ToF-SIMS in battery research: Advantages, limitations, and best practices

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful analytical technique whose application has great potential for battery research and that today is not used at its full potential. The goal of this article is to encourage battery researchers to add ToF-SIMS to their research toolbox and to incite ToF-SIMS experts to collaborate more strongly with battery researchers. It is, therefore, addressed to both new and experienced ToF-SIMS operators. First, an introduction to the analysis technique is given, in which the fundamental operating principle and the most common measurement modes are briefly explained. Additionally, we provide information on different machines commercially available. Based on this knowledge, we discuss the suitability of ToF-SIMS for battery research and highlight its method-specific characteristics for corresponding analytical tasks. We show that the high sensitivity of this analytical method (fractions < 10 ppm are detectable) combined with high flexibility for all analyzable materials (organic, inorganic, and hybrid) and sample formats (powders, thin films, electrodes, etc.) make ToF-SIMS particularly relevant for battery research, where the chemical nature of interfaces/interphases and traces of reaction products are of paramount importance. As practical guidance, we introduce and discuss the most common pitfalls when using ToF-SIMS for battery research and give hints on how they could be avoided or minimized. A major goal of this article is to review best practices, focusing on improving data quality, avoiding artifacts, and improving reproducibility.

[1]  J. Janek,et al.  Challenges in speeding up solid-state battery development , 2023, Nature Energy.

[2]  Samuel J. Cooper,et al.  MicroLib: A library of 3D microstructures generated from 2D micrographs using SliceGAN , 2022, Scientific Data.

[3]  J. Janek,et al.  In Situ Investigation of Lithium Metal–Solid Electrolyte Anode Interfaces with ToF‐SIMS , 2022, Advanced Materials Interfaces.

[4]  J. Sann,et al.  Storage of Lithium Metal: The Role of the Native Passivation Layer for the Anode Interface Resistance in Solid State Batteries , 2021, ACS Applied Energy Materials.

[5]  J. Tu,et al.  A Brief Review on Solid Electrolyte Interphase Composition Characterization Technology for Lithium Metal Batteries: Challenges and Perspectives , 2021, The Journal of Physical Chemistry C.

[6]  J. Sann,et al.  Analyzing Nanometer-Thin Cathode Particle Coatings for Lithium-Ion Batteries—The Example of TiO2 on NCM622 , 2021, ACS Applied Energy Materials.

[7]  Yan Yao,et al.  Microstructure engineering of solid-state composite cathode via solvent-assisted processing , 2021, Joule.

[8]  J. Kilner,et al.  Experimental determination of Li diffusivity in LLZO using isotopic exchange and FIB-SIMS , 2021 .

[9]  Liang Li,et al.  Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn2S4 Photoanode for Enhanced Photoelectrochemical Water Splitting , 2021, Advanced Energy Materials.

[10]  Felix H. Richter,et al.  Influence of Crystallinity of Lithium Thiophosphate Solid Electrolytes on the Performance of Solid‐State Batteries , 2021, Advanced Energy Materials.

[11]  Steve Kench,et al.  Generating three-dimensional structures from a two-dimensional slice with generative adversarial network-based dimensionality expansion , 2021, Nature Machine Intelligence.

[12]  J. Sann,et al.  The Working Principle of a Li2CO3/LiNbO3 Coating on NCM for Thiophosphate-Based All-Solid-State Batteries , 2021 .

[13]  C. Delacourt,et al.  3D Quantification of Microstructural Properties of LiNi0.5Mn0.3Co0.2O2 High‐Energy Density Electrodes by X‐Ray Holographic Nano‐Tomography , 2021, Advanced Energy Materials.

[14]  E. Ivers-Tiffée,et al.  Virtual Electrode Design for Lithium‐Ion Battery Cathodes , 2021, Energy Technology.

[15]  Yuki Nomura,et al.  Visualizing Lithium Distribution and Degradation of Composite Electrodes in Sulfide-based All-Solid-State Batteries Using Operando Time-of-Flight Secondary Ion Mass Spectrometry. , 2020, ACS applied materials & interfaces.

[16]  G. Hinds,et al.  Microstructural Evolution of Battery Electrodes During Calendering , 2020, Joule.

[17]  Wangda Li,et al.  Long-Term Cyclability of NCM-811 at High Voltages in Lithium-Ion Batteries: an In-Depth Diagnostic Study , 2020 .

