Si Anode Research Articles

Operando X-Ray Absorption Spectroscopy of Solid Electrolyte Interphase Formation on Silicon Anodes

Lithium-ion batteries (LIBs) are key to the transition from fossil fuels towards increased use of renewable energy sources. However, more widespread deployment requires improvements in energy density, cost and cycle-lifetime. Various cathode and anode materials are under consideration for next-generation LIBs, and the interfacial stability of these materials in contact with the electrolyte is a critical consideration. Interface-sensitive operando characterization techniques are thus urgently needed to reveal the reactions occurring in working batteries.1,2 The solid electrolyte interphase (SEI) that forms on Li-ion battery anodes is critical to their long-term performance, however observing SEI formation processes at the buried electrode-electrolyte interface is a significant challenge. Here we show that operando soft X-ray absorption spectroscopy in total electron yield mode can resolve the chemical evolution of the SEI during electrochemical formation in a Li-ion cell, with nm-scale interface sensitivity. O, F, and Si K-edge spectra, acquired as a function of potential, reveal when key reactions occur on high-capacity amorphous Si anodes cycled with and without fluoroethylene carbonate (FEC).3 Cross-referencing to cycling data, complementary bulk sensitive fluoresecent yield (FY) XAS measurements, and density functional theory (DFT) calculated spectra enables identification of the electrolyte and SEI species, and the dominant mechanisms of SEI formation. Without FEC present, LiF formation is detected at 0.6 V vs. Li/Li+ prior to significant lithiation of the a-Si, whilst at lower potentials the SEI grows in thickness with an increased contribution from organic components containing -C(=O)O- species. The observed sequential formation of inorganic and organic components is implicated in layering of the SEI. With FEC as an additive we see the onset of SEI formation at much higher potentials (1.0 V vs. Li/Li+), and attribute the improved cycle life seen with this additive to the rapid healing of SEI defects formed during delithiation. Operando TEY-XAS offers new insights into the formation mechanisms of electrode-electrolyte interphases and their stability for a wide variety of electrode materials and electrolyte formulations. References Wu et al. Phys. Chem. Chem. Phys. 2015, 17, 30229.Weatherup et al. Top. Catal. 2018, 61, 2085.Swallow et al. Nature Commun. 2022, 13, 6070.

Fabrication of Si Anode for Enhancing Electrochemical Performance by Electrodeposition Method

Silicon (Si) is one of the most abundant elements in the earth's crust and is important for the development of semiconductors, solar cells, and lithium ion battery (LIB)electrodes. silicon nanomaterials-based device production is currently hampered by high prices, high material consumption, and very sophisticated procedures of film deposition, including chemical vapour deposition (CVD) and plasma-enhanced chemical vapour deposition (PE-CVD).Future demand will need the development of cost-effective, simple, and high-throughput deposition techniques.moreover A large-scale use of Si anodes in LIB is hindered primarily by two factors: (a) a significant volume change (about 300%) during discharging and (b) the deterioration of silicon after several charging and discharging cycles. By covering silicon nanostructures with carbon nanomaterials that also improve the electrochemical performance of LIBs, these disadvantages may be eliminated. In order to meet all of these requirements, the electrodeposition approach may provide the means to create Si thin films in an aesthetic way. We studied We used water-contaminated BMImTf2N to electrolyze SiNPs on Graphene (Grn) -coated copper substrates at room temperature.SiNPs average 70-90 nanometres (nm). Grn layer on the Cu substrate enhances Si nucleation and prevents oxidation. At 0.5C, the charge capacity was 1350 mAh g-1 and the discharge capacity was 1588 mAh g-1. The columbic process's efficiency increased from 85% to 97% after 100 cycles. Grn's conductivity and volume expansion will boost Si's cycle life. Figure 1

On the Chemo-Mechanics of Advanced Electrode Materials Via Operando Acoustic Transmission

Silicon anodes have emerged as a viable strategy for a negative material in solid-state batteries to balance their reactivity with high energy density. Compared to conventional graphite electrodes, silicon anodes have a large theoretical capacity of 3600 mAh/g compared to 372 mAh/g in graphite. This large capacity comes from the fact that lithiated silicon (Si4Li15) can accommodate 15 Li atoms per 4 Si atoms as opposed to LiC6. As a result, silicon anodes experience large volumetric expansions up to ~300% as Li ions alloy into the Si negative electrode. Acoustic transmission utilizes sound propagation to nondestructively probe electrode chemo-mechanics in operando.c = √(E/ρ)The speed of sound through a material is proportional to its Young’s modulus (E) and inversely proportional to density. Previous works have shown that acoustic transmission can detect gas formation and dewetting in commercial Li-ion cells and Li metal cells. There has also been a study showing acoustics can detect void formation during Li stripping in solid-state Li symmetric cells. To the best of our knowledge, there has not been an acoustic study of an all solid state Li full cell.This work intends to show that acoustic transmission can monitor Si expansion and contraction as a function of waveform damping and the Young’s modulus of the Si electrode. This works gives insight into the mechanical considerations and possible loss of contact as Si lithiates and delithiates repeatedly. The reliance of Si anodes on stack pressure is not well understood and is further elucidated in this work. We hope to give a better understanding of the intersection between the electrochemical reactions at the Si electrode and the mechanical stresses induced on the cell. Figure 1

Understanding the Effect of Mechanical Degradation on the Performance of Solid-State Batteries through Particle Simulations

