Si Anode Research Articles

Layer effects on MXenes electrode and it applied to silicon composite structures

Despite the very high capacity of Si (4200mAh g−1), the widespread application of Si anodes has been hampered by drastic volume changes (up to 300 %) during cycling, leading to electrical contact losses and thus a sharp drop in capacity as the cycle life is shortened. Here we present a class of layered MXene/Si electrodes, which consist of nano-Si embedded in the interlayers of MXene to form a coupling effect, which can inhibit the huge volume change of Si during cycling. Therefore, layered MXene/Si has a highly reversible capacity, much improved cycling performance and excellent mechanical properties. First-principles calculations reveal the excellent electronic conductivity and good diffusion ability of layered MXene/Si, confirming the rapid storage of Li ions. This study provides useful information for the development and production of anode materials with high energy density and good mechanical properties.

Evaluating Polyacrylic Acid as a Universal Aqueous Binder for Ni-Rich Cathodes NMC811 and Si Anodes in Full Cell Lithium-ion Batteries.

Silicon (Si) and silicon/graphite (Si/Gr) composite anodes are promising candidates due to their high theoretical capacity, low operating potential and natural abundance for high energy density Li-ion batteries. Green electrode production, eliminating organic volatile solvents require advancement of aqueous electrodes. Engineering the binder plays a critical role for improving waterborne electrodes. Lithium substituted polyacrylic acid LiPAA has been demonstrated as a promising binder for Si/Gr anodes and for Ni-rich cathodes in different cell configurations. LiPAA is utilized to minimize the volume expansion during cycling for Si/Gr anodes. LiPAA is formed in situ during cathode slurry preparation to regulate the pH and dimmish the Li loss. Using advanced characterization techniques, we investigated the slurries, electrodes, and active material reaction with LiPAA and its effect to the cycling performance. Our results indicate that the performance of high Si containing anode is limited by the amount of Si in the electrode. The failure mechanism with respect to high Si content was studied thoroughly. Aqueous processed cathodes with LiPAA binder in combination with Si anodes outperformed NMP based cathodes. Hence, LiPAA was successfully utilized as an active binder for both a high Si containing anode and for a Ni rich cathode.

High-Performance Porous pSi/Ag@C Anode for Lithium-Ion Batteries

Silicon represents one of the most attractive anode materials in lithium-ion batteries (LIBs) due to its 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 anodes, 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 preparation of a porous silicon/silver/carbon composite (pSi/Ag@C) as an anode material. Porous silicon was embedded with Ag particles via the Ag-catalyzed chemical etching process, providing additional space to accommodate the large volume expansion of silicon. After carbon coating from polymerization of tannic acid on the surface of pSi/Ag, a high-speed conductive network over the surface of silicon was built and contributed to enhancing the electrochemical performance of the anode. The pSi/Ag@C electrode discharge capacity maintained at a stable value of 665.3 mAh g−1 after 100 cycles under 0.5 A g−1 and exhibited good rate performance. Therefore, this study recommends that the method is very promising for producing a silicon anode material for LIBs from KL Si.

Enhancing Charging Efficiency with Lithium Silicate in Silicon Composite Anode Materials Through Lithiothermic Reduction Reaction Synthesis

AbstractThis study synthesizes silicon (Si) powders with lithium silicates including lithium orthosilicate (Li4SiO4), lithium metasilicate (Li2SiO3), and lithium disilicate (Li2Si2O5), creating a composite structure of crystalline Si within a LixSiyOz matrix through the lithiothermic reduction reaction (LTRR) process. The reduction of Li‐ion consumption of the anode is investigated by 1) initial solid electrolyte interphase (SEI) layer formation, 2) SEI layer formation in response to Si expansion‐induced damage, 3) trapping of Li ions at Si defects, and 4) side reactions during initial charge and discharge cycles. Si/LixSiyOz electrode exhibits a specific capacity of 1522.2 mAh g−1 and an initial coulombic efficiency of 83.5%. The effect of the calendering process is observed, and a pressurization condition of 5000 kgf cm−2 or less is set, and the ICE is improved to 93.4%–96%. Si/LixSiyOz electrodes outperform pure crystalline Si electrodes in specific capacity (7.3%), ICE (42%), and retention characteristics (17%). The integration of the LixSiyOz matrix into Si anodes enhances Li‐ion transport and partially suppresses Si expansion. Additionally, the Si/LixSiyOz electrode exhibits superior rate capability in the 0.2–1.6 A g−1 range.