[18]  Felix H. Richter,et al.  Influence of Carbon Additives on the Decomposition Pathways in Cathodes of Lithium Thiophosphate-Based All-Solid-State Batteries , 2020 .

[19]  Evan M. Erickson,et al.  Insights into the Cathode-electrolyte Interphases of High-energy-density Cathodes in Lithium-ion Batteries. , 2020, ACS applied materials & interfaces.

[20]  Victor E. Brunini,et al.  Electrode Mesoscale as a Collection of Particles: Coupled Electrochemical and Mechanical Analysis of NMC Cathodes , 2020 .

[21]  Chao Di,et al.  U1 snRNP regulates cancer cell migration and invasion in vitro , 2020, Nature Communications.

[22]  Alejandro A. Franco,et al.  Lithium ion battery electrodes predicted from manufacturing simulations: Assessing the impact of the carbon-binder spatial location on the electrochemical performance , 2019 .

[23]  J. Janek,et al.  The Role of Intragranular Nanopores in Capacity Fade of Nickel-Rich Layered Li(Ni1-x-yCoxMny)O2 Cathode Materials. , 2019, ACS nano.

[24]  E. Ivers-Tiffée,et al.  Microstructural feature analysis of commercial Li-ion battery cathodes by focused ion beam tomography , 2019, Journal of Power Sources.

[25]  J. Sann,et al.  Visualization of the Interfacial Decomposition of Composite Cathodes in Argyrodite-Based All-Solid-State Batteries Using Time-of-Flight Secondary-Ion Mass Spectrometry , 2019, Chemistry of Materials.

[26]  M. Winter,et al.  Before Li Ion Batteries. , 2018, Chemical reviews.

[27]  Wangda Li,et al.  Extending the Service Life of High‐Ni Layered Oxides by Tuning the Electrode–Electrolyte Interphase , 2018, Advanced Energy Materials.

[28]  J. Janek,et al.  Molecular Surface Modification of NCM622 Cathode Material Using Organophosphates for Improved Li-Ion Battery Full-Cells. , 2018, ACS applied materials & interfaces.

[29]  A. Dolocan,et al.  Modified High-Nickel Cathodes with Stable Surface Chemistry Against Ambient Air for Lithium-Ion Batteries. , 2018, Angewandte Chemie.

[30]  Wangda Li,et al.  Mn versus Al in Layered Oxide Cathodes in Lithium‐Ion Batteries: A Comprehensive Evaluation on Long‐Term Cyclability , 2018 .

[31]  J. Goodenough.  How we made the Li-ion rechargeable battery , 2018 .

[32]  P. Pietsch,et al.  X-Ray Tomography for Lithium Ion Battery Research: A Practical Guide , 2017 .

[33]  Wangda Li,et al.  Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover. , 2017, ACS nano.

[34]  Wangda Li,et al.  Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries , 2017, Nature Communications.

[35]  J. Zakel,et al.  Large O2 Cluster Ions as Sputter Beam for ToF-SIMS Depth Profiling of Alkali Metals in Thin SiO2 Films. , 2017, Analytical chemistry.

[36]  Seokgwang Doo,et al.  The effect of diamond-like carbon coating on LiNi0.8Co0.15Al0.05O2 particles for all solid-state lithium-ion batteries based on Li2S–P2S5 glass-ceramics , 2016 .

[37]  D. Heller,et al.  Time-of-flight secondary ion mass spectrometry as a screening method for the identification of degradation products in lithium-ion batteries—A multivariate data analysis approach , 2016 .

[38]  D. Wheeler,et al.  Three‐Phase Multiscale Modeling of a LiCoO2 Cathode: Combining the Advantages of FIB–SEM Imaging and X‐Ray Tomography , 2015 .

[39]  K. Stevenson,et al.  Role of surface oxides in the formation of solid-electrolyte interphases at silicon electrodes for lithium-ion batteries. , 2014, ACS applied materials & interfaces.

[40]  David G Castner,et al.  Exploring the surface sensitivity of TOF-secondary ion mass spectrometry by measuring the implantation and sampling depths of Bi(n) and C60 ions in organic films. , 2012, Analytical chemistry.

[41]  Emilie Bekaert,et al.  Review—Post-Mortem Analysis of Aged Lithium-Ion Batteries: Disassembly Methodology and Physico-Chemical Analysis Techniques , 2016 .