Silicon-based Lithium-ion Batteries Research Articles

Design Principle and Development Trends of Silicon-Based Anode Binders for Lithium-ion Batteries: A Mini Review

Abstract: Silicon (Si), recognized as a promising alternative material for the anodes of lithium-ion batteries, boasts a high theoretical specific capacity and abundant natural availability. During the preparation of silicon-based anodes, binders play a pivotal role in ensuring the cohesion of silicon particles, conductive agents, and current collectors. The structure and performance of these binders are critical for the mechanical stability, electrical conductivity, and stress dissipation capacity of the anodes. This review initially outlines the structural characteristics of various binders, including linear, branched, and three-dimensional cross-linked types. It then delves into the relationship between the structure and properties of these binders in the context of their application in high-performance lithium-ion batteries, focusing on their mechanical properties, electrical conductivity, and self-healing capabilities. Particular attention is given to the design strategies for binders that facilitate stress dissipation, with an emphasis on integrating multifunctional polymer binders renowned for their superior conductive and self-healing features. Such binders contribute to the formation of a robust three-dimensional network structure via multiple bonding mechanisms, including chemical, non-covalent, and coordination interactions. This configuration significantly enhances the adhesion between silicon particles, thereby facilitating the efficient dissipation of stress, which is a key aspect for ensuring the long-term cycling stability of lithium-ion batteries. Lastly, the paper explores future development directions for silicon anode binders, advocating for a thorough investigation into the synergy of diverse structural and functional combinations, with the aim of advancing the performance and practical application of silicon-based lithium-ion batteries.

High-Branched Natural Polysaccharide Flaxseed Gum Binder for Silicon-Based Lithium-Ion Batteries with High Capacity.

Silicon-based anodes heavily depend on the binder to preserve the unbroken electrode structure. In the present work, natural flaxseed gum (FG) is used as a binder of silicon nanoparticles (SiNPs) anode for the first time. Owing to a large number of polar groups and a rich branched structure, this material not only anchors tightly to the surface of SiNPs through bonding interactions but also formed a hydrogen bonding network structure among molecules. As a result, the FG binder can endow the silicon electrode with stable interfacial adhesion and outstanding mechanical properties. In addition, FG with a high viscosity facilitates the homogeneous dispersion of the electrode components. When FG is used as a binder, the cycling performance of the Si anode is greatly improved. After one hundred cycles at an applied current density of 1 A g-1, the electrode continues to display remarkable electrochemical properties with a significant cyclic capacity (2213mAh g-1) and initial Coulombic efficiency (ICE) of 89.7%.

Porous carbon-coated silicon composites for high performance lithium-ion batterie anode

With the rapid development of silicon-based lithium-ion battery anode, the commercialization process highlights the importance of low-cost and short-flowproduction processes. The porous carbon/silicon composites (C/Si) are prepared by one-step calcination using zinc citrate and nano-silicon as the primary raw materials at a temperature of 950 °C. In this composite, silicon nanoparticles are coated with a porous carbon shell with an average pore diameter of 4.49 nm, which improves the structural stability and electrochemical performance of the anode. Density-functional theory calculations show that the porous carbon enhances the electrical conductivity, facilitates the interlayer migration of Li-ion, and strengthens the gain effect of stress on conductivity. Additionally, stress further reduces the diffusion barriers of Li-ion. The porous C/Si anode demonstrates outstanding specific capacity and rate capability, maintaining a stable specific capacity of 1170 mAh/g at a current density of 0.2 A g−1 after 100 cycles and retaining a reversible specific capacity of 944 mAh/g even at a charging current density of 2 A g−1. The carbon/silicon anode materials prepared using this strategy present a streamlined manufacturing process and exceptional performance, as well as avoiding the post-washing step, providing a pathway toward the scalable application of silicon-based anodes.