Thickness Variation of Conductive Polymer Coatings on Si Anodes for the Improved Cycling Stability in Full Pouch Cells.

Si-dominant anodes for Li-ion batteries provide very high gravimetric and volumetric capacity but suffer from low cycling stability due to an unstable solid electrolyte interphase (SEI). In this work, we improved the cycling performance of Si/NCM pouch cells by coating the Si anodes with the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) prior to cell assembly via an electropolymerization process. The thicknesses of the PEDOT coatings could be adjusted by a facile process parameter variation. Glow-discharge optical emission spectroscopy was used to determine the coating thicknesses on the electrodes prior to the cell assembly. During electrochemical testing, improvements were observed closely linked to the PEDOT coating thickness. Specifically, thinner PEDOT coatings exhibited a higher capacity retention and lower internal resistance in the corresponding pouch cells. For the thinnest coatings, the cell lifetime was 18% higher compared to that of uncoated Si anodes. Postmortem analyses via X-ray photoelectron spectroscopy and cross-sectional scanning electron microscopy revealed a better-maintained microstructure and a chemically different SEI for the PEDOT-coated anodes.

Enhancing performance of silicon/graphene composites by transition lattice interfaces constructed using plasma

The silicon-based (Si) anodes have not widely used due to their low conductivity and severe irreversible volume changes until now. Graphene (G) is considered a promising material for inhibiting volume expansion and enhancing conductivity of Si, a large amount of work has been exploring effective composite of graphene and silicon. A new SiG composite structure (PB-SiG-1) with transition lattice interface is provided by N plasma assisted technique in this work. The phase interface undergoes lattice changes on the atomic scale with silicon, oxygen, and carbon bonding in new chemical bonds (Si-O-C). More importantly, the lattice spacing of Si (111) increases from 0.31 nm to 0.325 nm due to the insertion of carbon or oxygen atom into the Si body, which promotes the diffusion kinetics of lithium ions. This PB-SiG-1 exhibits better electrochemical performance with reversible specific capacity of 2013.9 mAh g−1 after 100 cycles at 0.2 A g−1, high capacity retention of 98.53% and coulombic efficiency of 99.4%. The multiple advanced in situ methods reveal that the PB-SiG-1 not only has the ability to quickly transfer ions, electrons, and form stable SEI, but also has a low irreversible volume expansion of 33.1 %. This proves that the transition lattice interface endows PB-SiG-1 with isotropy characteristic of lithium diffusion, leading to dynamically stable electrodes during cycles. This work proposes a Si-C composite structure with transition lattice interface, which opens a new insight for volume expansion and lithium transmission in Si-C composite.

In Situ Integration of a Flame Retardant Quasisolid Gel Polymer Electrolyte with a Si-Based Anode for High-Energy Li-Ion Batteries.

Silicon (Si) stands out as a promising high-capacity anode material for high-energy Li-ion batteries. However, a drastic volume change of Si during cycling leads to the electrode structure collapse and interfacial stability degradation. Herein, a multifunctional quasisolid gel polymer electrolyte (QSGPE) is designed, which is synthesized through the in situ polymerization of methylene bis(acrylamide) with silica-nanoresin composed of nanosilica and a trifunctional cross-linker in cells, leading to the creation of a "breathing" three-dimensional elastic Li-ion conducting framework that seamlessly integrates an electrode, a binder, and an electrolyte. The silicon particles within the anode are encapsulated by buffering the QSGPE after cross-linking polymerization, which synergistically interacts with the existing PAA binder to reinforce the electrode structure and stabilize the interface. In addition, the formation of the LiF- and Li3N-rich SEI layer further improves the interfacial property. The QSGPE demonstrates a wide electrochemical window until 5.5 V, good flame retardancy, high ionic conductivity (1.13 × 10-3 S cm-1), and a Li+ transference number of 0.649. The advanced QSGPE and cell design endow both nano- and submicrosized silicon (smSi) anodes with high initial Coulombic efficiencies over 88.0% and impressive cycling stability up to 600 cycles at 1 A g-1. Furthermore, the NCM811//Si cell achieves capacity retention of ca. 82% after 100 cycles at 0.5 A g-1. This work provides an effective strategy for extending the cycling life of the Si anode and constructing an integrated cell structure by in situ polymerization of the quasisolid gel polymer electrolyte.

