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In this work a new expansion measurement methodology for the detection of ageing mechanisms in lithium ion cells is described and evaluated. For this purpose, a polarization-optical homodyne Michelson interferometer with a resolution of approx. 10 nm was set up to allow measurements of different cell types, cell sizes, and cell chemistry within a Memmert IP55 climate chamber. The used interferometric measurement setup is ten times more accurate than measurement systems commonly used for battery measurements in the literature. The better spatial resolution of an interferometer setup enables the recording of the expansion response to short current pulses with low transferred charge. This offers the possibility to detect ageing mechanisms such as lithium plating within short measuring times. With this measurement setup, a lithium iron phosphate pouch cell from the company A123, with the model identification AMP20M1HD-A, is measured. First, an expansion measurement over a full charge and discharge cycle with a constant load of ± C 20 (b=1 A) is performed. Here, the cell undergoes an expansion of about 42 μm. Subsequently, the in this work proposed measurement methodology is presented to show the influence of effects such as the formation of overshooting graphite stages or lithium plating on cell expansion. For this purpose, at a residual capacitance of 50%, the cell is pulsed with current of different intensity I ∈ {±20A,±80A} for t = {240 s, 60 s}, at T = {10 ◦C, 20 ◦C, 30 ◦C}, respectively, and the mechanical response is recorded using the high accuracy interferometer setup. A mechanical relaxation of the cell after the pulses with a time constant in the range between 10 s and 20 s can be observed. It is shown that this relaxation behavior can be associated with effects of the anode known from the literature, such as the formation of overshooting graphite stages or lithium plating. These effects can be recorded by the very high-resolution measurement already with little transferred charge and within a short measurement time.
High-resolution Interferometric Measurement of Thickness Change on a Lithium-Ion Pouch Battery
(2019)
Volume change of graphite leads to change in thickness of battery storage layers during discharging and charging. Pouch cell lithium ion batteries are used in the field of electric vehicles and solar home storage. This paper shows a measurement setup for the three-dimensional measurement of thickness change on a flat 6.7mm thick pouch cell using a white light interferometer. With a measuring field of 7.05mm diameter the resulting 3D thickness change record contains 226000 3D readings. The measuring points have a lateral distance of 13.1μm. The repeatability of the measurement is 312.8nm for the individual values and 64.1nm for the average value. In addition, this paper shows how the storage capacity of this pouch cell drops over 30 charge cycles.
In this work, a battery consisting of eight commercial NMC/graphite cells connected in series was cycled to 60% of its initial capacity. During the test, special care was taken to ensure that the results were not influenced by either the module assembly or the module design. For this purpose, the cells were virtually connected in a laboratory environment with the help of the test device as if they were operated together in a battery. Extrinsic influences that affect cell aging were thus reduced to a minimum. Differential Voltage Analysis (DVA), Electrochemical Impedance Spectrum (EIS), and relaxation measurements were performed to analyze the aging behavior of each cell. The results show that despite a theoretically perfect module design, Cell-to-Cell Variations (CtCV) occurred during aging. The shifting Depth of Discharge (DoD) values among the cells further amplify CtCV. Lithium plating was also observed in the faster aging cells after cyclic aging, suggesting that this aging effect contributes significantly to the development of CtCV. After the aging test, the battery was equipped with an active balancing system that maximizes capacity utilization. More important, the balancing charges which are calculated iteratively within the used balancing algorithm show a strong correlation to the pure capacity losses and thus provide a new way to determine the capacity values of each cell individually without disassembling the battery.
In lithium-ion batteries, depending on the requirements, many individual cells are connected in series and parallel. Despite very similar individual cell parameters after production, they can develop differently during the subsequent ageing process due to intrinsic and extrinsic influences. A pronounced parameter variation of the assembled cells ultimately leads to a reduced utilisation of the lithium-ion battery and thus also to a reduced lifetime. The aim of this work is therefore to gain a better understanding of the origin and development of parameter variation during the ageing process. The work is divided into three major parts. At the beginning, parameters such as capacity and internal resistance of 480 brand-new cells of one production batch are recorded. The obtained values allow the calculation of the production-related parameter variation of the cells. In order to investigate the development of the parameter variation during cell ageing, numerous ageing tests are carried out in this work. These are divided into single cell tests and module tests. With the help of single cell ageing tests, the development of the parameter variation of unconnected cells is investigated. Here, several cells are combined into groups and aged under identical conditions. In order to show the influence of different operating conditions on the parameter variation during single cell ageing, the cell groups are aged at different temperatures and different load currents. Finally, by ageing various self-built modules, the development of the parameter variation of cells connected in series and in parallel is investigated. By varying the load current and the number of cells connected in parallel, further dependencies are investigated. The measured data show that both the load on the cells and the ambient temperature have a decisive influence on the development of parameter variation. Operating conditions near the lithium plating boundary are particularly problematic. Since the onset of lithium plating varies slightly between the ageing cells, there are extreme differences in the ageing rate over a certain period of time. This ultimately leads to large parameter variations in the tests carried out. The cells used in this work are cylindrical cells in 18650 format with a nominal capacity of 2.6 Ah (Samsung ICR18650-26J). The high-energy cells consist of a NMC cathode and a graphite anode.