Investigating the failure mechanism of solid electrolyte interphase in silicon particles from an electrochemical-mechanical coupling perspective

Silicon is considered one of the most promising anode materials owing to its high theoretical energy density, however, the volume expansion/contraction during electrochemical lithiation/delithiation cycles leads to instability of the solid electrolyte interphase (SEI), which ultimately results in capacity degradation. Herein, the local stress and deformation evolution status of an SEI layer on an anode particle are investigated through a quantitative electrochemical-mechanical model. The impacts of structural uniformity, mechanical strength, and operating conditions on the stability of the SEI layer are investigated in detail. The simulation results demonstrate that when the silicon particle radius decreases from 800 ​nm to 600 and 400 ​nm, the failure time increases by 29% and 65%, respectively, of the original failure time; When the structural defect depth ratio is reduced from 0.6 to 0.4 and 0.2, the failure time increases by 72% and 132%, respectively; For the discharge rate, the condition at 0.1 C has 34% and 139% longer time to failure than that at 0.2 C and 0.3 C, respectively. This work provides insight into the rational design of stable SEI layers and sheds light on possible methods for constructing silicon-based lithium-ion batteries with longer cycling lives.

Over-lithiated NCM through Li5FeO4 for high energy silicon-based lithium-ion batteries.

Si/C composite material is a promising anode material for next-generation lithium-ion batteries due to its high capacity. However, it also exhibits significant initial capacity loss in a full cell due to the unstable SEI. To compensate for the loss of Li inventory, a pre-lithiation reagent, Li5FeO4 (LFO), is incorporated into the LiNi0.85Co0.12Mn0.03O2 (NCM85E) cathode for electrochemical evaluation. The results show that with the addition of LFO, the initial discharge capacity of SiC950/NCM85E full cells can increase from 151.0 mA h g-1 to 193.4 mA h g-1 by 28.1% with a high cathode loading up to about 20 mg cm-2. After 200 cycles, the specific capacity also increased by 25.1%.

Research progress of robust binders with superior mechanical properties for high-performance silicon-based lithium-ion batteries

The mechanical properties of binders are emphasized: the intrinsic mechanical properties of binders and the adhesive strength of the binders with current collectors and active materials. The electronic and ionic conductivities of binders are introduced.

Porous hybrid encapsulation enables high-rate lithium storage for a micron-sized SiO anode.

Establishing a durable interfacial layer between an electrode and electrolyte to enable micron-sized silicon-based lithium-ion battery (LIB) anodes to achieve superior electrochemical performance is highly desired. Recent studies have shown that heterogeneous encapsulation with enhanced ion/electron transport is an effective strategy. However, the structural design of the existing hetero-coated interface lacks a reasonable ion/electron transport channel, resulting in high interfacial impedance. Herein, we designed a heterogenous MXene-mesoporous polypyrrole (mPPy) encapsulation layer onto micron-sized SiO particles. The MXene coating layer functions as a bridging interface that can build a strong chemical link to internal SiO via covalent bonding, thus reinforcing interfacial charge transfer rate. Meanwhile, it forms a dynamic connection with the outer mPPy through hydrogen bonding, which contributes to high interfacial Li+ concentration and ion/electron coupling transport rate. Accordingly, the as-prepared SiO@MXene@mPPy anode delivers a boosted specific capacity of 673.9 mA h g-1 at 2 A g-1 after 1000 cycles and high-rate capability of 777.4 mA h g-1 at 5 A g-1. Further, electrochemical kinetic analysis indicates that the MXene@mPPy coating layer shows a pseudocapacitance controlled Li storage mechanism, thereby displaying improved high-rate capability. This porous hybrid encapsulation strategy offers new possibilities for a micron-sized SiO anode to achieve an excellent performance.

Modeling and Analysis of Coupled Thermal and Mechanical Capacity Degradation in Silicon-Based Lithium-Ion Batteries