All-solid-state batteries (ASSBs) have garnered significant interest as a promising alternative to conventional lithium-ion batteries, offering improved safety, higher energy density, longer lifespan, faster charging and wider operating temperature range. A key advantage of ASSBs is the use of solid electrolytes (SE), which eliminate the risks associated with flammable liquid electrolytes. However, the complex electrochemical behavior and multi-scale nature of ASSBs pose challenges in designing and optimizing their performance. This study employs Discrete Element Method (DEM) particle-based models to better understand degradation behavior of ASSBs by considering electrochemical reaction, mass and charge transfer, intercalation expansion and material deformationOur simulations were developed in MATLAB and were performed on a half-cell configuration comprising a SE-layer and an anode electrode. The anode electrode was composed of a particle mixture containing active material (AM) and SE. In our simulations, Si was employed as AM, which experiences substantial intercalation expansion during charge cycling 1. Our previously developed DEM model2,3 resolved elastic and plastic deformation of both AM and SE particles which become compressed due to the intercalation expansion. The simulation of intercalation was achieved by integrating the Newman electrochemical model,4 into the DEM mechanical model. Building on our earlier study5, where the Li concentration was resolved within each AM particle, this study is also accounting for the Li-ion potential within each SE particle. Interparticle conduction and diffusion were computed by determining the contact area of AM-AM and SE-SE contacts, which were affected by the compression of the electrode. The electrochemical reaction was calculated at the AM-SE interface using the Butler-Volmer equation, and in addition the influence of compressive stress on the reaction6 was included.Figure 1(a) depicts the Li concentration and Li-ion potential distribution within the half-cell during charging at different states of charge (SOC), while Figure 1(b) provides a 3D view of the distributions at a SOC of 50%. A considerable expansion of the Si anode is evident. The gradients of Li concentration and Li-ion potential signify significant mass and charge transfer resistance during the charging process. Comparing the distribution of the particles, the anode becomes more porous after the first cycle for the same value of SOC. This effect is attributed to the extensive expansion of the Si anode, leading to plastic compression of the SE layer, which becomes more compact after each cycle. The growing porosity diminishes the contact area between particles, ultimately resulting in the degradation of the half-cell's capacity. In addition to SE-layer compaction, this study aims to investigate several degradation mechanisms and their impact on the performance of ASSBs, including the development of shell voids resulting from AM-SE delamination, crack propagation through SE, and fragmentation of AM.The results of this study provide valuable insights into understanding the effect of mechanical degradation on the performance of ASSBs. By improving our understanding of these mechanisms, we can work towards enhancing the durability and lifespan of ASSBs, ultimately contributing to the development of next-generation energy storage systems. Acknowledgment This work was supported by JSPS KAKENHI Grant-in-Aid for Scientific Research on Innovative Areas, “Science on Interfacial Ion Dynamics for Solid State Ionics Devices, Computational & Data Science” (Gp-A03, grant number 19H05815); and MEXT “Program for Promoting Researches on the Supercomputer Fugaku” (Fugaku battery & Fuel Cell Project), grant number JPMXP1020200301. References M. N. Obrovac and L. Christensen, Electrochem. Solid-State Lett., 7, A93 (2004).M. So, G. Inoue, R. Hirate, K. Nunoshita, S. Ishikawa, and Y. Tsuge, J. Electrochem. Soc., 168, 030538 (2021).M. So, G. Inoue, R. Hirate, K. Nunoshita, S. Ishikawa, and Y. Tsuge, Journal of Power Sources, 508, 230344 (2021).J. Newman and K. E. Thomas-Alyea, Electrochemical Systems, 3rd edition., p. 672, Wiley-Interscience, Hoboken, N.J, (2004).M. So, S. Yano, A. Permatasari, T. D. Pham, K. Park, and G. Inoue, Journal of Power Sources, 546, 231956 (2022).G. Bucci, T. Swamy, S. Bishop, B. W. Sheldon, Y.-M. Chiang, and W. C. Carter, J. Electrochem. Soc., 164, A645 (2017). Figure 1

Understanding Electrochemical Properties for a Bio-Based Silicon Anode Electrode Enhanced with Carbon Nanostructure Conductive Additives and Water-Based Binders

Lithium Ion batteries (LIB) demand has shown an exciting increase lately, particularly looking for light-weight solution for portable devices [1], [2]. Recently, The development and implementation of electrode material production techniques pushed the LIB's current state performance to further improvement. Silicon (Si) anode-based electrodes are considered an attractvie alternative to conventional graphite electrodes due to their high specific capacity [3]. Theoretically, Si could alloy with Li up to Li4.4Si and result in a specific capacity of 4200 mAh/g, where the mechanical stress within the electrode material causes loss in the conductivity and breaking of the cell. To overcome this issue, different methodologies have been tested for further improvement of Si implementation with different nanostructures [4]. On the other hand, the production rate of LIB is very important to meet the high demand for different technologies. and, a commercial Si grade is highly recommended along with the conventional tape-casting production method. Furthermore, water-based binders, such as Polyacrylic Acid and Carboxy methyl Cellulose (cellulose-based binders) plays an important role in electrode preparation, where it is supporting the volume expansion of Si and preserveing electrode morphology [5]. Herein, we focus on producing a high-quality Si electrode with cellulose binder, enhanced by conductive carbon allotrope additives. In this study, different Si grades will be tested with different concentrations along with conductive and binder [6]. Electrochemical characterization of the Si anode half cell , such as cycling, cyclic voltammetry, and Impedance spectroscopy vs Li+ metal shows extended and stabilized cycling performance, inferring a reduced anode pulverization.

