High-performance Lithium-ion Batteries Research Articles

Title: Study of Structural Evolution of Silicon-Based Anodes in Lithium-Ion Batteries

The need for electrification across various sectors has led to increased demand for high-performance lithium-ion batteries (LIBs). Today’s commercial LIBs typically make use of a pure-graphite anode which offers long lifespans but a relatively meager capacity of 372 mAh/g. Silicon, by comparison, offers a theoretical capacity of 3600 mAh/g but generally suffers from short life spans due to numerous effects. Combining silicon and graphite active materials to form a composite anode can result in electrodes with improved capacities over pure-graphite systems and enhanced longevity over pure-silicon ones. However, introducing silicon to an otherwise stable graphite electrode can induce failure of the electrode partly due to the volumetric expansion/contraction that silicon experiences during lithiation/delithiation cycles. Understanding the morphological evolution of silicon particles in composite electrodes - particularly in a lithiated state - can yield a more comprehensive understanding of the interactions between the active materials which will contribute to the realization of anodes with improved capacities and lifespans. To date, characterizing lithiated silicon-containing anodes has been difficult owing to the reactivity of the lithiated materials and a lack of suitable methods to probe within an electrode’s bulk. In this work, we demonstrate recent successes in imaging lithiated silicon-composite and silicon oxide-composite electrodes via micro and nanoscale computed tomography (MicroCT, NanoCT) and electrochemical analysis to quantify (1) changes in particle size distributions over charge/discharge cycles, (2) lithium content in silicon particles as a function of depth from the electrode’s surface, (3) changes in particle morphology, and (4) electrode thickness. The development of this technique represents a significant step towards characterizing the physical behavior of silicon particles within electrodes without destroying the surrounding structures.

(Invited) Developing Lightweight Current Collectors and Separators for High-Energy Batteries via Scalable Manufacturing Methods

Improving energy density and thermostability is essential to achieve high-performance lithium batteries. Traditional copper (Cu) current collectors (CCs) made of metal foil possess high mass and cost. The unsatisfactory thermal stability of PP or PE-based separators necessitates the development of new separator materials. In this talk, I will demonstrate a fast and scalable chemical coating method for fabricating ultralight composite Cu CC with a thin Cu layer on an ultrathin polymer scaffold. I will also introduce a lignin-based, thin separator with outstanding thermostability via a dry processing method. The scalability of the chemical coating method for current collectors and the dry processing method for lignin-based separators provide promising solutions for the mass production of these important battery components.

(Invited) Towards Scalable and Low-Cost Direct Recycling of Lithium-Ion Batteries

The increasing amount of lithium-ion battery (LIBs) consumption will result in the resource shortage and price increase of lithium and precious transition metals that are critical for making high-performance LIBs. Also, future batteries that mainly use low-cost materials (Na, Fe, Mn) will have limited economic benefits to recycle even though the wastes generated from disposal of used batteries can cause severe environment pollution. In this context, design of low-cost and scalable recycling and regeneration process for spent batteries is attracting growing interest. This talk will focus on our recent progress on direct recycling and regeneration spent LIBs, which can lead to new electrode materials that can show the same level of performance as the native materials. We will show successful recycling of various battery materials, including cathode (LiMO2, LiMn2O4, and LiFePO4) and anode (graphite) using the direct regeneration approach. We will discuss how we integrate different operation steps into a pathway for scalable directly recycling.

(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).

Exploring the potential of 2D [formula omitted]-SiC[formula omitted] monolayer as an anode material for Li-ion batteries: Ab initio investigation

In the development of energy storage in 2D materials, low cost, high storage capacity, and fast ion diffusion remain desirable challenges. In this context, this study aims to systematically investigate the potential of α-SiC7 monolayer as an anode material for lithium-ion batteries through first-principles calculations. The results imply that α-SiC7 nanosheets have good electrical conductivity, outstanding dynamic and thermal stability. In addition, the α-SiC7 monolayer showed a high theoretical capacity of 1194.91 mA h/g which is almost three times that of graphite. Our findings also indicate that lithium-ion diffusion on the orthorhombic monolayer is extremely fast with a quite low energy barrier of 0.52 eV, much lower than many other anode materials reported for Li-ion batteries. Moreover, the Li atoms intercalated in the α-SiC7 monolayer show a low open-circuit voltage of 0.16 V. Ultimately, the results of our study suggest that the α-SiC7 monolayer is a promising anode material, offering high capacity and high-rate capability for the next generation of high-performance lithium-ion batteries.

