Engineering topics

Fenton, Kyle

Publications and source records attributed to Fenton, Kyle.

9 records

DOE OSTI2021

Silicon Consortium Project: No-Go on Moir Interferometry for Measuring SEI Strain as a Probe for Calendar Life Testing

Silicon is a promising candidate as a next generation anode to replace or complement graphite electrodes due to its high energy density and low lithiation potential. When silicon is lithiated, it experiences over 300% expansion which stresses the silicon as well as its solid electrolyte interphase (SEI) leading to poor performance. The use of nano-sized silicon has helped to mitigate volume expansion and stress in the silicon, yet the silicon SEI is still both mechanically and chemically unstable. Identifying the mechanical failure mechanism of the SEI will help enhance calendar and cycle life performance through improved SEI design. In situ moiré interferometry was investigated to try and track the in-plane strain in the SEI and silicon electrode for this purpose. Moiré can detect on the order of 10 nm changes in displacement and is therefore a useful tool in the measurement of strain. As the sample undergoes small deformations, large changes in the moiré fringe allow for measurements of displacement below the diffraction limit of light. Figure 1a shows how the moiré fringe changes as the sample grating deforms. As the sample contracts or expands, the frequency of the moiré fringe changes, and this change is proportional to the strain in the sample.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Effect of overcharge on Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 /Graphite cells–effect of binder

Cells based on NMC/graphite, containing styrene-butadiene rubber/carboxymethylcellulose binder in the anodes and pVdF latex/carboxymethykellulose in the cathodes, were systematically overcharged to 100, 120, 140, 160, 180, 250% and 270% state-of-charge. The impact of the binder was characterized by elemental analysis, SEM, and HPLC. These results were compared to similar cells just using the poly (vinylidene difluoride) binder. Not only did the binder impact the rate of transition metal transport from the cathode to the anode, it also had a marked effect on the microstructure and composition of the materials on the anode surface.

25 ENERGY STORAGE↗

DOE OSTI2020

Effect of binder on the overcharge response in LiFePO 4 -containing cells

Two types of small pouch cells based on LiFePO 4 /graphite, one containing a N-methyl pyrrolidinone (NMP)-soluble binder, poly(vinylidene difluoride), and the other an aqueous-soluble binder, styrene-butadiene rubber/carboxymethylcellulose were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). The cells were then discharged to 3.0 V at room temperature before being disassembled for postmortem analysis. Microstructural changes in the anode associated with increasing SOC were more pronounced in the aqueous processed cells in comparison to the NMP-processed cells. Dendrite formation was observed on the aqueous-processed anode at 120% SOC, while the NMP-processed anode surface does not show dendrites until 250% SOC. Overall, the aqueous-processed anode surfaces displayed more evidence of microstructural degradation as a function of increasing SOC. In the NMP-processed cells, four organic compounds on the anode surface were found to show a dependence on SOC, while only two displayed a similar dependency in the aqueous-processed cells. The nature of the binder changed the number and composition of the species found at the anode.

25 ENERGY STORAGE↗

DOE OSTI2019

Effect of overcharge on lithium-ion cells: Silicon/graphite anodes

Small pouch cells containing Si/graphite electrodes were systematically charged to 100, 120, 140, 160, 180 and 250% state of charge. Description of the Si/graphite electrode after the overcharge showed some features similar to those found in a pure graphite electrode. Since the amount of silicon in the electrode was ~15 wt%, this was not unexpected. The effect of silicon was observed in the composition of the SEI layer and the trends in two components of the SEI layer.

25 ENERGY STORAGE↗

DOE OSTI2018

Simple Stochastic Model of Multiparticle Battery Electrodes Undergoing Phase Transformations

Incorporation of ions into battery electrodes can lead to phase transformations. When multiparticle phase-transforming electrodes charge or discharge, two processes must occur in each particle: the new phase must nucleate, and then grow until the particle is fully charged or discharged. A fundamental question is which of these two processes is rate limiting. Here in this paper, we construct a simple stochastic model that shows how the relative rate of nucleation compared with growth determines the particle state-of-charge distributions in the electrode. We find that the number of particles that are partially charged at any time increases as the relative nucleation rate increases. The maximum number of particles that are actively charging occurs just before the time when the first particles are becoming completely charged. By comparing measured state-of-charge distributions with the model, we determine the relative rate of nucleation. We apply this procedure to measurements of the evolution of particles in LiFePO 4 cathodes and show we can account for the particle state-of-charge distribution as a function of the electrode state of charge.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Effect of overcharge on Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 /Graphite lithium ion cells with poly(vinylidene fluoride) binder. I - Microstructural changes in the anode

Cells based on NMC/graphite, containing poly(vinylidene difluoride) (PVDF) binders in the positive and negative electrodes, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state-of-charge (SOC). At 250% SOC the cell vented. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the anodes showed several state-of-overcharge-dependent trends. Starting at 120% SOC, dendrites appeared and increased in concentration as the SOC increased. Dendrite morphology appeared to be dependent on whether the active material was on the “dull” or “shiny” side of the copper collector. Significantly more delamination of the active material from the collector was seen on the “shiny” side of the collector particularly at 180 and 250% SOC. Transition metals were detected at 120% SOC and increased in concentration as the SOC increased. Finally, there was considerable spatial heterogeneity in the microstructures across each laminate with several regions displaying complex layered structures.

25 ENERGY STORAGE↗

DOE OSTI2018

Effect of overcharge on Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 cathodes: NMP-soluble binder. II — Chemical changes in the anode

For this study, cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO 3 , increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF 3 or O=PF 3 . Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.

25 ENERGY STORAGE↗

DOE OSTI2018

Effect of overcharge on Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 /graphite lithium ion cells with poly(vinylidene fluoride) binder. III — Chemical changes in the cathode

Here, 1.5 Ah pouch cells based on Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 cathodes and graphite anodes, both containing poly (vinylidene fluoride) (PVDF) binders, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state of charge (SOC), at which point they vented. The cells were subsequently discharged to 0% SOC and disassembled under an inert atmosphere for characterization. A combination of X-ray photoelectron spectroscopy (XPS), scanning-electron microscopy (SEM), energy-dispersive spectroscopy (EDS), 6 Li SSNMR, and X-ray diffraction (XRD) analysis of the NMC532 cathodes indicates the formation of a thin C- and O-rich cathode electrolyte interphase layer, progressive Li loss above 140% SOC, and retention of the bulk crystal structure at all states of charge.

25 ENERGY STORAGE↗

DOE OSTI2017

Open stack thermal battery tests

We present selected results from a series of Open Stack thermal battery tests performed in FY14 and FY15 and discuss our findings. These tests were meant to provide validation data for the comprehensive thermal battery simulation tools currently under development in Sierra/Aria under known conditions compared with as-manufactured batteries. We are able to satisfy this original objective in the present study for some test conditions. Measurements from each test include: nominal stack pressure (axial stress) vs. time in the cold state and during battery ignition, battery voltage vs. time against a prescribed current draw with periodic pulses, and images transverse to the battery axis from which cell displacements are computed. Six battery configurations were evaluated: 3, 5, and 10 cell stacks sandwiched between 4 layers of the materials used for axial thermal insulation, either Fiberfrax Board or MinK. In addition to the results from 3, 5, and 10 cell stacks with either in-line Fiberfrax Board or MinK insulation, a series of cell-free “control” tests were performed that show the inherent settling and stress relaxation based on the interaction between the insulation and heat pellets alone.

25 ENERGY STORAGE↗