Analysing Lithium Ion Batteries with XPS & Auger

Characterising degradation mechanisms in lithium-ion batteries requires both bulk and surface characterisation. XPS and Auger are useful techniques for analysing surfaces:

  • XPS – Chemical analysis of surface films on electrodes
  • Auger – Nanoscale analysis of electrode surfaces

Blue Scientific is the official UK distributor for Physical Electronics. If you have any questions, please get in touch.

XPS and Auger instruments

 Contact us on +44 (0)1223 422 269 or info@blue-scientific.com


  

Surface Films on Electrodes

Charge-discharge cycling and storage can cause surface films to form on electrodes. These surface films play a critical role in limiting battery performance and lifetime. With XPS you can characterise cycled Li ion battery electrodes for battery development and to improve performance.

Air Sensitive Li ion Battery Materials

Many Li ion battery materials are air sensitive. They must be handled in a controlled environment such as a glove box. A transfer vessel is also necessary to transfer the sample from a glove box to instrument safely.

Battery Testing with XPS at Argonne

PHI VersaProbe at Argonne National Laboratory, housed in a glove box so samples can be prepared and analysed without exposure to air.

Analysing Battery Degradation with XPS

Materials from from used and previously tested battery cells can be dissected and analysed to identify what caused the degradation. An ideal instrument for this work is the PHI VersaProbe II (XPS), which can be housed in a large glove box to protect the air-sensitive materials. This is the only way to ensure that changes in battery chemistry are caused by electrochemical operations and not contamination from the surrounding atmosphere.

The VersaProbe provides information about the electronic structure of materials, highlighting the physical and physical changes that happened as the battery aged.

Example: TOF-SIMS Analysis of a Li Ion Battery

In this example, electrode surfaces were characterised after 3 charge-discharge cycles.

Electrode materials:

  • Anode: Natural graphite particles with PVDF binder
    • Graphite – Binder ratio 9:1
  • Cathode: Li metal

The electrode samples were analysed with a PHI nanoTOF parallel imaging MS/MS system. They were transferred from a glove box to the instrument with an inert atmosphere transfer vessel.

  • Au3++ analysis beam for spectroscopy
  • Ar2500+ beam for sputtering

Precipitates were visible on the rough anode surfaces after the charge-discharge cycles, and TOF-SIMS was used to analyse them:

SEM image of precipitates on battery anode

Precipitates on anode surface. Sample courtesy of Professor Komaba, Tokyo University of Science.

 

Analysing battery anode surface

Analysing the anode surface with TOF-SIMS highlights changes in the molecular composition after the charge-discharge cycles. Sample courtesy of Prof. Komaba, Tokyo University of Science.

 

Imaging battery anode surface

High spatial resolution images of the anode after the charge-discharge test. The PHI nanoTOF is ideal for imaging this type of rough surface. Sample courtesy of Prof. Komaba, Tokyo University of Science.

 

Sputter tests

Gas cluster ion beam depth profile of the SEI layer on the anode after the charge-discharge test. Sample courtesy of Prof. Komaba, Tokyo University of Science.

Systems for Battery Analysis

PHI VersaProbe III

PHI VersaProbe III

PHI VersaProbe III and Quantera II

Scanning XPS Microprobes

  • Quantitative analysis of the chemical composition of surfaces
  • Superior micro-area XPS performance
  • Sample transfer vessel available

More about the VersaProbe III
More about the Quantera II

PHI 710 Scanning Auger Nanoprobe

PHI 710

Scanning Auger NanoProbe

  • Nanoscale surface characterisation
  • Superior 2D imaging and analysis of rough surfaces in Li ion batteries, with coaxial analyser / electron gun geometry
  • Sample transfer vessel available

More about the PHI 710

PHI nanoTOF II TOF-SIMS spectrometer

PHI nanoTOF

Parallel Imaging MS/MS

  • Molecular structure information
  • Detect trace elements
  • 2D and 3D imaging
  • Superior sensitivity for molecular spectroscopy and molecular imaging
  • Image rough electrode surfaces with TRIFT spectrometer
  • Sample transfer vessel available

More about the PHI nanoTOF

 

Publications

These publications are examples of how XPS and Auger have been used in battery research. If you have any questions or if you’d like to know more about these technologies, please get in touch.

PHI VersaProbe

PHI FE Auger

  • Study of lithiation mechanisms in silicon electrodes by Auger Electron Spectroscopy
    E. Radvanyi, E. De Vito, W. Porcher, J. Danet, P. Desbois, J.F. Colin and S.J. Si Larbi; CEA LITEN Grenoble
    J. Mater. Chem. A, 2013,1, 4956-4965; DOI: 10.1039/C3TA10212B

PHI nanoTOF

  • Electrochemical Properties of Polyaniline-Coated Li-Rich Nickel Manganese Oxide and Role of Polyaniline Coating Layer
    Dae-hyun Cho,a Hitoshi Yashiro,b Yang-Kook Sun,c, d and Seung-Taek Myunga
    aDepartment of Nano Science and Technology, Sejong University, Gwangjin-gu, Seoul 143-747, South Korea
    bDepartment of Chemical Engineering, Iwate University, Ueda, Morioka, Iwate 020-8551, Japan
    cDepartment of Energy Engineering, Hanyang University, Seoul 133-791, South Korea
    dDepartment of Chemistry, King Abdulaziz University, Jeddah 21589, Saudi Arabia
    Journal of The Electrochemical Society, 161 (1) A142-A148 (2014)

XPS and Auger instruments

More Technologies for Battery Research

 Contact us on +44 (0)1223 422 269 or info@blue-scientific.com