. Here we report a defect engineered hexagonal boron nitride (hBN) anode to mediate the safety dilemma. We demonstrate that the defects generated via cryomilling catalyze the reversible LiF formation and enable the pseudocapacitive type Li-ion storage on hBN. The non-flammability and excellent thermal tolerance of hBN allows high specific capacity (880 mAh/g @ 25 mA/g), rate performance (480 mAh/g @ 5 A/g) and stable cycling (5000 cycles) at 60 °C. The Li-ion full-cell with the defective hBN anode and the conventional cathode (LiNiMnCoO2) delivers significantly higher energy (400 Wh kg−1) and power density (1 kW kg−1) when compared to graphite/LiNiMnCoO2 full-cells (121 Wh kg−1 and 250 W kg−1). First-principles calculations confirm that nitrogen antisite (NBVN) defects are responsible for the electrochemical activation of otherwise inactive hBN. The strategy of defect-induced electrochemical activation opens up new avenues in the design of high-performance electrode materials for numerous secondary batteries.

Construction of 2D/1D rGO/H2Ti3O7 composite as anode for high performance lithium-ion batteries

Ultrafine one-dimensional (1D) H2Ti3O7 nanowires were prepared by a hydrothermal reaction with high concentration of KOH as base source. Then 2D/1D rGO/H2Ti3O7 architecture was constructed and investigated as the anode material for lithium-ion batteries. Benefiting from the addition of rGO nanosheets and the retention of ultrafine 1D H2Ti3O7 nanowires, the rGO/H2Ti3O7 electrode presented superior electrochemical performance with excellent rate capability, long cycling stability and high capacity in half cells. It delivered high reversible capacities of 274 mAh g−1 at 0.1 A g−1 and 163 mAh g−1 at 1 A g−1, as well as a long-term cycling performance (259.3 mAh g−1 at 0.2 A g−1 after 1000 cycles). The excellent electrochemical performance of the composite can be attributed to the unique architecture with smaller diameter of 1D H2Ti3O7 nanowires and conductive rGO nanosheets to shorten the transmission distance of electrons and Li+ and improve the electrical conductivity in rGO/H2Ti3O7 composite.

MoS2/SnS heterostructure composite for high-performance lithium-ion battery anodes

Layered metal sulfides are potential anode materials for lithium-ion batteries (LIBs) because their unique structure makes them suitable for Li+ de-intercalation. As a typical 2D layered material, MoS2 is a potential anode material for LIBs due to the weak van der Waals forces between the layers, which facilitates the de-intercalation of Li+ and supports multiple Li+. However, when MoS2 is used as anodes for LIBs material, rapid capacity decay hinders the application. Coupling two different materials to form a heterogeneous structure is an effective way to solve the above problems. In this work, one-pot hydrothermal method is proposed to construct MoS2/SnS heterostructure composites. The electrochemical properties are significantly enhanced, which could be attributed to the presence of heterogeneous structures, leading to increase the electrode charge transfer rate and interfacial reaction kinetics. The results show that the discharge capacity of the MoS2/SnS-1.5 electrode is about 1492.1 mAh/g at 500 mA/g. Furthermore, assembled MoS2@SnS-1.5||LiCoO2 full cell displays a high discharge capacity of 226.1 mAh/g after 50 cycles at 500 mA/g. This facile method provides the application value of layered metal sulfides as LIBs anode materials.

Constructing Si@CN@MXene from silicon waste as high-performance lithium-ion battery anodes

Silicon represents one of the most attractive materials for anodes in lithium-ion batteries (LIBs) due to highest theoretical specific capacity. Thus, there is a most urgent need to prepare Si-based nano materials in a very efficient way, and develop some reasonable approaches for their modification in order to resolve the short-falls of Si anode, which include both low conductivity and huge volume changes during intercalation of lithium ions. In this work, the kerf loss silicon (KL Si) from the photovoltaic industry has been used as an inexpensive Si source for the synthesis of the Si@CN@MXene (SCM) composite to be applied as an anode material. Meanwhile, the chitosan works as the charge bridge in sequence with the Si and MXene nanosheets under electrostatic force during composite preparation. The MXene nanosheet and N-doped carbon layer that build up during chitosan calcination can be attributed to forming a hierarchical high-speed conductive network over the surface of silicon, which contributed to alleviate the volume expansion of silicon. The SCM electrode discharge capacity was obtained at a stable value of 900.8 mAh g−1 at 0.5 A g−1, 861.9 mA g−1 at 1 A g−1 and 657.6 mA g−1 even at 2 A g−1 after 100 cycles. The SCM electrode also exhibited good rate performance from 0.2 to 5 A g−1. Therefore, this study recommends that the method is very promising for producing the silicon anode material for LIBs from KL Si.

Self-assembled Si-based anode combined with electrostatic spinning method to realize high-performance lithium-ion batteries

Addressing the volume expansion when silicon and metal oxides alone are used as anode materials for lithium-ion batteries. This study used a simple self-assembly method and electrostatic spinning technique to prepare silicon@copper oxide@carbon nanofibres (CNFs) anodes with dual modification. The high rigidity of metal oxide CuO and the excellent cycling stability of CNFs effectively reduce the buildup of silicon particles, alleviate the volume expansion effect, and improve the electrical conductivity, which leads to better cycling stability and larger specific capacity of lithium-ion batteries. An excellent reversible specific capacity of 748.5 mAh g-1 was observed after 800 cycles at a high current density of 1Ag-1. In addition, the surface of Si@CuO@CNFs electrodes remains smooth and undamaged after 800 cycles, and the increase in cross-sectional thickness is about 68%, which is significantly smaller than the 300% increase in cross-sectional thickness of pure Si anode and effectively improves the specific capacity of Li-ion batteries. This research optimizes the design of silicon-based anode materials with simple and mature process technology, which makes an indispensable contribution to developing high-efficiency, long-life, and environmentally friendly lithium-ion batteries. The easy availability and non-polluting nature of the materials used also effectively reduce the reliance on rare or expensive elements, minimize the production process's environmental impact, and vigorously promote the global energy transition and low-carbon green development strategy.