Engineering a Low-Strain Si@TiSi2@NC Composite for High-Performance Lithium-Ion Batteries.

The huge volume expansion/contraction of silicon (Si) during the lithium (Li) insertion/extraction process, which can lead to cracking and pulverization, poses a substantial impediment to its practical implementation in lithium-ion batteries (LIBs). The development of low-strain Si-based composite materials is imperative to address the challenges associated with Si anodes. In this study, we have engineered a TiSi2 interface on the surface of Si particles via a high-temperature calcination process, followed by the introduction of an outermost carbon (C) shell, leading to the construction of a low-strain and highly stable Si@TiSi2@NC composite. The robust TiSi2 interface not only enhances electrical and ionic transport but also, more critically, significantly mitigates particle cracking by restraining the stress/strain induced by volumetric variations, thus alleviating pulverization during the lithiation/delithiation process. As a result, the as-fabricated Si@TiSi2@NC electrode exhibits a high initial reversible capacity (2172.7 mAh g-1 at 0.2 A g-1), superior rate performance (1198.4 mAh g-1 at 2.0 A g-1), and excellent long-term cycling stability (847.0 mAh g-1 after 1000 cycles at 2.0 A g-1). Upon pairing with LiNi0.6Co0.2Mn0.2O2 (NCM622), the assembled Si@TiSi2@NC||NCM622 pouch-type full cell exhibits exceptional cycling stability, retaining 90.1% of its capacity after 160 cycles at 0.5 C.

From bulky Si to porous medium entropy alloy: Enabling highly efficient Li storage via the simultaneous reconstruction of microstructure and component

We show here that the Li-storage performance of Si anode can be substantially improved by engineering a multilevel nanoporous SiGeTiZnCuAl medium entropy alloy (NP-MEA). The NP-MEA is directly engineered through a corrosion-driven phase and structure simultaneous reconstruction by partially etching Al and Zn from the multi-element master alloy. The unique multi-elemental interactions can revolutionize the chemical microenvironment, and thus stabilize the structure and impel the transportation of the electrons and ions. The metallic sponge offers multilevel pore channels for electrolyte permeation and ample space for volume change accommodation, abundant accessible active sites for lithiation/delithiation, as well as the rigid skeleton for expediting the electron transportation and stabilizing the structure. Benefiting from the synergy of component and structure, the NP-MEA delivers a high reversible capacity of 646.1 mAh g−1 after 500 cycles at a current density of 2 A g−1.

Enhancing Electrochemical Stability of Silicon-Carbon and NMC based Lithium-Ion Batteries through the Synergistic Impact of Charge Balance and Direct-Contact Pre-Lithiation Strategy

The commercial feasibility of silicon (Si) anodes (≥ 30%) in full-cell systems is constrained by poor cyclic stability and capacity balancing due to continuous active lithium (Li) consumption in each cycle. We proposed a capacity balancing approach by adding additional Li at the cathode side (i.e., ratio of capacity at negative to positive electrode (N/P) ∼ 0.9) and anode side (i.e., pre-lithiated Si) before full-cell fabrication. This approach provided a capacity-balanced full-cell with 91.7% of initial Coulombic efficiency (ICE) and stability up to 50 cycles. In-situ electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis have been utilized to examine the interface of bare and balanced full cells. In a large format cell, electrolyte wettability is an issue and it has been investigated even at high temperature (50 °C). The post-cycle investigation also indicates the Si particles retained their integrity after cycling. A 110 mAh pouch cell has been constructed, and the pouch cell demonstrated exceptional cyclic stability up to 200 cycles, with a capacity retention of 83.2% at a current rate of 0.1 C. These findings present a capacity balancing approach for high-loading silicon-based anodes that eventually can scale up to high-quality and long-cycle life lithium-ion batteries.