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.

Intelligent dual-anode strategy for high-performance lithium-ion batteries

Intelligent dual-anode strategy for high-performance lithium-ion batteries

One-step fabrication of binder-free nanoSi-CNT-carbon black/cyclized PAN composite anode for high-performance lithium-ion batteries

Silicon is one of the most promising anode materials for lithium-ion batteries (LIBs) due to its high theoretical capacity. However, its non-conductive nature and significant volume expansion during lithiation pose challenges. In this study, we developed a novel electrode comprising silicon nanoparticles (nanoSi), carbon nanotubes (CNTs), and carbon black (CB) in cyclized polyacrylonitrile (cPAN), referred to as nanoSi-CNT-CB/cPAN. This electrode is fabricated through a one-step thermal process by heating a cast nanoSi-CNT-CB/PAN film on Cu foil at 310 °C. The LIB performance using the nanoSi-CNT-CB/cPAN electrode shows an impressive initial coulombic efficiency of 93.1 % at 0.1 A g−1, a high specific capacity of 2267.2 mAh g−1 at 0.5 A g−1, and a retention of 89.2 % over 390 cycles, achieving 783 mAh g−1 at 5 A g−1. We attribute these results to the fused cPAN, which provides good adhesion to nanoSi, CNTs, CB, and Cu foil, acting as a binder, active material, and ionic conductive medium. The well-dispersed CNTs and CB form an effective conductive network in the electrode. Additionally, the one-step electrode fabrication is a simple and cost-effective process for next-generation Si-based LIBs.

The study of electrochemical stabilization mechanism of Pt, GC, SS304, Ti and Cu as current collectors for aqueous lithium-ion batteries by electrochemical approaches

This paper employs electrochemical methods (linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS)) to investigate the electrochemical behavior of platinum, glassy carbon, 304 stainless steel, titanium, and copper in 21 and 1 M LiTFSI electrolytes. The LSV results indicate that the electrochemical stability window of the materials varies with the electrolyte concentration, and the stability window is wider in the high-concentration system. Through Tafel polarization curves and EIS analysis, the overpotential of the charge exchange process differs due to the type of material and the concentration of the electrolyte, mainly attributed to the influence of the proportion of free water, electrolyte viscosity, and SEI film formation on electrode process kinetics. After comparative analysis, glassy carbon exhibits a higher overpotential than other materials at both the cathode and anode, effectively suppressing water decomposition. These findings provide theoretical support for the development of high-performance aqueous lithium-ion battery current collector materials.

Optimization of the Operating Voltage of Cobalt-Free Nickel-in-Medium Cathodes for High-Performance Lithium-Ion Batteries

Medium-nickel cobalt-free cathode materials have attracted much attention in recent years for their low cost and high energy density. However, the structural stability of nickel-based cathode materials becomes compromised when accompanied by the increasing of voltage, leading to poor cycling performance and, thus, hindering their widespread industrial application. In this work, we investigated the optimal charge cut-off voltage for the nickel-based cathode material LiNi0.6Mn0.4O2 (NM64). Within the voltage range of 3.0 to 4.5 V, the electrode energy density reached 784.08 Wh/kg, with an initial Coulombic efficiency of 84.49%. The reversible specific capacity at 0.1 C reached 197.84 mAh/g, and it still maintained a high reversible specific capacity of nearly 150 mAh/g, with a capacity retention rate of 86% after 150 cycles at 1 C. Furthermore, NM64 exhibited an intact morphological structure without noticeable cracking after 150 cycles, indicating excellent structural stability. This study emphasizes the relationship between the stability of NM64 cathodes and different operating voltage ranges, thereby promoting the development of high-voltage layered nickel-based cathode materials.