(Invited) Binder Investigation for Silicon Electrode of Lithium-Ion Batteries

Though the binder is not an active material and does not contribute capacity to lithium ion batteries (LIBs), it is an important ingredient for maintaining the integrity of the electrode, which helps to improve electrical contact between the active materials and conductive carbon black, improves the Li+ transport efficiency, reduces the internal resistance of Li-ion batteries and effectively depresses the crack formations and phase separation.Polyvinylidene fluoride (PVDF) is a polymer that is commonly used as a binder for both anode and cathode materials in LIBs. However, it is not suitable for Si electrode due to its poor binding capability and stability. Viewed as a next generation anode material, Si has been extensively studied due to its extremely high theoretical specific capacity of 3578 mAh/g (assuming Li15Si4 as intermediate product). However, silicon undergoes huge volume variations during repeated discharge and charge, which requires a strong binder to maintain the electrode mechanical integrity. Developing a high strength binder for silicon anodes has been considered as an efficient pathway to alleviate various capacity decay pathways.Polyacrylic acid (PAA) and its lithiated version (LiPAA), rich with carboxy function group, can provide stronger binding and are widely used as binder for Si electrode. In this work, we optimized Si electrode formulation by varying the binder composition. The optimized Si electrodes were electrochemically tested in both half cells and full cells. With improvement in electrochemical performance, cracks at the electrode level can still be observed for the cycled electrodes, which suggests that a stronger binder is required to mitigate volume expansion of Si electrodes and hold the particles together.We further studied the polyimide (PI) materials as binders for Si anodes in an attempt to achieve more stable cycling performance. In this work, we explore various PI crosslinking conditions and their effects on electrochemical performance. The optimized silicon electrode exhibits a higher tensile strength than that of conventional PAA binder. The strong adhesion of the PI binder suppresses the structural collapse of the Si negative electrode during lithiation/delithiation, enabling good capacity retention and stable cycle life.

High Precision Coulometry and Calorimetry Measurements of Side Reactions for Si/NCA and G/NMC811 Cells

Side reactions taking place at both anode and cathode can be investigated via different methods. Common methods include the high precision coulometry [1-3] and the isothermal calorimetry [4, 5]. In this study, pure silicon anode (70 wt%) Si/NCA cells and pure graphite G/NMC811 cells are investigated via the methods mentioned above. These measurements include voltage holds and charge and discharge endpoint slippage analysis, which is described in [6]. Glazier et al. [4] already showed that after sufficient time, the heat flow during a voltage hold is equivalent to the side reactions taking place. The aim of this study is to investigate the dependency of side reaction currents and parasitic heat on different voltages and temperatures. In addition, their behaviour during the transient phase caused via relaxation processes and edge effects [7] comparing silicon and graphite materials.The cells voltage was held at different state-of-charge (SOC) conditions, low, medium, and high as well as at different temperatures. At the beginning and at the end of the experiment, check-ups were performed to compare the capacity loss and to analyse the endpoint slippage. During the measurements, the heat flow and the leakage current of the cells were measured simultaneously.The preliminary results show that for the low and for the high SOCs, a strong opposing transient phase is present at the beginning of the voltage hold. The strong transient phase is expected for silicon-based materials due to their high relaxation characteristics, meaning also higher leakage currents for this material. Additionally, it was found that the different pre-histories of the cells influence the amount of leakage current measured. Meaning that the actual side reaction current is only achieved after edge effects and relaxation processes cease, which can take a long time for pure Si anodes, up to 1000 hours at 25°C. Moreover, the transient phase of the thermal and the electrical signals was correlated for the different materials.The study of side reactions for lithium ion cells is investigated in the project “ExZellTUM III”, funded by the German Federal Ministry of Education and Research (BMBF) under grant number 03XP0255. [1] Smith, A.; Burns, J.; Dahn, J.: A high precision study of the coulombic efficiency of Li-ion batteries, In: Electrochemical and Solid-State Letters 13, pp. A177, 2010 [2] Smith, A.; Burns, J.; Xiong, D.; Dahn, J.: Interpreting High Precision Coulometry Results on Li-ion Cells, In: Journal of The Electrochemical Society 158, S. A1136– A1142, 2011 [3] Burns, J. C.; Jain, G.; Smith, A. J.; Eberman, K. W.; Scott, E.; Gardner, J. P.; Dahn, J. R.: Evaluation of effects of additives in wound Li-ion cells through high precision coulometry, In: Journal of The Electrochemical Society, 158 (3), A255-A261, 2011 [4] Glazier, S. L.; Downie, L. E.; Xia, J.; Louli, A. J.; Dahn, J. R.: Effects of fluorinated carbonate solvent blends on high voltage parasitic reactions in lithium ion cells using OCV isothermal microcalorimetry, In: Journal of The Electrochemical Society, 163 (10), A2131-A2138, 2016 [5] Glazier, S. L.; Odom, S. A.; Kaur, A. P.; Dahn, J. R.: Determining parasitic reaction enthalpies in lithium-ion cells using isothermal microcalorimetry, In: Journal of The Electrochemical Society, 165 (14), A3449-A3458, 2018 [6] Streck, L.; Roth, T.; Keil, P.; Strehle, B.; Ludmann, S.; Jossen, A.: A comparison of voltage hold and voltage decay methods for side reactions characterization, In: Journal of The Electrochemical Society, 170, 040520, 2023 [7] Roth, T.; Streck, L.; Graule, A.; Niehoff, P.; Jossen, A.: Relaxation effects in self-discharge measurements of lithium-ion batteries, In: Journal of The Electrochemical Society, 170, 020502, 2023