On the Specific Capacity and Cycle Stability of Si@void@C Anode: Effects of Electrolytes

Electrolytes play a critical role in the formation of stable solid electrolyte interphase (SEI) for Si anodes. This study investigates the impacts of five different electrolytes on the specific capacity and cycle stability of Si-based anodes and confirms the advantages of the second-generation (Gen2) electrolyte over the first-generation (Gen1) electrolyte in the first 200 cycles, beyond which the advantages of Gen2 electrolyte disappear. Addition of more FEC and VC additives to Gen2 electrolyte does not offer significant advantages in the cycle stability and specific capacities. However, very high FEC electrolytes with 20 wt% FEC and 80% dimethyl carbonate exhibits strong dependance on the lithiation cutoff voltage. This electrolyte results in durable SEI layers when the lithiation cutoff voltage is at 0.01 V vs Li/Li+. Furthermore, lowering the lithiation cutoff voltage from 0.1 V to 0.01 V vs Li/Li+ has raised the specific capacity of Si-based anodes, leading to higher specific capacities than those of graphite anodes at the electrode level for 380 cycles investigated in this study. The understandings developed here provide unambiguous guidelines for selection of electrolytes to achieve long cycle stability and high specific capacity of Si-based cells simultaneously in the future.

Understanding and Enhancing Silicon Nanoparticle Distribution during Electrode Processing

Silicon-dominant anodes are of great interest because of their potential to boost the cell-level energy of state-of-the-art Li-ion batteries. While silicon materials have been extensively studied, understanding interactions at the electrode level has recieved little attention, especially the coating process of Si particles, which plays an equally important role in unlocking the full potential of silicon anodes. Herein, the electrode processing of a Si-dominated anode (52.8 wt%, 3.5–4.5 mAh cm−2) is being investigated to understand the relationship of processing on the morphology and properties of Si anodes at the electrode level. It has been found that almost-undetectable Si agglomerates easily form during electrode processing, which grow into largeprotrusions after lithiation and trigger potential internal shorting and self-discharge problems. A facile slurry filtration step is proposed to homogenize the particle distribution within Si-dominant electrodes which improves the electrochemical performance and storage stability of Si-based Li ion batteries.

Enhanced Silicon Anodes with Robust SEI Formation Enabled by Functional Conductive Binder

AbstractThe application of silicon (Si) anode is limited by the drastic volume change of silicon in the lithiation/delithiation process, the repeated formation of the solid electrolyte interface (SEI), and the low intrinsic conductivity. In this work, a small amount of poly (3,4‐ethylenedioxythiophene):poly (styrene sulfonic acid) (PEDOT:PSS) (PP), citric acid (CA), isopropyl alcohol (IPA), and silicon nanoparticles (SiNPs) are mixed and vacuum treated at a specific temperature to obtain silicon‐based anode electrode composite Si@PP@CA. The interphase forms a robust elastic network with hydrogen and chemical bonds, which have good mechanical properties and self‐repairing characteristics. The modified PEDOT:PSS as the conductive medium significantly improves the charge transfer rate. Moreover, the rapid formation of SEI by CA on the surface of SiNPs enhances the structural stability of the material. The electrochemical results show that the capacity of Si@PP@CA composite electrode canretain more than 2200 mAh g−1 after 200 cycles at 0.2 A g−1. It still shows a high capacity retention of 89% even at the current density of 1.0 A g−1 after 2000 cycles. More importantly, such excellent performance can be obtained using an electrode with an active material content of up to 90 wt%, which is essential for practical applications.