Li1.2Ni0.13Co0.13Mn0.54O2 of Al2O3-coating cathode for high-performance lithium-ion batteries

Li1.2Ni0.13Co0.13Mn0.54O2 of Al2O3-coating cathode for high-performance lithium-ion batteries

Interfacial engineering in SnO2-embedded graphene anode materials for high performance lithium-ion batteries

Tin dioxide is regarded as an alternative anode material rather than graphite due to its high theoretical specific capacity. Modification with carbon is a typical strategy to mitigate the volume expansion effect of SnO2 during the charge process. Strengthening the interface bonding is crucial for improving the electrochemical performance of SnO2/C composites. Here, SnO2-embedded reduced graphene oxide (rGO) composite with a low graphene content of approximately 5 wt.% was in situ synthesized via a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal method. The structural integrity of the SnO2/rGO composite is significantly improved by optimizing the Sn–O–C electronic structure with CTAB, resulting a reversible capacity of 598 mAh g−1 after 200 cycles at a current density of 1 A g−1. CTAB-assisted synthesis enhances the rate performance and cyclic stability of tin dioxide/graphene composites, and boosts their application as the anode materials for the next-generation lithium-ion batteries.

Controllable Growth of Crystal Facets Enables Superb Cycling Stability of Anode Material for Potassium Ion Batteries

AbstractTo enrich the crystal growth strategies for the booming applications concerning lattice structure, a preferred facet‐growth method is proposed for solvothermal synthesis of target (BiO)2CO3 in the two‐phase system. The dominant crystal phase can be regulated from α‐Fe2O3 to (BiO)2CO3 by properly increasing dosage of Bi feedstock, and the optimized composite is composed of (BiO)2CO3 nanocrystal (≈10 nm) and amorphous iron oxide (defined as “FOB‐50”). Based on experimental characterizations and theoretical calculations, the highly matched lattice between (006)/(0012) facets of α‐Fe2O3 and {010} facet group of (BiO)2CO3 involving orientation of Fe─O─Fe bond and Bi─O─Bi bond is verified to facilitate the interaction between the above facets, resulting in preferred growth of {010} dominated by (040) facet in (BiO)2CO3 and its composites. The structural merits can not only enable the FOB‐50‐based electrodes to achieve a high capacity and unprecedentedly stable cyclic performances for 1500 cycles/a long time‐span of 32 months as anode materials, but also ensure the full‐cell to well inherit the electrochemical features of the cathode in potassium ion batteries (PIBs). This work can provide new insight into lattice regulation for bismuth‐based materials and expand their application as electrodes for high performance PIBs and lithium ion batteries.

Tailoring Alkalized and Oxidized V2CTx as Anode Materials for High-Performance Lithium Ion Batteries.

V2CTx MXenes have gained considerable attention in lithium ion batteries (LIBs) owing to their special two-dimensional (2D) construction with large lithium storage capability. However, engineering high-capacity V2CTx MXenes is still a great challenge due to the limited interlayer space and poor surface terminations. In view of this, alkalized and oxidized V2CTx MXenes (OA-V2C) are envisaged. SEM characterization confirms the accordion-like layered morphology of OA-V2C. The XPS technique illustrates that undergoing alkalized and oxidized treatment, V2CTX MXene replaces -F and -OH with -O groups, which are more conducive to pseudocapacitive properties as well as Na ion diffusion, providing more active sites for ion storage in OA-V2C. Accordingly, the electrochemical performance of OA-V2C as anode materials for LIBs is evaluated in this work, showing excellent performance with high reversible capacity (601 mAh g-1 at 0.2 A g-1 over 500 cycles), competitive rate performance (222.2 mAh g-1 and 152.8 mAh g-1 at 2 A g-1 and 5 A g-1), as well as durable long-term cycling property (252 mAh g-1 at 5 A g-1 undergoing 5000 cycles). It is noted that the intercalation of Na+ ions and oxidation co-modification greatly reduces F surface termination and concurrently increases interlayer spacing in OA-V2C, significantly expediting ion/electron transportation and providing an efficient way to maximize the performance of MXenes in LIBs. This innovative refinement methodology paves the way for building high-performance V2CTx MXenes anode materials in LIBs.