Surface Controlled Silicon Nanoparticles Production and Their Effects on High Capacity and High Cyclability of All-Solid-State Lithium-Ion Batteries

Si nanoparticle is expected as anode for high density Lithium-ion batteries as as it facilitates high capacity and high cyclability simultaneously owing to its structural robustness to suppress fracture during cycled (de)lithiation reactions. Direct TEM observation has revealed that the particle size of 150 nm is the threshold for facture and the particles smaller than 150 nm are anticipated to contribute to the structural stability during cycles. However, the surface of silicon nanoparticle is oxidized spontaneously and the specific surface area increases significantly with decreasing the particle size. Accordingly, the specific oxygen content of the Si active material becomes inevitably high for smaller nanoparticles. High oxygen content in Si anode decreases the initial efficiency and capacityas a result of irreversible silicate formation. Therefore, smaller nanoparticle with a limited amount of oxidation would be ideal and necessary to attain high capacity and high cyclability. However, there is few report on the approach to suppress oxidation of smaller silicon nanoparticles and discuss the effect of size and oxygen content separately. Also, no general understanding of the effect of the particle size and oxygen for the case of all-solid-state batteries (ASSBs). In this work, we have produced Si nanoparticles with differently controlled size and oxygen content by plasma flash evaporation (PFE) from low-cost powder feedstock, and the effect of characteristic oxide surface structure on the battery performance of ASSBs with Argyrodite electrolyte has been identified.We have successfully produced the nanoparticles as small as 20 nm and reduced the oxygen content x in SiOx representation from the standard amount of 0.24 to 0.049. As a result, the initial discharged capacity can be improved by 110% while attaining similar cyclabilities. When we compare the nanoparticles with different sizes ranging from 20 nm to 165 nm and having small oxygen content x < 0.05, although the initial discharged capacities are almost the same for these particles, only the particle with 165 nm shows rapid capacity decay in 10 cycles, whereas the 20 nm and 84 nm particles tend to maintain the capacity similarly. This confirms that the particles smaller than 100 nm are effective to maintain high capacity also in ASSBs under a low 0.1 C-rate condition. Furthermore, XPS analysis revealed that the surface of the particles with less oxidation is composed of suboxide Si-O bond oxide preferentially and the amount of Si-O4 bond is less than the conventional particles covered by the oxide shell, with which the Si-O bond ratio is described by the conventional random bond model. No apparent dependence of the capacity with the amount of Si-O4 bond. However, the surface oxide shell thickness estimated by the Si-O bond amount and the total oxygen content has shown a clear linear correlation with the charged capacity, irrespective of the particle size. This suggests that the surface oxide thickness affects significantly the amount of the lithiation reaction and is ideally as thin as possible to attain high capacity, especially for the case of ASSBs.

Alternating Si/C Thin-Films as Model Anode Material for Lithium-Ion Batteries

Graphite is currently the state-of-art material for the anode-side of lithium-ion batteries (LIB) with a theoretical capacity of 372 mAh g-1. However, its technological potential is already largely exhausted, shifting research focus to other materials, such as silicon (Si) with its high theoretical capacity (3579 mAh g-1) [1]. However, Si cannot be used on its own because of its low electrical conductivity. Moreover, it suffers from a strong increase in volume and amorphization during lithiation, which is the primary origin of several degradation mechanisms, e.g. as pulverization, delamination and an unstable solid electrolyte interface. There are various approaches to counteract these issues, amongst them the structuring of Si into nanowires or hollow structures [2]. Silicon is most often used with graphite in a composite material, due to decades of experience in graphite synthesis an application [3].In this work we investigate anodes consisting of alternating Si and C thin-films with a layer thickness of a few hundred nanometers each. In general, Si thin-film anodes show a higher performance than its bulk counterparts [4]. The layers are produced by deposition from the gas phase. This process enables good adhesion between the particles and the substrate, which can counteract delamination and provide a longer cycle life. Additionally, it can also be performed in a binder-free fashion, thereby reducing the need for inactive electrode components.The alternation of carbon and silicon layers improves the electrical conductivity and also separates the silicon layers from each other aiding to reduce the mechanical stress caused by volume expansion. The characterization of the layers is done by cross sectional SEM, EDX and AFM. Furthermore, the crystallinity of the deposited layers is determined via XRD. The manufacturing process influences the morphology of the layers, which in turn affects the electrochemical properties. For this reason, galvanostatic cycling and electrochemical impedance spectroscopy are subsequently carried out in a coin cell type Swagelok half-cell setup with 2- and 3-electrode arrangements. Constant current cycling is used to investigate the long-term stability of the cells in order to analyze the change in the respective Si layers as a function of their distance from the surface. In addition, the electrodes are analyzed post-mortem via SEM and XRD to investigate which degradation mechanisms play a role in the observed behavior.[1] Kasavajjula, U. et al., Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells, J. of Power Sources 163 (2), 1003 – 1039, 2007.[2] Wu, H., Cui Y., Designing nanostructured Si anodes for high energy lithium ion batteries, Nano Today 7 (5), 414 – 429, 2012.[3] You, S. et al., Design Strategies of Si/C Composite Anode for Lithium-Ion Batteries, Chem. Eur. J. 27 (48), 12237 – 12256, 2021 [4] Graetz, J. et al., Highly reversible Lithium storage in nanostructures Silicon, Electrochem. Solid-State Lett. 6 (9), A194, 2003.

