Monitoring the dynamic chemical and thermal state of a cell during operation is crucial to making meaningful advancements in battery technology as safety and reliability cannot be compromised. Here we demonstrate the feasibility of incorporating optical fibre Bragg grating sensors into commercial 18650 cells. By adjusting fibre morphologies, wavelength changes associated with both temperature and pressure are decoupled with high accuracy, which allows tracking of chemical events such as solid electrolyte interphase formation and structural evolution. We also demonstrate how multiple sensors are used to determine the heat generated by the cell without resorting to microcalorimetry. Unlike with conventional isothermal calorimetry, the cell’s heat capacity contribution is readily assessed, allowing for full parametrization of the thermal model. Collectively, these findings offer a scalable solution for screening electrolyte additives, rapidly identifying the best formation processes of commercial cells and designing battery thermal management systems with enhanced safety.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All relevant data are included in the paper and its Supplementary Information.
Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).
Grey, C. & Tarascon, J.-M. Sustainability and in situ monitoring in battery development. Nat. Mater. 16, 45–56 (2017).
Bright, C. T. et al. Remarks on “On reversible lead batteries and their use for electric lighting”. J. Soc. Telegr. Eng. Electr. 16, 184–218 (1887).
Lamoureux Jr, T. L. Flight Proofing Test Report for Main Missile Remotely Activated Primary Battery, ESB DWG. NO. 27-06359-3 (General Dynamics/Astronautics San Diego CA, 1959).
Jasinski, L. Rapid battery charging system and method. US patent 3,852,652 (1974).
Louli, A., Ellis, L. & Dahn, J. Operando pressure measurements reveal solid electrolyte interphase growth to rank Li-ion cell performance. Joule 3, 745–761 (2019).
Worrell, C. & Redfern, B. Acoustic emission studies of the breakdown of beta-alumina under conditions of sodium ion transport. J. Mater. Sci. 13, 1515–1520 (1978).
Day, R. et al. Differential thermal analysis of Li-ion cells as an effective probe of liquid electrolyte evolution during aging. J. Electrochem. Soc. 162, A2577–A2581 (2015).
Keddam, M., Stoynov, Z. & Takenouti, H. Impedance measurement on Pb/H2SO4 batteries. J. Appl. Electrochem. 7, 539–544 (1977).
Liebhart, B., Komsiyska, L. & Endisch, C. Passive impedance spectroscopy for monitoring lithium-ion battery cells during vehicle operation. J. Power Sources 449, 227297 (2020).
Schmidt, J. P. et al. Measurement of the internal cell temperature via impedance: evaluation and application of a new method. J. Power Sources 243, 110–117 (2013).
Schmidt, J. P., Manka, D., Klotz, D. & Ivers-Tiffée, E. Investigation of the thermal properties of a Li-ion pouch-cell by electrothermal impedance spectroscopy. J. Power Sources 196, 8140–8146 (2011).
Forgez, C., Do, D. V., Friedrich, G., Morcrette, M. & Delacourt, C. Thermal modeling of a cylindrical LiFePO4/graphite lithium-ion battery. J. Power Sources 195, 2961–2968 (2010).
Yang, G., Leitão, C., Li, Y., Pinto, J. & Jiang, X. Real-time temperature measurement with fiber Bragg sensors in lithium batteries for safety usage. Measurement 46, 3166–3172 (2013).
Cheng, X. & Pecht, M. In situ stress measurement techniques on li-ion battery electrodes: a review. Energies 10, 591 (2017).
Peng, J. et al. High precision strain monitoring for lithium ion batteries based on fiber Bragg grating sensors. J. Power Sources 433, 226692 (2019).
Nascimento, M., Paixão, T., Ferreira, M. S. & Pinto, J. L. Thermal mapping of a lithium polymer batteries pack with FBGs network. Batteries 4, 67 (2018).
Raghavan, A. et al. Embedded fiber-optic sensing for accurate internal monitoring of cell state in advanced battery management systems part 1: Cell embedding method and performance. J. Power Sources 341, 466–473 (2017).
Ganguli, A. et al. Embedded fiber-optic sensing for accurate internal monitoring of cell state in advanced battery management systems part 2: Internal cell signals and utility for state estimation. J. Power Sources 341, 474–482 (2017).
Nascimento, M. et al. Internal strain and temperature discrimination with optical fiber hybrid sensors in Li-ion batteries. J. Power Sources 410, 1–9 (2019).
Bernardi, D., Pawlikowski, E. & Newman, J. A general energy balance for battery systems. J. Electrochem. Soc. 132, 5–12 (1985).
Thomas, K. E. & Newman, J. Thermal modeling of porous insertion electrodes. J. Electrochem. Soc. 150, A176–A192 (2003).
Downie, L., Hyatt, S. & Dahn, J. The impact of electrolyte composition on parasitic reactions in lithium ion cells charged to 4.7 V determined using isothermal microcalorimetry. J. Electrochem. Soc. 163, A35–A42 (2016).
Assat, G., Glazier, S. L., Delacourt, C. & Tarascon, J.-M. Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry. Nat. Energy 4, 647–656 (2019).
Shen, Z., Cao, L., Rahn, C. D. & Wang, C.-Y. Least squares galvanostatic intermittent titration technique (LS-GITT) for accurate solid phase diffusivity measurement. J. Electrochem. Soc. 160, A1842–A1846 (2013).