Ultrahigh rate and cycling properties of Li2CuTi3O8 anode derived from HKUST-1 copper source for high-performance lithium-ion batteries

Rational design and preparation of titanium-based anode materials with superior fast charge and discharge are a key focuses of the lithium-ion batteries research. Herein, a novel and facile synthesis of uniformly carbon-coated Li2CuTi3O8 (LCuTO) nanoparticles with excellent high-rate lithium storage properties is presented using HKUST-1 with pore structure and active metal sites as a copper source. The well-designed LCuTO@HKUST with carbon bridges between the particles and the carbon layer on the outer surface offers high electronic conductivity for fast charge and discharge. The LCuTO@HKUST exhibits extraordinary lithium storage performance: high capacity (251.8 mAh/g after 1000 cycles at a current density of 1.0 A/g), a superior high-rate capability (160.3 mAh/g after 500 cycles at 3.0 A/g and 138.1 mAh/g after 500 cycles at 5.0 A/g), and excellent cycle reversibility and cycle stability under various current densities. In addition, the lower Li+ migration barrier in LCuTO@HKUST demonstrated by density functional theory (DFT) calculations is beneficial to the long-cycle stability and high-rate performance. The proposed preparation method and the strategy of using the MOF as a metal source for lithium-ion battery anode materials provide a new approach for advanced fast charge–discharge energy storage applications.

In-situ synthesis of Fe3O4@Fe3C nanoparticles with heterostructures embedded in the N-doped porous carbon for high-performance lithium ion batteries

Metal oxides (Fe3O4) have attracted immense attention as high-capacity anode materials for high-performance electrochemical energy storage systems. However, the large structural change and sluggish reaction kinetics in the lithiation and delithiation reactions critically limit their practical development. Here, we design a novel composite consisting of Fe3O4@Fe3C nanoparticles embedded in N-doped porous carbon (Fe3O4@Fe3C-NPC) for lithium ion batteries. Benefiting from the synergistic effect of heterostructures, the Fe3O4@Fe3C-NPC delivers high reversible capacities (911.9 mAh g−1 at 0.2 A g−1, 319.6 mAh g−1 at 5.0 A g−1). The formed heterointerfaces can build an internal electric field, which help to improve reaction kinetics with fast ion diffusion kinetics and low charge transfer resistance. Furthermore, the Fe3O4@Fe3C-NPC//LiFePO4 full cell also displays great performance. The structural design concept and efficient synthesis method in the work can be extended to construct metal oxide/carbide heterostructures for anode materials.

Microfiber/Nanofiber/Attapulgite Multilayer Separator with a Pore-Size Gradient for High-Performance and Safe Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) have an extremely diverse application nowadays as an environmentally friendly and renewable new energy storage technology. The porous structure of the separator, one essential component of LIBs, provides an ion transport channel for the migration of ions and directly affects the overall performance of the battery. In this work, we fabricated a composite separator (GOP-PH-ATP) via simply laminating an electrospun polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) nanofibrous membrane coated with attapulgite (ATP) nanoparticles onto a PP nonwoven microfibrous fabric, which exhibits a unique porous structure with a pore-size gradient along the thickness direction that ranges from tens of microns to hundreds of nanometers. As a result, besides the enhanced thermal stability given by the chosen materials, the GOP-PH-ATP separator was endowed with a superhigh porosity of ~95%, strong affinity with electrolyte, and great electrolyte uptake of ~760%, thus effectively enabling an ionic conductivity of 2.38 mS cm-1 and a lithium-ion transference number of 0.62. Furthermore, the cell with the GOP-PH-ATP separator shows an excellent cycling performance with a capacity retention of 91.2% after 150 cycles at 1 C, suggesting that the composite separator with a pore-size gradient structure has great potential to be applied in LIBs.