Extending Cycle Life of Li-Ion Batteries Via Gas-Phase Nanocoating of Cathode Active Materials

The further penetration of the electric vehicles is dependent on the development of high-performance Li-ion batteries in terms of cost, cycle life, energy density, safety as well as sustainability. It is expected, in the short term, EVs will rely more on Li-ion technologies using active materials such as Ni-rich NMC cathode and Si anode for developing high specific energy and lower cost batteries1.However, these active materials are facing multiple serious challenges which could hinder their targeted performance. Regarding this, Ni-rich NMC cathode active materials (CAM), in spite of their high energy density as a result of higher Ni content, tend to undergo dramatic capacity fade. Since most degradation mechanisms are related to the surface of active materials, immense research and development efforts have been dedicated to surface modification techniques, and especially coating strategies2,3.Examples of surface modification strategies include sol-gel, hydro/solvothermal deposition, and dry coating. A main drawback of these techniques is that they are not capable of precise control of the film thickness and uniformity. On the other hand, gas-phase coating techniques, such as atomic or molecular layer deposition, can address these shortcomings by offering a precise thickness control even in the range of angstroms and pinhole-free conformal coatings. As such, these coatings are better suited at mitigating interfacial degradation. Various nanocoating chemistries, such as oxides, fluorides, nitrides, phosphates and aluminates protect and stabilize the surface of Ni-rich cathode materials through the different pathways. In this talk, we explore the benefits of gas-phase nanocoatings, and will show how we can produce surface modified Ni-rich CAM (e.g. NMC-811) in a continuous process that is ready for mass production. References M. S. E. Houache, C. H. Yim, Z. Karkar, and Y. Abu-Lebdeh, Batteries, 8 (2022).D. Weber, Đ. Tripković, K. Kretschmer, M. Bianchini, and T. Brezesinski, Eur. J. Inorg. Chem., 2020, 3117–3130 (2020).M. Lee et al., Chem. Mater., 34, 3539–3587 (2022).Y. Zhao, K. Zheng, and X. Sun, Joule, 2, 2583–2604 (2018).

(Digital Presentation) Unraveling of the Morphology and Chemistry Dynamics in the FEC-Generated Silicon Anode SEI across Delithiated and Lithiated States

The silicon solid electrolyte interphase (SEI) faces cyclical cracking and reconstruction due to the ~350% volume expansion of Si which leads to shortened cell life during electrochemical cycling. Understanding the SEI morphology/chemistry and more importantly its dynamic evolution from delithiated and lithiated states is paramount to engineering a stable Si anode. Fluoroethylene carbonate (FEC) is a preferred additive with widely demonstrated enhancement of the Si cycling. Thus, insights into the effects of FEC on the dynamics of the resulting SEI may provide hints toward engineering the Si interface. Herein, ATR-FTIR, AFM, tip IR, and XPS probing all show pronounced relative invariance of the FEC-generated SEI compared to the FEC-free SEI between adjacent lithiated and delithiated states beyond the formation cycles. The SEI of Si thin film model surfaces in the baseline 1 M LiPF6 in EC:EMC (1:1) undergoes major morphological and chemical speciation swings between half-cycles while comparatively the SEI upon addition of FEC displays far less dynamic evolution. This morphology and chemistry stability of the FEC-SEI supports the enhanced cycling stability of silicon anodes in FEC-containing electrolytes. The experimental evidence gathered suggests that the FEC-SEI invariance is enabled by an elastomeric polycarbonate matrix that preserves the SEI integrity against the expansion of silicon upon lithiation. In turn, less electrolyte-consuming reconstruction occurs which manifests as and high LiF content from one half-cycle to the next. This work provides critical insights to enhance the silicon anode stability via targeted SEI engineering, namely that LiF protected by an elastomeric protective matrix may be key to buffering the unavoidable mechanical disruption. Figure 1

Pre-Lithiation of Silicon-Based Anode Materials: Concepts and Realization

The capacity in lithium ion battery (LIB) relies on active lithium, i.e., lithium-ions and electrons, which separately shuttle between the electrodes during charge and discharge. Given state-of-the art active materials for anodes, loss of active lithium and capacity remains a major challenge during LIB operation, in particular in the first charge/discharge cycle due to electrolyte decomposition and formation of solid electrolyte interphase (SEI).Pre-lithiation, i.e., artificial increase in active lithium amount into the battery is a promising strategy to counteract active lithium loss. Electrochemical(1) and chemical(2,3) methods of pre-lithiation can be distinguished. While electrochemical methods are based on the use of an external power source, the driving force of the chemical reaction is a negative change in the Gibb´s free energy which in the case of pre-lithiation is provided by the use of highly reactive chemical compounds (e.g. lithium-organic complex solutions or lithium metal). The use of lithium metal allows for a wide range of technological processes, including lamination of lithium foil, gas-phase deposition, application of lithium melts or suspensions containing lithium powder. In this contribution, various concepts of pre-lithiation will be discussed from experimental and up-scaling point of view on the example of Si-based anodes.(1) Haneke, L.; Pfeiffer, F.; Bärmann, P.; Wrogemann, J.; Peschel, C.; Neumann, J.; Kux, F.; Nowak, S.; Winter, M.; Placke, T., Insights into Electrolytic Pre‐Lithiation: A Thorough Analysis Using Silicon Thin Film Anodes. Small 2022, 2206092.(2) Adhitama, E.; Bela, M. M.; Demelash, F.; Stan, M. C.; Winter, M.; Gomez‐Martin, A.; Placke, T., On the Practical Applicability of the Li Metal‐Based Thermal Evaporation Prelithiation Technique on Si Anodes for Lithium Ion Batteries. Advanced Energy Materials 2023, 13 (3), 2203256.(3) Bärmann, P.; Mohrhardt, M.; Frerichs, J. E.; Helling, M.; Kolesnikov, A.; Klabunde, S.; Nowak, S.; Hansen, M. R.; Winter, M.; Placke, T., Mechanistic Insights into the Pre‐Lithiation of Silicon/Graphite Negative Electrodes in “Dry State” and After Electrolyte Addition Using Passivated Lithium Metal Powder. Advanced Energy Materials 2021, 11 (25), 2100925.

