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Table of contents
1 Redox flow battery technology
1.1 The energy storage challenge
1.2 The Redox Flow Battery solution
1.2.1 Concept and advantages
1.2.2 Existing chemistries
1.2.3 Kemiwatt’s industrial challenge and opportunity
1.3 General understanding of the Redox Flow Battery
1.3.1 Fundamentals
1.3.2 Modeling
1.3.3 Analytical platforms
1.3.4 Internal cell instrumentation
1.4 Methodology of the PhD study
2 Diagnostic tools
2.1 Materials and pretreatments
2.1.1 Electrolytes
2.1.2 Standard test cell
2.2 Battery tests
2.2.1 Assembly
2.2.2 Cycling
2.2.3 Polarization curves
2.2.4 Electrochemical impedance spectroscopy
2.3 Symmetric cell
2.3.1 Principle
2.3.2 Impedance variation with SOC
2.4 Segmented cell
2.4.1 Internal design
2.4.2 Segmentation and local currents
2.4.3 Challenges of local potential probing
2.4.4 Assessment of the local RHE
2.4.5 Test bed
2.5 Conclusion
3 Separate characterization of the components
3.1 Electrochemical analysis
3.1.1 Electrolytes and assumptions
3.1.2 Electrochemical cell
3.1.3 Potential window and reversibility of a redox couple
3.1.4 RDE voltammetry
3.1.5 Cyclic voltammetry
3.1.6 Discussion of the results
3.2 Physico-chemical electrolyte properties
3.2.1 Conductivity
3.2.2 Viscosity
3.2.3 Material compatibility and photodegradation of catholyte
3.3 Membrane characterization
3.3.1 Membrane pretreatments: FTIR-ATR study
3.3.2 Membrane affinity with solutions
3.4 Porous electrode characterization
3.4.1 Structural observation
3.4.2 NMR analysis
3.4.3 Comparison of two materials by blocking electrode model
3.5 Conclusion
4 Half-cell characterization
4.1 Stationary porous electrode model
4.1.1 Fundamental relations
4.1.2 Analytical expression with infinite electronic conductivity
4.1.3 Electrode impedance
4.1.4 Electrode impedance in blocking electrode conditions
4.2 Global impedance of the symmetric cell: methodology
4.3 Catholyte symmetric cell
4.3.1 Effect of the light exposure of the catholyte on cell impedance
4.3.2 Effect of the electrode material on cell impedance
4.3.3 Rcell vs SOC curves: Identification of the degradation mechanisms
4.4 Anolyte symmetric cell
4.4.1 Impedance evolution in circulation
4.4.2 Analysis of the cell overcharge
4.4.3 Rcell vs SOC curves
4.5 Conclusion
5 Full cell study
5.1 Standard cycling
5.1.1 Comparison standard / segmented cell
5.1.2 Parameters evolution during cycling
5.2 Influence of operating conditions
5.2.1 Strategy to investigate internal heterogeneity of battery operation
5.2.2 Current density
5.2.3 Flow rate
5.2.4 Temperature
5.3 Summary of the parameter study
5.3.1 Comparison of the impact of the three parameters
5.3.2 Development of an operational map
6 Industrial cell study
6.1 Hydraulic study
6.1.1 Model development
6.1.2 Computational results
6.1.3 Clear flow cell experiment
6.2 Flow rate optimization
6.2.1 Strategy
6.2.2 Results
6.3 Conclusion
Conclusions
Appendices
Bibliography