Large-format cells are gaining popularity for battery electric vehicles (BEVs) to maximize volumetric and gravimetric energy densities but are associated with challenges in ensuring adequate thermal management. Spatial current density and temperature variations negatively affect overall cell utilization and lifetime.In addition, the mechanical stresses generated within the silicon-based battery electrodes also cause aging and resultant capacity loss. The coupled effects of the thermal and mechanical factors could thus particularly exacerbate cell capacity degradation. Rigorous mechano-thermo-electrochemical models for battery degradation can be a powerful complementary tool to understand these phenomena better. Simulating performance scenarios can significantly improve cell design and experimentation while reducing time and cost commitments. Model-based design approaches thus have the potential to yield substantial economic benefits.This work shall serve as an extension to the previously developed thermal degradation model for non-uniform aging in lithium-ion batteries by coupling with mechanical models predicting the effects of volume change within the batteries over cycling. The observed capacity fade trend for a given battery is ultimately the result of an interplay between multiple degradation mechanisms, which depend on a range of design and operating parameters. The errors between the model predictions and experimental data can provide information on the suitability of a given model and the relative prevalence of a given degradation mechanism, with functional and practical benefits, as there exists significant variation in the parameters, mechanisms, and predictive capability of models in the literature. In addition, a rigorous model of volume changes increases the accuracy of predictions of dynamic stress-strain profiles, which in turn helps improve predictions of associated mechanical degradation phenomena. As a first step towards including mechanical effects, the current model builds on the previously reported studies for modeling volume change in porous electrodes due to intercalation (deintercalation) during lithiation (delithiation). This volume change leads to dimensional and porosity changes in the porous electrodes. Furthermore, these mechanical models will help predict generated stresses and strain profiles within the battery and will be related to models of resultant degradation, especially in the case of silicon/graphite electrodes characterized by substantial volume changes.

Dual-Additive Approach for Tuning Si-Based Anode Interphase Realized By Operando ATR-FTIR

Dual-additive approach for tuning Si-based anode interphase realized by Operando ATR-FTIRMasoud Baghernejad1, Matthias Weiling1, Felix Pfeiffer1, Diddo Diddens1, Lars Frankenstein2, Christian Lechtenfeld2 1Helmholtz-Institute Münster, IEK-12, Forschungszentrum Jülich GmbH, Corrensstraße 46, 48149 Münster, Germany 2MEET Battery Research Center, Institute of Physical Chemistry, University of Münster, Corrensstraße 46, 48149 Münster, GermanySilicon is a promising next-generation anode material, offering a high gravimetric capacity. However, silicon-based anodes suffer from significant volume expansion during lithiation that can cause particle pulverization and capacity fade, continuous solid-electrolyte interphase (SEI) (re-)formation, and constant electrolyte consumption. To alleviate these issues, the effect of 2-Sulfobenzoic anhydride (2-SBA) as an SEI electrolyte additive was investigated through complementary electrochemical and operando spectroscopic techniques.The electrochemical performance was evaluated through galvanostatic charge/discharge cycling. The results show that the optimum concentration of 2-SBA improves the cycling stability and capacity retention of NMC811||AG+20% SiOx (4.5 – 2.8 V) cells to more than 100 cycles compared to 70 cycles with the baseline electrolyte (BE) before cell failure. Introducing lithium difluorophosphate (LiDFP), a common additive for high-voltage applications, to the electrolyte containing 2-SBA further increased the cycle life to 160 cycles. Interestingly, LiDFP alone in the electrolyte did not lead to improved electrochemical performance or longer cycle life of the cells compared to BE, proving a beneficial dual-additive approach of combining inorganic and organic compounds for sufficient SEI formation on AG+20% SiOx anodes. The analysis of the electrochemical performance concludes that the improved SEI structure formed by 2-SBA and LiDFP mitigates pulverization. In this regard, the SEI structure is further analyzed using operando ATR-FTIR spectroscopy.Operando ATR-FTIR spectroscopy proves to be a powerful technique in battery research, particularly for investigating SEI. The ATR mode's surface sensitivity enables studying the composition of the SEI without bulk signal interference. In this work, we employed the internal reflection mode of the ATR-FTIR spectroscopy, for which the electrode of interest has to be IR permeable. Furthermore, by variation of the incident angle of the IR beam, the penetration depth can be varied to obtain an interphase profile from electrode to bulk electrolyte. In this study, the SEI composition on the silicon anode in the presence of BE and the corresponding additives, 2-SBA and LiDFP, was investigated under real-working conditions. The results elucidate that 2-SBA is accumulated and decomposed via ring-opening on the silicon surface to form a stable SEI layer. However, in the presence of LiDFP and 2-SBA, a hybrid organic and inorganic SEI layer is formed, which proves to enhance electrochemical performance and cycle life. The findings of this study provide valuable structural insights into the silicon particle surface for the development of high-voltage silicon-based lithium-ion batteries with Ni-rich cathodes.

