Exploring the Promise of Multifunctional "Zintl-Phase-Forming" Electrolytes for Si-Based Full Cells.

Li-M-Si ternary Zintl phases have gained attention recently due to their high structural stability, which can improve the cycling stability compared to a bulk Si electrode. Adding multivalent cation salts (such as Mg2+ and Ca2+) in the electrolyte was proven to be a simple way to form Li-M-Si ternary phases in situ in Si-based Li-ion cells. To explore the promise of Zintl-phase-forming electrolytes, we systematically investigated their application in pouch cells via electrochemical and multiscale postmortem analysis. The introduction of multivalent cations, such as Mg2+, during charging can form LixMySi ternary phases. They can stabilize Si anions and reduce side reactions with electrolyte, improving the bulk stability. More importantly, Mg2+ and Ca2+ incorporate into interfacial side reactions and generate inorganic-rich solid-electrolyte interphase, thus enhancing the interfacial stability. Therefore, the full cells with Zintl-phase-forming electrolytes achieve higher capacity retentions at the C/3 rate after 100 cycles, compared to a baseline electrolyte. Additionally, strategies for mitigating the electrode-level fractures of Si were evaluated to make the best use of Zintl-phase-forming electrolytes. This work highlights the significance of synergistic impact of multifunctional additives to stabilize both bulk and interface chemistry in high-energy Si anode materials for Li-ion batteries.

[1]  I. Bloom,et al.  Extreme Fast Charging: Effect of Positive Electrode Material on Crosstalk , 2022, Journal of The Electrochemical Society.

[2]  Andrew M. Colclasure,et al.  Critical Evaluation of Potentiostatic Holds as Accelerated Predictors of Capacity Fade during Calendar Aging , 2022, Journal of The Electrochemical Society.

[3]  D. Abraham,et al.  Examining Effects of Negative to Positive Capacity Ratio in Three-Electrode Lithium-Ion Cells with Layered Oxide Cathode and Si Anode , 2022, ACS Applied Energy Materials.

[4]  Zhengcheng Zhang,et al.  Enabling Non-Carbonate Electrolytes for Silicon Anode Batteries Using Fluoroethylene Carbonate , 2022, Journal of The Electrochemical Society.

[5]  I. Bloom,et al.  Understanding the Effect of Cathode Composition on the Interface and Crosstalk in NMC/Si Full Cells. , 2022, ACS applied materials & interfaces.

[6]  I. Bloom,et al.  Evaluating the roles of electrolyte components on the passivation of silicon anodes , 2022, Journal of Power Sources.

[7]  Zhengcheng Zhang,et al.  Enabling Silicon Anodes with Novel Isosorbide-Based Electrolytes , 2022, ACS Energy Letters.

[8]  I. Bloom,et al.  Chemical Interplay of Silicon and Graphite in a Composite Electrode in SEI Formation. , 2021, ACS applied materials & interfaces.

[9]  Liquan Chen,et al.  Interplay between solid-electrolyte interphase and (in)active LixSi in silicon anode , 2021, Cell Reports Physical Science.

[10]  Weimin Zhao,et al.  Graphene mitigated fracture and interfacial delamination of silicon film anodes through modulating the stress generation and development , 2021, Nanotechnology.

[11]  G. G. Eshetu,et al.  Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes , 2021, Nature Communications.

[12]  K. Persson,et al.  Silicon Anodes with Improved Calendar Life Enabled By Multivalent Additives , 2021, Advanced Energy Materials.

[13]  Zhengcheng Zhang,et al.  Engineering the Si Anode Interface via Particle Surface Modification: Embedded Organic Carbonates Lead to Enhanced Performance , 2021, ACS Applied Energy Materials.

[14]  James A. Gilbert,et al.  Investigating Ternary Li–Mg–Si Zintl Phase Formation and Evolution for Si Anodes in Li-Ion Batteries with Mg(TFSI)2 Electrolyte Additive , 2021, Chemistry of Materials.

[15]  I. Bloom,et al.  Effect of temperature on capacity fade in silicon-rich anodes , 2021 .

[16]  M. Winter,et al.  Case study of N-carboxyanhydrides in silicon-based lithium ion cells as a guideline for systematic electrolyte additive research , 2021 .

[17]  I. Bloom,et al.  Review—The Lithiation/Delithiation Behavior of Si-Based Electrodes: A Connection between Electrochemistry and Mechanics , 2021 .

[18]  Zhengcheng Zhang,et al.  Chemical Switch Enabled Autonomous Two-Stage Crosslinking Polymeric Binder for High Performance Silicon Anodes , 2021, Journal of Materials Chemistry A.

