Switching between solid solution and two-phase regimes in the Li1-xFe1-yMnyPO4 cathode materials during lithium (de)insertion: combined PITT, in situ XRPD and electron diffraction tomography study

Drozhzhin, Oleg A.; Sumanov, Vasiliy D.; Karakulina, Olesia M.; Abakumov, Artem M.; Hadermann, Joke; Баранов, А. Н.; Stevenson, Keith J.; Antipov, Evgeny V.

doi:10.1016/j.electacta.2016.01.018

Cited by 50 publications

(45 citation statements)

References 34 publications

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“…[31][32][33][34][35] We believe that extending the technique to 3D may be possible with further development of the measurement technique. 36 Monitoring the time evolution of these 2D and 3D maps will allow us to determine local internal thermal conductivities 37-39 as well as time-dependent heat transfer rates from the pouch interior to the environment. …”

mentioning

confidence: 99%

Simultaneous Operando Measurements of the Local Temperature, State of Charge, and Strain inside a Commercial Lithium-Ion Battery Pouch Cell

Feng

Ren

et al. 2018

J. Electrochem. Soc.

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A high energy X-ray diffraction technique is employed in a new way to make operando through-thickness measurements inside a large format commercial Li-ion pouch cell. The technique, which has a sub-mm in-plane spatial resolution, simultaneously determines the local temperature, the local state of charge of both electrodes (as opposed to the global average state of charge determined electrochemically), and the local in-plane elastic strain in the current collectors, all without embedding any intrusive sensors that alter battery behavior. As both thermal strain and mechanical strain develop during the charge-discharge cycling of the pouch cell, a novel approach developed herein makes it possible to separate them, allowing for measurement of the local temperature inside the battery. The operando experiment reveals that the temperature inside the cell is substantially higher than the external temperature. We propose that mechanical strain is due primarily to load transfer from the electrode to the current collector during lithiation, allowing determination of the local binder. Detailed local SOC mapping illustrates non-uniform degradation of the battery pouch cell. The possibility for 3D measurements is proposed. We believe that this new approach can provide critically needed data for validation of detailed models of processes inside commercial pouch cells. Today's electric vehicles generally use pouch cells rather than the more traditional cylindrical cells. An important advantage of pouch cells is their much higher surface-to-volume ratio for a given capacity, which permits better cooling. Batteries tend to heat up because of the hot environments that cars experience, internal electric resistance heating, and exothermic chemical reactions during operation. The performance of batteries fades over time, and high temperatures (say, above 45• C) greatly accelerate the fade rate 1,2 and may promote thermal runaway, 3 making temperature control critical. 4,5 Ideally, temperature control should be guided by the temperature inside the pouch cell, but making measurements inside an operating pouch cell has been difficult. Instead, the outside temperature has usually been taken as a surrogate for the internal temperature. [6][7][8] If pouch cells are sufficiently thin, and if the thermal conductivity is high enough, then it is reasonable to assume that the temperature measured at an x-y location on the outside of a pouch cell, with a thermocouple or with a thermal infrared (IR) camera, is close to the temperature at that x-y location all the way through its thickness. However, auto makers are motivated to make pouch cells thicker, reducing the number of expensive seals, electrical connections, and controls. Since local temperatures inside a thick cell might well be too high under some conditions, knowledge of the spatial distribution of internal temperature is of vital importance for achieving long life at low cost.A number of techniques have been developed to measure internal cell temperatures, 10-17 but measurement of loca...

