Monitoring of lithium-ion batteries is of critical importance in electric vehicle applications in order to manage the operational condition of the cells. Measurements on a vehicle often involve current, voltage and temperature which enable in-situ diagnostic techniques. This paper presents a novel diagnostic technique, termed differential thermal voltammetry, which is capable of monitoring the state of the battery using voltage and temperature measurements in galvanostatic operating modes. This tracks battery degradation through phase transitions, and the resulting entropic heat, occurring in the electrodes. Experiments to monitor battery degradation using the new technique are compared with a pseudo-2D cell model. Results show that the differential thermal voltammetry technique provides information comparable to that of slow rate cyclic voltammetry at shorter timescale and with load conditions easier to replicate in a vehicle.
Accelerated ageing of lithium-ion cells under various storage/loading conditions. Degradation analysis was performed using various in-situ diagnosis methods. Differential thermal voltammetry (DTV) suitable for electric vehicle application. State-of-health estimation through quantitative analyses of DTV peak evolution.
AUTHOR E-MAIL ADDRESSYu Merla -yu.merla09@imperial.ac.uk Billy Wu -billy.wu@imperial.ac.uk Vladimir Yufit -v.yufit@imperial.ac.uk Nigel P. Brandon -n.brandon@imperial.ac.uk Ricardo F. Martinez-Botas -r.botas@imperial.ac.uk Gregory J. Offer -gregory.offer@imperial.ac.uk ABSTRACT Understanding and tracking battery degradation mechanisms and adapting its operation have become a necessity in order to enhance battery durability. A novel use of differential thermal voltammetry (DTV) is presented as an in-situ state-of-health (SOH) estimator for lithium-ion batteries.Accelerated ageing experiments were carried on 5Ah commercial lithium-ion polymer cells operated and stored at different temperature and loading conditions. The cells were analysed regularly with various existing in-situ diagnosis methods and the novel DTV technique to determine their SOH. The diagnosis results were used collectively to elaborate the degradation mechanisms inside the cells. The DTV spectra were decoupled into individual peaks, which each represent particular phases in the negative and positive electrode combined. The peak parameters were used to quantitatively analyse the battery SOH.
2A different cell of the same chemistry with unknown degradation history was then analysed to explore how the cell degraded. The DTV technique was able to diagnose the cell degradation without relying on supporting results from other methods nor previous cycling data.
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Diagnosing the state-of-health of lithium ion batteries in-operando is becoming increasingly important for multiple applications. We report the application of differential thermal voltammetry (DTV) to lithium iron phosphate (LFP) cells for the first time, and demonstrate that the technique is capable of diagnosing degradation in a similar way to incremental capacity analysis (ICA). DTV has the advantage of not requiring current and works for multiple cells in parallel, and is less sensitive to temperature introducing errors. Cells were aged by holding at 100% SOC or cycling at 1C charge, 6D discharge, both at an elevated temperature of 45 °C under forced air convection. Cells were periodically characterised, measuring capacity fade, resistance increase (power fade), and DTV fingerprints. The DTV results for both cells correlated well with both capacity and power, suggesting they could be used to diagnose SOH in-operando for both charge and discharge. The DTV peak-to-peak capacity correlated well with total capacity fade for the cycled cell, suggesting that it should be possible to estimate SOC and SOH from DTV for incomplete cycles within the voltage hysteresis region of an LFP cell
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