Multifunctional Additive Ethoxy(pentafluoro)Cyclotriphosphazene Enables Safe Carbonate Electrolyte for SiOx-Graphite/NMC811 Batteries

The silicon or silicon monoxide (SiO x )-graphite/nickel-rich (≥80% Ni) LiNi x Mn y Co z O2 (x+y+z = 1, NMC) cell chemistry is widely regarded as one of the most promising chemistries for next-generation electric vehicle batteries for due to its higher energy density compared to state-of-the-art graphite/Ni-rich NMC batteries. However, the drastic volume change during lithiation and delithiation of silicon poses a significant challenge to realize its high capacity with a practical cycle life. Besides performance degradation, it is desirable to address safety risks stemming from, e.g., the high flammability of carbonate solvents and oxygen release from highly delithiated Ni-rich NMC materials.To address these problems, one of the most effective methods is to develop advanced electrolytes that combine flame-retardant properties and excellent electrochemical performance. Generally, in consideration of the balanced trade-offs between cost, scalability, safety, and electrochemical compatibility, the use of flame retardants is a very promising approach to realize the next-generation nonflammable electrolytes.However, it is still a huge challenge to optimize the electrolyte composition to stabilize Si-based and Ni-rich lithium-ion batteries.Here, the compatibility of the flame retardant ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as additive for carbonate electrolytes is studied, for the first time, in the SiO x -graphite/NMC811 full cells. [1] A synergistic effect is found between PFPN and lithium hexafluorophosphate (LiPF6) for the flame retardancy, and a modified electrolyte (1.35M LiPF6 in ethylene carbonate (EC):ethyl methyl carbonate (EMC) (3:7 by vol.) with 10 wt.% fluoroethylene carbonate (FEC) and 5 wt.% PFPN) displays a very low self-extinguishing time of only 3 s/g while also maintaining a high ionic conductivity of 8.4 mS/cm at 25 °C. Furthermore, the morphology evolution and interphase composition of both anode and cathode are investigated, gaining important insights into the decomposition mechanism of PFPN to stabilize the electrode-electrolyte interfaces. Meanwhile, the wetting properties of the modified electrolyte are also improved due to the excellent wettability of PFPN. As a result, half and full coin cells with SiO x -graphite anode and NMC811 cathode display better capacity retention during long-term cycling with the modified electrolyte than with 1M LiPF6 in EC:EMC (3:7 by vol.) with 10 wt.% FEC. In addition, the enhanced cycling performance with the modified PFPN-contained electrolyte is also confirmed for 1 Ah SiO x -graphite/NMC811 pouch cells cycled under various pressures. These results open a promising avenue for the development of safe and high-performance electrolytes for silicon-based lithium-ion batteries.

Engineering of Siloxanes for Stabilizing Silicon Anode Materials.

Silicon (Si) is considered the most promising anode material for the next generation of lithium-ion batteries (LIBs) because of its high theoretical specific capacity and abundant reserves. However, the volume expansion of silicon in the cycling process causes the destruction of the electrode structure and irreversible capacity loss. As a result, the commercial application of silicon materials is greatly hindered. In recent years, siloxane-based organosilicon materials have been widely used in silicon anode of LIBs because of their unique structure and physical and chemical properties, and have shown excellent electrochemical properties. The comprehensive achievement of siloxanes in silicon-based LIBs can be understood better through a systematic summary, which is necessary to guide the design of electrodes and achieve better electrochemical performance. This paper systematically introduces the unique advantages of siloxane materials in electrode, surface/interface modification, binder, and electrolyte. The challenges and future directions for siloxane materials are presented to enhance their performance and expand their application in silicon-based LIBs.