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mentioning

confidence: 99%

Simultaneous Operando Measurements of the Local Temperature, State of Charge, and Strain inside a Commercial Lithium-Ion Battery Pouch Cell

Feng

Ren

et al. 2018

J. Electrochem. Soc.

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“…Asymmetric phase transition behavior between LiFePO 4 and FePO 4 are also observed at high rates charge-discharging [52,53,66] . This explains the irreversible charge-discharge property at high rate cycling.…”

Section: Electrochemical In Situ Characterization Of Phase Transformamentioning

confidence: 82%

“…Excellent rate capability can be obtained for LiFePO 4 when carbon coated and nanosized, which is contrary to its initially reported first order two phase delithiation/lithiatioin reaction mechanism, a kinetically limited process involving a volume http://engine.scichina.com/doi/10.1016/j.jechem.2018.03.020 change of 6.8% [41,43] . This contradictory has stimulated numerous both theoretical and experimental studies that attempt to explain the charge-discharge mechanism in LiFePO 4 [43][44][45][46][47][48][49][50][51][52][53][54][55] . Important new insights have been revealed with the use of advanced synchrotron based in situ XRD.…”

Section: Electrochemical In Situ Characterization Of Phase Transformamentioning

confidence: 99%

The application of synchrotron X-ray techniques to the study of rechargeable batteries

Gong

Yang

2018

Journal of Energy Chemistry

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“…Still, in certain cases, the introduction of partial occupancies allowed significant improvements in both agreement parameters and crystallo-chemical reliability of the refined models (Palatinus et al, 2015;Lepoittevin, 2016). Because electrons are very sensitive to light atoms when compared to X-rays, in certain cases they might even allow a quantitative estimation of partially occupied positions for very light atomic species, such as Li (Drozhzhin et al, 2016) and H (Palatinus et al, 2017). Palatinus et al (2015) also demonstrated that the Mg/Fe mixed occupancy in orthopyroxene can be refined by 3D ED data to the expected value taking into account dynamical effects.…”

Section: Mixed Occupancies and Vacanciesmentioning

confidence: 99%

“…ED has also been successfully applied to incommensurate materials (Palatinus et al, 2011;Steciuk et al, 2016), and to macromolecules (Shi et al, 2013;Yonekura et al, 2015;Clabbers et al, 2017;de la Cruz et al, 2017;Xu et al, 2018;Lanza et al, 2019) and other structures of biological relevance (Rodriguez et al, 2015;Zee et al, 2019). Additionally, compared with X-rays, electrons can locate more easily light atoms such as Li (Hadermann et al, 2011(Hadermann et al, , 2012Kolb et al, 2011;Drozhzhin et al, 2016) and H (Palatinus et al, 2017;Clabbers et al, 2019), possibly employing refinement algorithms that take into consideration the dynamical scattering (Palatinus et al, 2013(Palatinus et al, , 2015.…”

Section: Introductionmentioning

confidence: 99%

Structure analysis of materials at the order–disorder borderline using three-dimensional electron diffraction

Mugnaioli

Gorelik

2019

Acta Crystallogr Sect B

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Diffuse scattering, observed as intensity distribution between the Bragg peaks, is associated with deviations from the average crystal structure, generally referred to as disorder. In many cases crystal defects are seen as unwanted perturbations of the periodic structure and therefore they are often ignored. Yet, when it comes to the structure analysis of nano-volumes, what electron crystallography is designed for, the significance of defects increases. Twinning and polytypic sequences are other perturbations from ideal crystal structure that are also commonly observed in nanocrystals. Here we present an overview of defect types and review some of the most prominent studies published on the analysis of defective nanocrystalline structures by means of three-dimensional electron diffraction.

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Switching between solid solution and two-phase regimes in the Li1-xFe1-yMnyPO4 cathode materials during lithium (de)insertion: combined PITT, in situ XRPD and electron diffraction tomography study

Abstract: Switching between solid solution and two-phase regimes in the cathode materials during lithium (de)insertion : combined PITT, in situ XRPD and electron diffraction tomography study Electrochimica acta -

Cited by 50 publications

References 34 publications

Simultaneous Operando Measurements of the Local Temperature, State of Charge, and Strain inside a Commercial Lithium-Ion Battery Pouch Cell

Simultaneous Operando Measurements of the Local Temperature, State of Charge, and Strain inside a Commercial Lithium-Ion Battery Pouch Cell

The application of synchrotron X-ray techniques to the study of rechargeable batteries

Structure analysis of materials at the order–disorder borderline using three-dimensional electron diffraction

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