(Invited) Extending Cycle and Calendar Life of Si Based Li-Ion Batteries By Localized High Concentration Electrolytes

Si is one of the most promising anode materials for the next generation of lithium (Li) ion batteries (LIBs). Recently, we have developed a porous Si with a unique carbon coating structure (“carbon on Si” instead of “Si on carbon”). The nano-porosity of the materials absorbed most of volume expansion so the particles (between 3-5 mm) can retain their integrity during cycling instead of breakdown observed in bulk Si particles. Although single layer pouch cells (Si/NMC622, 62 mAh) with this porous Si anode and baseline electrolyte (1.2 M LiPF6 in EC-EMC (3:7 by wt.) +10 wt.% FEC) can retain 91% capacity after 800 cycles, their calendar life is still far shorter from 10-year target required by electrical vehicles.In this work, we present a systematic investigation of the application of localized high concentration electrolyte (LHCE) to extend the cycle life and calendar life of Si-LIBs. A typical LHCE contains a Li salt (typically LiFSI) with high solubility in a common solvent (such as DMC), and a diluent (such as TTE) with minimal solubility of the Li salt. Compared with other electrolyte design, one distinct advantage of LHCE is that solvent and diluent in LHCE can be largely decoupled from each other: change in once components will have not significantly affect the functionality of other components. This characteristic of LHCE enables much more freedom in the electrolyte designs to satisfy different practical application needs (such as long cycle life, long calendar life, high rate, high temperature, and high voltage). For example, Si/NMC622 cells with a composition of LiFSI-2.15DMC-0.17VC-0.69FEC-4.31TTE (in molar ratio) have increased cycle life of Si/NMC622 pouch cells to 2000 cycles with 80% capacity retention at 25°C as compared with 1000 cycles when baseline electrolyte was used. However, this electrolyte is less stable when LiCoO2 is used as the cathode, leading to rapid capacity loss at elevated temperatures (45°C). One possible reason for this is that cobalt in the cathode leads to more rapid decomposition of FEC than in the case of NMC622 at 45°C. On the other hand, the stability of LHCE is significantly affected by the amount of free (unbound) solvent (including DMC, VC, and FEC in the above example) in the electrolyte. By minimizing the amount of total free solvents, an electrolyte with a composition of LiFSI-2DMC-0.1EC-0.1FEC-3TTE has led to a long cycle life of Si/NMC622 cells at 25°C. Increasing the amount of main solvent in the electrolyte can further increase the conductivity of the electrolyte and significantly increase the charge/discharge rate of the cells.The long calendar life of Si-LIBs can be measured by accelerated tests at elevated temperatures (up to 55°C). Although FEC-containing electrolytes can increase the cycle life of Si-LIBs at room temperature, most Si-LIBs with FEC-containing electrolytes exhibit a rapid increase in impedance at elevated temperature, leading to a short projected-calendar-life. We designed a series of experiments to investigate the effect of FEC on the calendar life of Si-LIBs. The results clearly indicate that the formation of a high impedance interphase layer on the anode and cathode surfaces due to the decomposition of FEC at high temperatures is one of the fundamental reasons for the short calendar life of Si-LIBs. By replacing FEC with an alternative additive, a new LHCE electrolyte has been designed that led to much better cycling stability of Si-LIBs at 45°C (less than 5% capacity loss in 500 cycles) and much longer calendar life. More details of these investigations will be reported in this presentation.

(Energy Technology Division Walter van Schalkwijk Award in Sustainable Energy Technology Address) Exploring New Electrode Designs with Nanofibers