Tailored Interphases Construction for Enhanced Si Anode and Ni-Rich Cathode Performance in Lithium-Ion Batteries

Tailored Interphases Construction for Enhanced Si Anode and Ni-Rich Cathode Performance in Lithium-Ion Batteries

Remarkably improved cycling stability of commercial micron-sized silicon enabled by a novel organic/inorganic hybrid binder

Silicon (Si) anode with ultra-high capacity and low cost are highly desirable for next-generation high-energy lithium-ion batteries, whereas suffers from severe volume change that causes rapid capacity decay upon lithiation/delithiation. The development of high-performance binders to alleviate volumetric expansion and maintain integrity of Si particles remains a significant challenge. Here, reported is a novel organic/inorganic hybrid binder composed of partial neutralized polyacrylic acid (PAAS) and sodium metaborate tetrahydrate (SMTH), which achieves in-situ crosslinking upon drying wafer electrodes. The robust crosslinked network structure with borate ester bonds is successfully attained, and can be modulated by changing the content of sodium metaborate. The strong covalent bond network endows the hybrid binder system with superior mechanical properties and powerful adhesion, which improve the contact and integrity of wafer silicon electrode by suppressing volume expansion and exfoliation, therefore facilitating Li-ion migration and enhancing electrochemical performance. The resulting commercial micro-silicon wafer electrode with PAAS/0.08SMTH binder remains a reversible specific capacity of 1670 mAh g−1 after 150 cycles at 300 mA g−1, largely superior to that prepared with the original PAAS binder because its reversible specific capacity was determined to be only 1046 mAh g−1 under identical conditions. The in-situ crosslinked 3D network structure provides a facile feasible way to improve the high-capacity anode materials for lithium-ion batteries.

Highly Stable Silicon Anode Enabled by a Water-Soluble Tannic Acid Functionalized Dual-Network Binder.

Silicon (Si), a high-capacity electrode material, is crucial for achieving high-energy-density lithium-ion batteries. However, Si suffers from poor cycling stability due to its significant volume changes during operation. In this work, a tannic acid functionalized aqueous dual-network binder with an intramolecular tannic acid functionalized network has been synthesized, which is composed of covalent-cross-linked polyamide and ionic-cross-linked alginate (Alg(Ni)-PAM-TA), and employed as an advanced binder for stabilizing Si anodes. The resultant Alg(Ni)-PAM-TA binder, incorporating diverse functional groups including amide, carboxylic acid, and dynamic hydrogen bonds, can easily interact with both Si nanoparticles and the Cu foil, thereby facilitating the formation of a highly resilient network characterized by exceptional adhesion strength. Moreover, molecular dynamics (MD) simulations indicate that the Alg(Ni)-PAM-TA network shows an increased intramolecular hydrogen bond number with increasing concentration of TA and a decreased intramolecular hydrogen bond between PAM and Alg as a result of the aggregation behavior of tannic acids themselves. Consequently, the binder significantly enhances the Si electrode's integrity throughout repeated charge/discharge cycles. At a current density of 0.84 A g-1, the Si electrode retains a capacity of 1863.4 mAh g-1 after 200 cycles. This aqueous binder functionalized with the intramolecular network via the incorporation of TA molecules holds great promise for the development of high-energy-density lithium-ion batteries.

Influence of defects on enhancing lithium diffusivity in crystalline silicon anodes for fast charging lithium-ion batteries

The energy storage sector requires high capacity, long cycling life batteries. Silicon (Si) arises as a pivotal anode material for next-generation lithium-ion batteries owing to its exceptional capacity. However, challenges arise from lithium interactions, causing volumetric expansion and structural concerns like cracking. Si anodes also exhibit diverse phenomena during lithiation, influenced by crystal orientations. A thorough comprehension of the (de)lithiation process is essential to address challenges, despite existing gaps in knowledge, with strategic design and complementary materials, offering potential solutions by enhancing ion mobility and minimizing diffusion barriers. Here we have developed and applied first-principles simulations to offer fundamental insights into atomic interactions, providing a realistic atomistic representation of lithiation processes. Our simulations systematically incorporate Li+ into Si and Si- nitrogen vacancies (NV) orientations, and evaluation between Si and Si-NV (110) indicates a more favorable behavior in ionic diffusion for Si-NV(110), with a range of 2.55 × 10−3 to 1.64 × 10−2 (cm2/s) and a 15 % decrease in volume expansion. Our results explain the ternary Si–Li–N electrode materials and the identification of optimal site disorders to maximize the rate of Li+ diffusion in crystalline Si anodes.

