Microscopy and Microanalysis for Lithium-Ion Batteries

Cover
Half Title
Title Page
Copyright Page
Table of Contents
Preface
Acknowledgments
Editor
Contributors
Chapter 1 Lithium-Ion Batteries
1.1 Introduction
1.2 Origin of Li-Ion Batteries
1.3 History of Lithium-Ion Batteries
1.3.1 Brief History
1.3.2 Basic Structure of Lithium-Ion Batteries
1.3.3 Beyond Lithium-Ion Batteries
1.4 Cathode Materials for Lithium-Ion Batteries
1.4.1 Layered Cathodes
1.4.2 Spinel-Structured Cathode Materials
1.4.3 Polyanion Cathodes
1.4.4 Disordered Rock-Salt Cathodes
1.4.5 Conversion Cathode Materials
1.4.6 Sulfur and Oxygen
1.5 Anode Materials for Lithium-Ion Batteries
1.5.1 Intercalation Anodes
1.5.1.1 Carbon-Based Materials
1.5.1.2 Insertion-Type Transition Metal Oxide Anodes
1.5.2 Alloying Anodes
1.5.2.1 Si and Si-Based Compounds
1.5.2.2 Tin (Sn) and Sn-Based Compounds
1.5.3 Conversion Anodes
1.5.4 Metallic Li Anode
1.6 Electrolytes
1.6.1 Electrode/Electrolyte Interfaces
1.6.2 Organic Electrolytes
1.6.3 Aqueous Electrolytes
1.6.4 Ionic Liquids
1.6.5 Solid-State Electrolytes
1.7 Summary and Outlook
References
Chapter 2 Electron Microscopy for Advanced Battery Research
2.1 Basic Principle of Electron Microscopy (EM)
2.1.1 Interaction Between Electron and Specimen
2.1.2 EM System: Guns, Lens, Aberrations, and Resolutions
2.1.2.1 Electron Guns
2.1.2.2 The Lens of EM
2.1.2.3 The Aberrations in the EM
2.1.2.4 The Resolutions of EM Imaging
2.1.3 General Information From EMs
2.1.3.1 Information From SEM
2.1.3.2 Information From TEM
2.1.3.3 Information From Electron Diffraction
2.1.3.4 Information From EDS
2.1.3.5 Information From EELS
2.2 Scanning Electron Microscopy
2.2.1 General Information From SEM for Battery Materials and Interfaces
2.2.2 In Situ/Operando SEM: Heating and Biasing
2.2.3 Advanced SEM Integrated with Other Techniques, Such as Raman and SIMS
2.3 Focused Ion Beam
2.3.1 FIB for Cross-Section Imaging
2.3.2 FIB for 3D Morphology
2.3.3 FIB for Preparing Thin Samples for TEM
2.3.4 Cryogenic FIB for Beam-Sensitive Samples
2.4 Transmission Electron Microscopy (TEM)
2.4.1 Introduction of High-Resolution TEM, STEM, Diffraction, and EELS
2.4.1.1 High-Resolution TEM
2.4.1.2 Scanning TEM
2.4.1.3 Electron Energy Loss Spectroscopy
2.4.2 Atomic Structure: Bulk, Surface Construction, Coating, Doping, and Phase Transitions
2.4.2.1 Bulk Structure
2.4.2.2 Surface Construction
2.4.2.3 Coating Methods
2.4.2.4 Doping Methods
2.4.3 In Situ/Operando TEM: Biasing, Mechanical, and Heating
2.4.4 Cryo-TEM for Beam-Sensitive Samples: Li Metal, Solid Electrolyte Interphase (SEI), and Interfaces in Solid Batteries
2.5 Summary
2.5.1 Challenges and Issues Associated with the Higher Energy and Safer Batteries
2.5.2 Future Development of EMs
References
Chapter 3 Characterizing the Localized Electrochemical Phenomena in Li-Ion Batteries by Using SPM-Based Techniques
3.1 Introduction
3.2 Briefing Introduction of Relevant Scanning Probe Microscopy (SPM)-Based Techniques
3.2.1 Atomic Force Microscopy (AFM)
3.2.2 Surface-Strain-Based SPM Techniques
3.2.2.1 Dual AC Resonance Tracking
3.2.2.2 Band Excitation Technique
3.2.3 Conductive AFM
3.2.4 SPM-Based Techniques for Characterizing Mechanical Properties
3.3 Characterization of Electrodes Materials for Li-Ion Battery
3.3.1 In Situ and Ex Situ SPM Characterization
3.3.2 Current-Based SPM
3.3.3 Electrochemical Strain Microscopy Techniques
3.3.4 Characterization of Local Mechanical Properties for Li-Ion Battery Materials
3.4 Characterization of Solid Electrolyte for Li-Ion Battery
3.5 Conclusion Remarks
Acknowledgment
References
Chapter 4 Atom Probe Tomography
4.1 APT Analysis of Li-Ion Batteries
4.2 Introduction to APT
4.2.1 Technology Roadmap
4.2.2 Laser Pulsing