In recent years, electrospinning has been gaining popularity as a robust and scalable technique for the fabrication of non-woven mats of sub-micron diameter polymer fibers. Although not as well studied, the technique can also be used to prepare particle/polymer fiber networks with high intra- and inter-fiber porosity. Such fibrous mats can be used as porous electrodes in fuel cells and batteries, where a high electrode/electrolyte interfacial area is needed. In this talk, particle/polymer electrospinning will be presented as a platform technique to fabricate a variety of electrode and membrane-electrode-assembly (MEA) products with unique and desirable compositions, architectures, and performance characteristics. Laboratory results will be presented for: (1) hydrogen/air fuel cell cathodes with Pt/C and PGM-free catalysts, (2) Pt/C hydrogen electrodes in a H2/Br2 redox flow battery, and (3) Si anodes for lithium-ion batteries.High particle content fibers containing Pt/C or Pt-alloy catalyst powder and a Nafion®perfluorosulfonic acid binder have shown great promise as electrodes in H2/air fuel cells. During electrospinning, Nafion ionomer migrates to the outer edges of the fiber, effectively creating a core-shell fiber morphology, with a low I/C ratio in the fiber interior. Additionally, the interior of the fiber contains nm-size pores and the outer surface of the Nafion shell exhibits enhanced hydrophobicity, due presumably to an accumulation of the polytetrafluoroethylene backbone chains (-CF2-CF2-) of Nafion. The resulting structure is advantageous in that the majority of catalyst particles are in a low I/C environment, nanopores in the fiber interior trap electro-generated water via capillary condensation, and the hydrophobic surface of the fibers facilitates electrogenerated water removal from the mat during fuel cell operation. The fuel cell power output using fiber mat anodes and cathodes is very high for a low Pt loading (0.10 -0.20 mg/cm2), near or above 1.0 W/cm2 for H2/air feeds in the range of 60-100% relative humidity.1,2 Additionally, the fiber mat cathodes exhibit excellent durability, with minimal power loss after accelerated voltage cycling tests. The hydrophobicity of fibers can be enhanced by adding polyvinylidene fluoride (PVDF) directly to the Nafion binder. Such blended binders in fiber/particle hybrid electrodes extend the operational lifetime of fuel cells with iron-based PGM-free cathode MEAs.As an extension of the fuel cell electrode work, electrospun Pt/C-Nafion nanofiber mat hydrogen electrodes have been made and tested for a H2-Br2 redox flow battery.3 The hydrophobic surface coating of core-shell fibers effectively blocks bromine species from poisoning the hydrogen electrode. In a 6.6 M HBr electrolyte lab-scale redox flow battery, the fiber mat electrodes worked extraordinarily well, with: (i) high power at low Pt loading, e.g., 650 mW/cm2 at 0.70 Vfor a loading of 0.11 mgPt/cm2 (6.4 kW/gPt) and 550 mW/cm2 at 0.65 V for a loading of 0.048 mgPt/cm2 (11.5 kW/gPt), (ii) no loss in power for more than 170 charge/discharge cycles, and (iii) a roundtrip current efficiency of 95%at both 0.2 and 0.3 A/cm2.For Li-ion battery applications, single and dual fiber anode mats have been prepared and evaluated, where the fibers contain a polymer binder (e.g., polyacrylic acid, polyamidimide, or polyvinylidene fluoride), Si nanoparticles as the electrochemically active material, and carbon powder as an electron conductor.4 Here, the gravimetric and areal capacities of the fiber anode are considerably higher than those of a conventional carbon particle anode. Inter-fiber voids allow for volume changes in Si during lithiation/delithiation, thus minimizing capacity fade during charge/discharge cycling (up to 600 cycles).AcknowledgmentsThis work was funded by the U.S. Department of Energy, Contract No. DE-EE0007653 from the Fuel Cell Technologies Office, through the Fuel Cell Performance and Durability Consortium (Fuel Cells Program Manager: Dimitrios Papageoropoulos) and Contract No. DE-EE0007215 from the Vehicle Technology Office.

Electrochemical Performances Ti4Ti5O12/Si Composite Anodes for Li-Ion Batteries

LTO /Si anode material for lithium-ion batteries were successfully synthesized by two-step hydrothermal method and ball milling synthesis , using tetrabutyl titanate, lithium acetate,silicone powder. In this work, LTO/Si composites with different weight ratios (50%,70%) were prepared and tested as anodes of Li-Ion Batteries.The electrochemical properties of the electrodes were investigated using by cyclic voltammetry , charge-discharge galvanostatic and impedance spectroscopy .Both the anodic and cathodic peaks from LTO and silicon were seen in the composites.LTO/SI Composites with higher Si contents (LTO =30 %et Si = 70%) have higher specific capacity .the results confirme that This material can be used as a high-power anode material in lithium-ion batteries.

Mitigating Chemo-Mechanical Degradation in Sulfide-Based All-Solid-State Batteries Comprising Sulfur Composite Cathode and Li–Si Alloy Anode

In this study, all-solid-state batteries consisting of an Li2S5–P2S5 (LPS) glass electrolyte, a sulfur/LPS glass/carbon composite cathode, and an Li–Si anode are prepared and tested under high cut-off voltage conditions (0.5–3.7 V) to elucidate the effect of LPS redox activity on the chemo-mechanical stability of LPS-based cells. The cell cycled in the voltage range 0.5–3.7 V exhibits unstable charging behaviors and voltage noise, with substantial LPS oxidative decomposition. X-ray photoelectron spectroscopy and impedance spectra analyses of a three-electrode system reveal that the cathode resistance is remarkably increased by the oxidative decomposition of LPS when the cell is charged to 3.7 V, which induces dendritic lithium growth at the anode side, resulting in a micro-short circuit through the electrolyte. Composite anodes of Li3PS4 glass+Li–Si alloy (Type 1) and Li3N+LiF+Li–Si alloy (Type 2) are also prepared for all-solid-state batteries (ASSBs) with LPS glass electrolyte and sulfur/LPS glass/carbon composite cathode. Using a three-electrode system, the anode and cathode potentials are separated, and their polarization resistances are individually traced. Even under high-cutoff-voltage conditions (3.7 V), Type 1 and 2 cells are stably cycled without voltage noise for >200 cycles. Although cathode polarization resistance drastically increases after 3.7 V charge owing to LPS oxidation, LPS redox behavior is fairly reversible upon discharge–charge unlike the non-composite alloy anode cell. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis reveals that the enhanced cyclability is attributed to uniform Li–Si alloying throughout the composite anode, providing more pathways for lithium ions even when these ions are over-supplied via LPS oxidation. These results imply that LPS-based cells can be reversibly cycled with LPS redox even under high-cutoff voltages, as long as non-uniform alloying (lithium dendrite growth) is prevented.