[19]  I. Bloom,et al.  Effect of cathode on crosstalk in Si-based lithium-ion cells , 2021, Journal of Materials Chemistry A.

[20]  C. Stetson,et al.  Improving Interface Stability of Si Anodes by Mg Coating in Li-Ion Batteries , 2020 .

[21]  Zhengcheng Zhang,et al.  Stabilized Electrode/Electrolyte Interphase by a Saturated Ionic Liquid Electrolyte for High-Voltage NMC532/Si-Graphite Cells. , 2020, ACS applied materials & interfaces.

[22]  G. Veith,et al.  Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers , 2020 .

[23]  L. Monconduit,et al.  Si and Ge-Based Anode Materials for Li-, Na-, and K-Ion Batteries: A Perspective from Structure to Electrochemical Mechanism. , 2020, Small.

[24]  Jaephil Cho,et al.  Integration of Graphite and Silicon Anodes for the Commercialization of High-Energy Lithium-Ion Batteries. , 2020, Angewandte Chemie.

[25]  Michael A. Danzer,et al.  Effects of Mechanical Compression on the Aging and the Expansion Behavior of Si/C-Composite|NMC811 in Different Lithium-Ion Battery Cell Formats , 2019, Journal of The Electrochemical Society.

[26]  Yang-Tse Cheng,et al.  Effects of polymeric binders on the cracking behavior of silicon composite electrodes during electrochemical cycling , 2019, Journal of Power Sources.

[27]  J. Vaughey,et al.  Using Mixed Salt Electrolytes to Stabilize Silicon Anodes for Lithium-Ion Batteries via In situ Formation of Li-M-Si Ternaries (M=Mg, Zn, Al, Ca). , 2019, ACS applied materials & interfaces.

[28]  G. G. Eshetu,et al.  Confronting the Challenges of Next-Generation Silicon Anode-Based Lithium-Ion Batteries: Role of Designer Electrolyte Additives and Polymeric Binders. , 2019, ChemSusChem.

[29]  Lysander De Sutter,et al.  Analysis of the effect of applying external mechanical pressure on next generation silicon alloy lithium-ion cells , 2019, Electrochimica Acta.

[30]  J. Dahn,et al.  LiPO2F2 as an Electrolyte Additive in Li[Ni0.5Mn0.3Co0.2]O2/Graphite Pouch Cells , 2018 .

[31]  James A. Gilbert,et al.  Capacity Fade and Its Mitigation in Li-Ion Cells with Silicon-Graphite Electrodes , 2017 .

[32]  Wenquan Lu,et al.  Silicon Nanoparticles: Stability in Aqueous Slurries and the Optimization of the Oxide Layer Thickness for Optimal Electrochemical Performance. , 2017, ACS applied materials & interfaces.

[33]  Jaephil Cho,et al.  Confronting Issues of the Practical Implementation of Si Anode in High-Energy Lithium-Ion Batteries , 2017 .

[34]  Jeff Dahn,et al.  Volume, Pressure and Thickness Evolution of Li-Ion Pouch Cells with Silicon-Composite Negative Electrodes , 2017 .

[35]  Daniel P. Abraham,et al.  Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes , 2017 .

[36]  K. Komvopoulos,et al.  Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries , 2016, Nature Communications.

[37]  Matthew C. Dixon,et al.  Quantification of the Mass and Viscoelasticity of Interfacial Films on Tin Anodes Using EQCM-D. , 2015, ACS applied materials & interfaces.

[38]  L. Trahey,et al.  Interfacial study of the role of SiO 2 on Si anodes using electrochemical quartz crystal microbalance , 2015 .

[39]  G. Veith,et al.  Direct measurement of the chemical reactivity of silicon electrodes with LiPF6-based battery electrolytes. , 2014, Chemical communications.

[40]  Yi Cui,et al.  Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control. , 2012, Nature nanotechnology.

[41]  Fredrik J. Lindgren,et al.  Nanosilicon Electrodes for Lithium-Ion Batteries: Interfacial Mechanisms Studied by Hard and Soft X-ray Photoelectron Spectroscopy , 2012 .

[42]  Candace K. Chan,et al.  High-performance lithium battery anodes using silicon nanowires. , 2008, Nature nanotechnology.

[43]  Margret Wohlfahrt-Mehrens,et al.  A room temperature study of the binary lithium–silicon and the ternary lithium–chromium–silicon system for use in rechargeable lithium batteries , 1999 .