4.2.3 Spatial Resolution and Chemical Sensitivity
4.2.4 Working Principles
4.2.4.1 Field Evaporation
4.2.4.2 Ion Detection
4.2.4.3 Time-of-Flight Mass Spectrometry
4.2.5 Tomographic Reconstruction
4.3 Specimen Preparation
4.3.1 FIB-Based Lift-Out Method for Large Particles
4.3.2 Edge to Center Specimen Preparation for Large Particles
4.3.3 Methodologies for Nanoparticles
4.3.4 Sharpening and Cleaning
4.3.4.1 Sharpening
4.3.4.2 Low-Energy Ion Beam Cleaning
4.3.5 Cryogenic Vacuum Transfer to Atom Probe
4.3.6 A Word on the Data Acquisition Conditions
4.3.6.1 Base Temperature Considerations
4.3.6.2 Detection Rate
4.3.6.3 Laser Pulsing
4.3.6.4 Summary
4.4 Case Studies
4.4.1 Layered NMC Cathode Materials
4.4.1.1 Experimental
4.4.1.2 Mass-to-Charge Spectrum
4.4.1.3 Compositional Analysis of NMC 622
4.4.1.4 NMC622 & 811 Comparison
4.4.1.5 Li Distribution and Concentration Profiles
4.4.1.6 Interface Analysis of Primary Particles
4.4.1.7 Summary
4.4.2 Charge/Discharge Cycles
4.4.2.1 Li Migration and Transition Metal Loss
4.4.2.2 Evolution of Li Concentration Gradient
4.4.2.3 Summary
4.4.3 Spinel LiMn[sub(2)]O[sub(4)] Cathode Materials
4.4.3.1 Atomic Resolution
4.4.3.2 In Situ Li Deintercalation
4.4.3.3 Summary
4.5 Correlative and Combined Methods
4.6 Future Development
4.7 Concluding Remarks
Acknowledgment
References
Chapter 5 In Situ X-Ray Diffraction Studies on Lithium-Ion and Beyond Lithium-Ion Batteries
5.1 Introduction
5.2 Operando Studies on Cathode Materials
5.3 Operando Studies on Anode Materials
5.4 Beyond Lithium-Ion Batteries
5.4.1 Lithium-Sulfur Batteries
5.4.2 Sodium-Ion Batteries
5.5 Summary and Outlook
References
Chapter 6 ICP-Based Techniques for LIBs Characterization
6.1 Basic Principles of ICP-Based Techniques
6.1.1 Sample Preparation and Introduction
6.1.2 Excitation and Ionization
6.1.3 Detection
6.1.3.1 ICP-OES
6.1.3.2 ICP-MS
6.2 ICP-MS and ICP-OES in LIB Research
6.2.1 Bulk Analysis
6.2.2 (Nano)-Particle Analysis
6.3 Combination with Laser Ablation (Surface Analysis)
6.3.1 Basic Principles and Background
6.3.2 Application
6.4 Combination with Chromatographic Techniques (Speciation Analysis)
6.4.1 Basic Principles and Background
6.4.2 Application
6.5 Summary and Outlook
6.5.1 Next-Generation Batteries
6.5.2 Outlook on Future Instrumentation
References
Chapter 7 Secondary Ion Mass Spectrometry
7.1 Introduction
7.2 Principles of the Technique
7.2.1 Basic Phenomena
7.2.2 An Overview of Different Instruments
7.3 Challenges and Pitfalls of SIMS Characterization of LIBs
7.3.1 Matrix Effect
7.3.2 Sputtering Rate
7.3.3 Mass Spectrum Analysis
7.3.4 Mixing Effect
7.3.5 Lithium Mobility
7.3.6 Non-Planar Surface
7.3.7 Battery Sample Extraction and Transfer
7.4 Lithium Distribution Analysis
7.4.1 Isotopically Labeled Materials
7.4.2 ToF-SIMS FIB/SEM Multimodal Microscopy
7.4.3 Operando Measurements
7.5 Electrode Materials Characterization
7.5.1 The Composition of Electrodes
7.5.2 Coatings
7.5.3 Degradation Analysis
7.6 Formation of Solid Electrolyte Interface
7.7 Summary
References
Chapter 8 Nuclear Magnetic Resonance Microscopy: Atom to Micrometer
8.1 Introduction
8.2 Principle of NMR
8.3 NMR of Cathode Materials
8.4 NMR of Anode Materials
8.5 NMR of Electrolytes in Batteries
8.6 NMR of Solid Electrolyte Interface
8.7 Ex Situ and in Situ NMR
8.8 Nuclear Magnetic Resonance Imaging
8.9 Summary and Perspectives
Acknowledgments
Abbreviations
References
Chapter 9 Differential Electrochemical Mass Spectrometry for Lithium-Ion Batteries
9.1 A Brief History
9.1.1 Membrane Inlet
9.1.2 Carrier Gas Inlet
9.1.3 Leak Valve Inlet
9.2 Basic Knowledge and Experimental Setup
9.2.1 Electrochemical Cell
9.2.2 Carrier Gas Inlet System
9.2.3 Mass Spectrometer
9.2.4 Electrochemical Method