Performance of Lithium-Ion Pouch Cells with Silicon Composite Anodes under External Mechanical Pressure

The external forces have significant effects on the mechanical and electrochemical properties of lithium-ion pouch cells with silicon composite electrodes, but the behaviors under the constant pressure condition have been lacking for a long time. In this study, on the basis of the in situ testing equipment that can provide good precision and good stability under constant pressure conditions, the mechanical and electrochemical performance of silicon-composite-based batteries is studied in detail. First, the optimal constant pressure for the battery is proposed with the value of 0.02 MPa. Then, the cycle life is started on the basis of this pressure, but it is found that the improvement in the capacity retention rate is limited. Through non-destructive computed tomography detection and morphology characterization, the silicon composite electrode under a constant pressure leads to a change in the battery spacing, which, in turn, increases the polarization and results in lithium precipitation on the surface, and lithium precipitation consumes the electrolyte and causes the gas formation and eventually battery failure. Finally, an improved strategy that can effectively prolong the battery cycle period is proposed. In the experiment, it is observed that, when the battery operates under a constant pressure, its capacity undergoes a slow decline followed by a rapid drop at a specific capacity point known as the “inflection point”. When the inflection point occurs, increasing the external pressure applied to the battery can delay the aging behavior of the battery. This work has certain guidance for improving the cycle life of silicon-based lithium-ion batteries and pushes their engineering applications in battery pack systems.

Impact of solid-electrolyte interphase reformation on capacity loss in silicon-based lithium-ion batteries

High-density silicon composite anodes show large volume changes upon charging/discharging triggering the reformation of the solid electrolyte interface (SEI), an interface initially formed at the silicon surface. The question remains how the reformation process and accompanied material evolution, in particular for industrial up-scalable cells, impacts cell performance. Here, we develop a correlated workflow incorporating X-ray microscopy, field-emission scanning electron microscopy tomography, elemental imaging and deep learning-based microstructure quantification suitable to witness the structural and chemical progression of the silicon and SEI reformation upon cycling. The nanometer-sized SEI layer evolves into a micron-sized silicon electrolyte composite structure at prolonged cycles. Experimental-informed electrochemical modelling endorses an underutilisation of the active material due to the silicon electrolyte composite growth affecting the capacity. A chemo-mechanical model is used to analyse the stability of the SEI/silicon reaction front and to investigate the effects of material properties on the stability that can affect the capacity loss.

High cycling stability anode of interlayer silicon film with carbon buffer layer on 3D collector

The application scope of silicon-based anode is limited by its poor electrical conductivity and massive volume expansion. Herein, we propose a method to modify electrochemical performance of silicon-based anode with 3D collector and carbon buffer layer by magnetron sputtering. With foam Ni as collector, at a current density of 1 A/g, the first reversible specific capacity reached 1973 mAh/g, and the specific capacity after 100 cycles was1700 mAh/g. With carbon cloth as collector, the first reversible specific capacity was 1543 mAh/g, and the specific capacity after 100 cycles was 1337 mAh/g. The 3D collector was used to buffer the internal stress caused by the bulk effect of silicon. The carbon buffer layer not only improved the material conductivity but also avoided the repeated growth of SEI film, thus providing more buffer space for silicon. This work provides a new promising solution to silicon-based lithium-ion batteries.

Effect of Porosity in Activated Carbon Supports for Silicon-Based Lithium-Ion Batteries (LIBs).

Activated carbon supports for Si deposition with different porosities were prepared, and the effect of porosity on the electrochemical characteristics was investigated. The porosity of the support is a key parameter affecting the Si deposition mechanism and the stability of the electrode. In the Si deposition mechanism, as the porosity of activated carbon increases, the effect of particle size reduction due to the uniform dispersion of Si was confirmed. This implies that the porosity of activated carbon can affect the rate performance. However, excessively high porosity reduced the contact area between Si and activated carbon, resulting in poor electrode stability. Therefore, controlling the porosity of activated carbon is essential to improving the electrochemical characteristics.

Cycling-induced damage of silicon-based lithium-ion batteries: Modeling and experimental validation

Currently, there are few analyses available to quantitatively uncover the effects of cycling-induced damage in silicon-based batteries on the stress evolution and capacity loss. We develop a comprehensive model to address this issue. The comparisons between numerical and experimental results validate the proposed model and illustrate the damage effects on the decrease of structural stiffness and the stress evolution. In contrast to the common perception that damage is unfavorable to batteries, we propose a concept of training of batteries which introduces sufficient damage to batteries to improve retention performance. The training process is implemented by electrochemical cycling under a large C-rate, and its merit is validated experimentally. We also discuss optimization of the training method.