Achieving a Double Advantage Through Design of TiO2/C Interlaced Coating for Si Anode

AbstractMultifunctional coating strategy shows promising prospective in advancing Si‐based anodes towards practical applications in Li‐ion batteries. Dual coating of amorphous carbon and TiO2 shows demonstrable advantages owing to high elasticity of amorphous carbon and mechanical toughness of TiO2. However, for past design of Si@C@TiO2 composite electrode, wherein C and TiO2 are configured layer‐by‐layer, a long‐standing problem exists as that a thin TiO2 coating is insufficient to stabilize the electrode's architecture while a thick one prevents the core active material of Si far from fully electrochemically utilization due to the too strong structural constraint effect. Herein, it presents that a facial heat treatment of Si@C@TiO2 with thick enough TiO2 can readily avert the problem. Such a strategy promotes the capacity utilization rate from 39% to 61% for the initial cycle and from 43% to 85% after 200 cycles. Model structure of C/TiO2 multilayer films is employed to reveal the role of the heat treatment. It finds that the heat treatment can transform a layer‐by‐layer structure of C@TiO2 into an interlaced structure of C/TiO2 which exhibits a dual advantage in withstanding mechanical strain and simultaneously promoting Li‐ion storage and electron/Li‐ion transport.

Double Nitrogenation Layer Formed Using Nitric Oxide for Enhancing Li+ Storage Performance, Cycling Stability, and Safety of Si Electrodes.

To enhance Li storage properties, nitrogenation methods are developed for Si anodes. First, melamine, urea, and nitric oxide (NO) precursors are used to nitrogenize carbon-coated Si particles. The properties of the obtained particles are compared. It is found that the NO process can maximize the graphitic nitrogen (N) content and electronic conductivity of a sample. In addition, optimized N functional groups and O─C species on the electrode surface increase electrolyte wettability. However, with a carbon barrier layer, NO hardly nitrogenizes the Si cores. Therefore, bare Si particles are reacted with NO. Core-shell Si@amorphous SiNx particles are produced using a facile and scalable NO treatment route. The effects of the NO reaction time on the physicochemical properties and charge-discharge performance of the obtained materials are systematically examined. Finally, the Si@SiNx particles are coated with N-doped carbon. Superior capacities of 2435 and 1280 mAh g-1 are achieved at 0.2 and 5Ag-1, respectively. After 300 cycles, 90% of the initial capacity is retained. In addition, differential scanning calorimetry data indicate that the multiple nitrogenation layers formed by NO significantly suppress electrode exothermic reactions during thermal runaway.

Functionalized interfacial cover design toward pure silicon anode for high power density lithium–ion capacitor

A lithium–ion capacitor, comprising a capacitor–type cathode and battery–type anode, exhibits high power and energy density; however, the integration of different charge storage mechanisms in one cell naturally leads to a kinetic mismatch between the two electrodes, reducing the power density and cycle stability. To solve this problem, high–capacity anode materials with thinner electrodes are required. Silicon, with its high specific capacity, is considered a promising anode material with high energy and power density; however, pure Si anodes undergo rapid capacity fading and exhibit increased internal resistance owing to volume changes during cycling. In this study, both sides of the electrode are covered with functional layers consisting of functionalized herringbone–type carbon nanofibers to protect the Si electrode from degradation. The polar functional groups on the nanofibers weakly interact with the native oxide layer of the Si surface and the carboxyl groups of the binder, ensuring stable contact between electrode materials over repeated cycles. Moreover, the conductive functional cover promotes uniform lithium ion fluxes, aiding the formation of a stable solid electrolyte interphase layer. This study investigates the effects of this strategy on pure Si electrodes by surface morphology analysis, assessment of chemical interactions, and electrochemical testing. This approach has the potential to overcome the degradation of Si electrodes and significantly improve the power and energy density of lithium–ion capacitors.