9.2.5 Data Analysis
9.3 Anode
9.3.1 Graphite
9.3.2 Lithium
9.3.3 Silicon
9.4 Cathode
9.4.1 Lattice Oxygen
9.4.2 Surface Impurity
9.4.3 Electrolyte Chemistry
9.5 Cross-Talk of Gas in Full Battery
9.6 Summary
References
Chapter 10 Thermal Analysis of Li-Ion Batteries
10.1 Fundamental Principles of Heat Transfer Analysis
10.1.1 Heat Transfer Mechanisms
10.1.1.1 Conduction Heat Transfer
10.1.1.2 Convection Heat Transfer
10.1.1.3 Radiation Heat Transfer
10.1.1.4 Multi-Mode Heat Transfer
10.1.2 Material Properties
10.1.3 Heat Transfer Analysis Methods
10.1.3.1 Analytical Methods
10.1.3.2 Numerical Methods
10.1.4 Coupling Between Heat Transfer and Other Physical Phenomena
10.2 Li-Ion Cell as a Thermal System
10.2.1 Heat Generation
10.2.2 Key Modes of Heat Transfer in a Cell
10.2.3 Boundary Conditions
10.2.4 Thermal Properties
10.2.5 Thermal Management
10.3 Modeling Frameworks and Governing Equations
10.3.1 0D Lumped Capacitance Models
10.3.2 Spatially Resolved Framework
10.4 Solution Methods for Governing Energy Equations
10.4.1 Analytical Heat Transfer Tools for Li-Ion Cells
10.4.2 Iterative Semi-Analytical Solutions
10.4.3 Numerical Analysis Tools
10.4.3.1 Finite Difference Method (FDM)
10.4.3.2 Finite Element Method (FEM)
10.4.3.3 Finite Volume Method (FVM)
10.5 Thermal Runaway Modeling
10.5.1 Introduction
10.5.2 Numerical Heat Transfer Simulation for Thermal Runaway
10.5.3 Analytical Heat Transfer Modeling of Thermal Runaway
References
Chapter 11 Electrochemical Impedance Spectroscopy
11.1 Introduction
11.2 Principle and Process of EIS Method
11.2.1 Principle of EIS
11.2.2 Stages, Steps, and Iterations in EIS Study
11.2.2.1 Stage 1: EIS Measurement to Acquire Repeatable and Valid Spectrum
11.2.2.2 Stage 2: Interpretation to Identify and Understand Features in the Spectrum
11.2.2.3 Stage 3: Validation From Non-EIS Techniques
11.3 Characterizing LIB Using EIS
11.3.1 EIS Measurement of LIB
11.3.1.1 Measurement Setup
11.3.1.2 Instrument Settings
11.3.1.3 Procedure and Sequence
11.3.2 EIS Features of LIB
11.3.2.1 Major EIS Features of LIB
11.3.2.2 Minor EIS Features of One Electrode
11.3.3 EIS Models of LIB
11.3.3.1 EEC Models
11.3.3.2 Analytic Models
11.3.3.3 Numerical Modeling
11.3.4 Interpretation and Validation of EIS for LIB
11.3.4.1 Interpretation
11.3.4.2 Validation
11.4 Exemplary EIS Application Across the Lifetime of LIB
11.5 Conclusion
Acknowledgment
Abbreviations
Notes
References
Chapter 12 Synchrotron X-Ray and Neutron Techniques
12.1 Basic Principle of Advanced X-Ray and Neutron Techniques
12.1.1 Interactions of X-Rays with Matter
12.1.1.1 What is an X-Ray?
12.1.1.2 General Description of the Interactions
12.1.2 Interactions of Neutrons with Matter
12.1.2.1 What is a Neutron?
12.1.2.2 General Description of the Interactions
12.1.3 The Needs of X-Ray and Neutron Techniques
12.2 Elastic Scattering Techniques
12.2.1 XRD
12.2.1.1 Time-Resolved in Situ XRD
12.2.1.2 Microbeam XRD
12.2.1.3 EDXRD
12.2.2 Neutron Diffraction
12.2.3 Small-Angle X-Ray Scattering
12.2.4 Small-Angle Neutron Scattering
12.2.5 Pair Distribution Function
12.2.6 Neutron Pair Distribution Function
12.3 X-Ray Absorption and Emission Spectroscopies
12.3.1 Overview of XAS, XES and RIXS
12.3.1.1 XES
12.3.1.2 RIXS
12.3.1.3 Comparison of Hard X-Ray and Soft X-Ray Absorption
12.3.2 Applications
12.3.2.1 Redox Reactions Through XAS, XES and RIXS
12.3.2.2 Probe of Local Structure
12.3.2.3 Study of Surface Chemistry
12.4 Neutron Absorption and Inelastic Scattering
12.4.1 NDP
12.4.2 INS and QENS
12.5 X-Ray and Neutron Imaging
12.5.1 Contrast Mechanism
12.5.2 Imaging Methods
12.5.2.1 TXM
12.5.2.2 STXM
12.5.2.3 X-Ray CT
12.5.2.4 Neutron Imaging
12.6 Perspective
Acknowledgments
References
Index