Hydrogen Bond-Enabled High-ICE Anode for Lithium-Ion Battery Using Carbonized Citric Acid-Coated Silicon Flake in PAA Binder.

A silicon-based lithium-ion battery (LIB) anode is extensively studied because of silicon's abundance, high theoretical specific capacity (4200 mAh/g), and low operating potential versus lithium. Technical barriers to large-scale commercial applications include the low electrical conductivity and up to about 400% volume changes of silicon due to alloying with lithium. Maintaining the physical integrity of individual silicon particles and the anode structure is the top priority. We use strong hydrogen bonds between citric acid (CA) and silicon to firmly coat CA on silicon. Carbonized CA (CCA) enhances electrical conductivity of silicon. Polyacrylic acid (PAA) binder encapsulates silicon flakes by strong bonds formed by abundant COOH functional groups in PAA and on CCA. It results in excellent physical integrity of individual silicon particles and the whole anode. The silicon-based anode shows high initial coulombic efficiency, around 90%, and the capacity retention of 1479 mAh/g after 200 discharge-charge cycles at 1 A/g current. At 4 A/g, the capacity retention of 1053 mAh/g was achieved. A durable high-ICE silicon-based LIB anode capable of high discharge-charge current has been reported.

Dual-Salt Localized High-Concentration Electrolyte for Long Cycle Life Silicon-Based Lithium-Ion Batteries.

Silicon-based materials are considered the most promising anodes for next-generation lithium-ion batteries (LIBs) owing to their high specific capacity. However, poor interfacial stability due to enormous volume changes severely restricts their mass application in LIBs. Here, we design a fluoroethylene carbonate (FEC)-containing dual-salt (LiFSI-LiPF6) ether-based localized high-concentration electrolyte (D-LHCE-F) for enhancing the interfacial stability of silicon-based electrodes. It is revealed that the dominating LiFSI salt of superior chemical and thermal stability prevents the formation of corrosive HF, while the addition of FEC improves the interface stability by promoting the formation of protective LiF-rich SEI and increasing the flexibility of the interface. This robust and flexible SEI layer can adapt to substantial variations in the volume of silicon electrodes while preserving the integrity of the interface. The SiOx/C electrode using the unique D-LHCE-F retains up to 78.5% of its initial capacity after 500 cycles at 0.5C, well surpassing that of the control electrolyte (3.4% capacity retention). More notably, the cycle life of the SiOx/C||NCM90 (LiNi0.9Co0.05Mn0.05O2) full batteries is effectively enhanced thanks to the stabilized electrode/electrolyte interfaces. The key findings of this work offer crucial knowledge for rationally designing electrolyte chemistry to enable the practical application of high-energy-density LIBs adopting silicon-based anodes.

Recent advances in modification strategies of silicon-based lithium-ion batteries

Recent advances in modification strategies of silicon-based lithium-ion batteries

Mechanism study on the cycling stability of silicon-based lithium ion batteries as a function of temperature

Adapting to a wide operating temperature range is an inevitable trend in the development of rechargeable batteries. This work investigates the cycling stability of silicon (Si)-based half and full cells at a wide temperature range and the associated capacity fading mechanisms. Results show that compared with room temperature (25 °C), low temperature (0 °C) causes a decrease in capacity due to sluggish kinetics, and high temperature (60 °C) results in the lowest first Coulombic efficiency and the worst cycling stability with different capacity fading mechanisms in the half and full cells. In addition, composition and stability of solid-electrolyte interphase films are strongly temperature sensitive. Specifically, high temperature aggravates the dissolution of organic layer and the degradation of lithium hexafluorophosphate, and low temperature is not conducive to the formation of lithium carbonate. This work clearly reveals the problems that need to be solved to realize the application of Si anodes at a wide temperature range, which has important guiding significance for promoting the development and application of Si anodes in lithium ion batteries.