Operando Investigation of Silicon Anodes During Electrochemical Cycling in Li-ion Batteries.

Silicon (Si) is recognized as a promising anode material for next-generation anodes due to its high capacity. However, large volume expansion and active particle pulverization during cycling rapidly deteriorate the battery performance. The relationship between Si anode particle size and particle pulverization, and the structure evolution of Si particles during cycling is not well understood. In this study, a quantitative, time-resolved "operando" small angle X-ray scattering (SAXS) investigation into the morphological change of unwrapped and reduced graphene oxide (rGO) wrapped Si nanoparticles (Si@rGO) is conducted with respect to the operating voltage. The results provide a clear picture of Si particle size change and the role of nonrigid rGO in mitigating Si volume expansion and pulverization. Further, this study demonstrates the advantage of "operando" SAXS in electrochemical environments as compared to other approaches.

Insights into the SiO2 Stress Effect on the Electrochemical Performance of Si anode.

Silicon (Si) is regarded as the most potential anode material for next-generation lithium-ion batteries (LIBs). However, huge volume expansion hinders its commercial application. Here, a yolk-shell structural nitrogen-doped carbon coated Si@SiO2 is prepared by SiO2 template and HF etching method. The as-prepared composite exhibits superior cycling stability with a high reversible capacity of 577mA h g-1 at 1 A g-1 after 1000 cycles. The stress effect of SiO2 on stabilizing the electrochemical performance of Si anode is systematically investigated for the first time. In situ thickness measurement reveals that the volume expansion thickness of Si@SiO2 upon charge-discharge is obviously smaller than Si, demonstrating the electrode expansion can be effectively inhibited to improve the cyclability. The density functional theory (DFT) calculation further demonstrates the moderate young's modulus and enhanced hardness after SiO2 coating contribute significantly to the mechanical reinforcement of overall Si@SiO2@void@NC composite. Various post-cycling electrode analyses also address the positive effects of inner stress from the Si core on effectively relieving the damage to electrode structure, facilitating the formation of a more stable inorganic-rich solid electrolyte interphase (SEI) layer. This study provides new insights for mechanical stability and excellent electrochemical performance of Si-based anode materials.

Dynamic hydrogen bond cross-linking binder with self-healing chemistry enables high-performance silicon anode in lithium-ion batteries

The structure instability and cycling decay of silicon (Si) anode triggered by stress buildup hinder its practical application to next-generation high-energy–density lithium-ion batteries (LIBs). Herein, a cross-linking polymeric network as a self-healing binder for Si anode is developed by in situ polymerization of tannic acid (TA) and polyacrylic acid (PAA) binder labelled as TA-c-PAA. The branched TA as a physical cross-linker complexes with PAA main chains through abundant dynamic hydrogen bonds, endowing the cross-linking TA-c-PAA binder with unique self-healing property and strong adhesion for Si anode. Benefiting from the mechanical robust and hard adhesion, the Si@TA-c-PAA electrode exhibits high reversible specific capacities (3250 mAh/g at 0.05C (1C = 4000 mA g−1)), excellent rate capability (1599 mAh/g at 2C), and impressive cycling stability (1742 mAh/g at 0.25C after 450 cycles). After Ex situ morphology characterization, in situ swelling analysis, and finite element simulation, it is found that the TA-c-PAA binder allows the Si anode to dissipate stress and prevent pulverization during lithiation and delithiation, thus the hydrogen bonds among interpenetrating network may be adaptable to the stress intensity. Our work paves a new avenue for the design of efficient and cost-effective binders for next-generation Si anode in LIBs.

Facile Synthesis of 2D SiOx-3D Si Hybrid Anode Materials by Ca Modification Effect for Enhanced Lithium Storage Performance.

Al-Si dealloying method is widely used to prepare Si anode for alleviating the issues caused by a drastic volume change of Si-based anode. However, this method suffers from the problems of low Si powder yield (<20wt.% Si) and complicated cooling equipment due to the hindrance of large-size primary Si particles. Here, a new modification strategy to convert primary Si to 2D SiOx nanosheets by introducing a Ca modifier into Al-Si alloy melt is presented. The thermodynamics calculation shows that the primary Si is preferentially converted to CaAl2Si2 intermetallic compound in Al-Si-Ca alloy system. After the dealloying process, the CaAl2Si2 is further converted to 2D SiOx nanosheets, and eutectic Si is converted to 3D Si, thus obtaining the 2D SiOx-3D Si hybrid Si-based materials (HSiBM). Benefiting from the modification effect, the HSiBM anode shows a significantly improved electrochemical performance, which delivers a capacity retention of over 90% after 100 cycles and keeps 98.94% capacity after the rate test. This work exhibits an innovative approach to produce stable Si-based anode through Al-Si dealloying method with a high Si yield and without complicated rapid cooling techniques, which has a certain significance for the scalable production of Si-based anodes.