Srinivasan, V. & Newman, J. Discharge model for the lithium iron-phosphate electrode. J. Electrochem. Soc. 151, A1517–A1529 (2004).
Maher, K. & Yazami, R. A study of lithium ion batteries cycle aging by thermodynamics techniques. J. Power Sources 247, 527–533 (2014).
Bianchini, M. et al. Comprehensive investigation of the Na3V2(PO4)2F3–NaV2(PO4)2F3 system by operando high resolution synchrotron X-ray diffraction. Chem. Mater. 27, 3009–3020 (2015).
Berlinsky, A., Unruh, W., McKinnon, W. & Haering, R. Theory of lithium ordering in LixTiS2. Solid State Commun. 31, 135–138 (1979).
Yan, G. et al. Assessment of the electrochemical stability of carbonate-based electrolytes in Na-ion batteries. J. Electrochem. Soc. 165, A1222–A1230 (2018).
Hall, D. S., Glazier, S. L. & Dahn, J. R. Isothermal microcalorimetry as a tool to study solid-electrolyte interphase formation in lithium-ion cells. Phys. Chem. Chem. Phys. 18, 11383–11390 (2016).
Cometto, C., Yan, G., Mariyappan, S. & Tarascon, J.-M. Means of using cyclic voltammetry to rapidly design a stable DMC-Based electrolyte for Na-ion batteries. J. Electrochem. Soc. 166, A3723–A3730 (2019).
Cha, J., Han, J.-G., Hwang, J., Cho, J. & Choi, N.-S. Mechanisms for electrochemical performance enhancement by the salt-type electrolyte additive, lithium difluoro (oxalato) borate, in high-voltage lithium-ion batteries. J. Power Sources 357, 97–106 (2017).
Qi, X. et al. Lifetime limit of tris (trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries. RSC Adv. 6, 38342–38349 (2016).
David, N., Wild, P., Jensen, J., Navessin, T. & Djilali, N. Simultaneous in situ measurement of temperature and relative humidity in a PEMFC using optical fiber sensors. J. Electrochem. Soc. 157, B1173–B1179 (2010).
Yan, G. et al. A new electrolyte formulation for securing high temperature cycling and storage performances of Na‐ion batteries. Adv. Energy Mater. 9, 1901431 (2019).
Htein, L., Liu, Z., Gunawardena, D. & Tam, H.-Y. Single-ring suspended fiber for Bragg grating based hydrostatic pressure sensing. Opt. Express 27, 9655–9664 (2019).
Krause, L., Jensen, L. & Dahn, J. Measurement of parasitic reactions in Li ion cells by electrochemical calorimetry. J. Electrochem. Soc. 159, A937–A943 (2012).
Downie, L., Hyatt, S., Wright, A. & Dahn, J. Determination of the time dependent parasitic heat flow in lithium ion cells using isothermal microcalorimetry. J. Phys. Chem. C 118, 29533–29541 (2014).
Glazier, S., Li, J., Louli, A., Allen, J. & Dahn, J. An analysis of artificial and natural graphite in lithium ion pouch cells using ultra-high precision coulometry, isothermal microcalorimetry, gas evolution, long term cycling and pressure measurements. J. Electrochem. Soc. 164, A3545–A3555 (2017).
Glazier, S. et al. The effect of methyl acetate, ethylene sulfate, and carbonate blends on the parasitic heat flow of NMC532/graphite lithium ion pouch cells. J. Electrochem. Soc. 165, A867–A875 (2018).
Aiken, C. et al. An apparatus for the study of in situ gas evolution in Li-ion pouch cells. J. Electrochem. Soc. 161, A1548–A1554 (2014).
Zhu, Y., Li, Y., Bettge, M. & Abraham, D. P. Positive electrode passivation by LiDFOB electrolyte additive in high-capacity lithium-ion cells. J. Electrochem. Soc. 159, A2109–A2117 (2012).
J.-M.T. J.H. and L.A.B. acknowledge funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA and DIM RESPORE. J.B., S.T.B. and H.-Y.T. acknowledge funding from the General Research Fund Project (152087/18E) and the Hong Kong Polytechnic University (1-ZVGB). J.R.D. and E.R.L. thank the auspices of the NSERC/Tesla Canada IRC programme. E.R.L. thanks NSERC and The Nova Scotia Graduate Scholarship programme for scholarship support. We thank L. Htein from the Hong Kong Polytechnic University for his assistance in fabricating the microstructured optical fibres, and F. Rabuel and T. Lombard for preparing the NMC(111)/C 18650 cells. We thank TIAMAT for providing the NVPF/HC 18650 cells as well as Faurecia for supporting part of this work and IDIL for providing part of the FBG sensors. Finally, we gladly thank G. Assat, G. Yan, C. Cometto, B. Li and S. Mariyappan for extensive and valuable discussions and comments.
A patent related to the work has been filed.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Huang, J., Albero Blanquer, L., Bonefacino, J. et al. Operando decoding of chemical and thermal events in commercial Na(Li)-ion cells via optical sensors. Nat Energy 5, 674–683 (2020). https://doi.org/10.1038/s41560-020-0665-y