Electron paramagnetic resonance as a tool to determine the sodium charge storage mechanism of hard carbon.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
08 Apr 2024
08 Apr 2024
Historique:
received:
23
11
2022
accepted:
19
01
2024
medline:
9
4
2024
pubmed:
9
4
2024
entrez:
8
4
2024
Statut:
epublish
Résumé
Hard carbon is a promising negative electrode material for rechargeable sodium-ion batteries due to the ready availability of their precursors and high reversible charge storage. The reaction mechanisms that drive the sodiation properties in hard carbons and subsequent electrochemical performance are strictly linked to the characteristic slope and plateau regions observed in the voltage profile of these materials. This work shows that electron paramagnetic resonance (EPR) spectroscopy is a powerful and fast diagnostic tool to predict the extent of the charge stored in the slope and plateau regions during galvanostatic tests in hard carbon materials. EPR lineshape simulation and temperature-dependent measurements help to separate the nature of the spins in mechanochemically modified hard carbon materials synthesised at different temperatures. This proves relationships between structure modification and electrochemical signatures in the galvanostatic curves to obtain information on their sodium storage mechanism. Furthermore, through ex situ EPR studies we study the evolution of these EPR signals at different states of charge to further elucidate the storage mechanisms in these carbons. Finally, we discuss the interrelationship between EPR spectroscopy data of the hard carbon samples studied and their corresponding charging storage mechanism.
Identifiants
pubmed: 38589362
doi: 10.1038/s41467-024-45460-3
pii: 10.1038/s41467-024-45460-3
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
3013Subventions
Organisme : RCUK | Engineering and Physical Sciences Research Council (EPSRC)
ID : NS/A000055/1
Informations de copyright
© 2024. The Author(s).
Références
Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
pubmed: 11713543
doi: 10.1038/35104644
Goodenough, J. B. How we made the Li-ion rechargeable battery. Nat. Electron. 1, 204–204 (2018).
doi: 10.1038/s41928-018-0048-6
Hwang, J. Y., Myung, S. T. & Sun, Y. K. Sodium-ion batteries: present and future. Chem. Soc. Rev. 46, 3529–3614 (2017).
pubmed: 28349134
doi: 10.1039/C6CS00776G
Yabuuchi, N. et al. Research development on sodium-ion batteries. Chem. Rev. 114, 11636–11682 (2014).
pubmed: 25390643
doi: 10.1021/cr500192f
Wen, Y. et al. Expanded graphite as superior anode for sodium-ion batteries. Nat. Commun. 5, 4033 (2014).
pubmed: 24893716
doi: 10.1038/ncomms5033
Zhang, B. et al. Correlation between microstructure and Na storage behavior in hard carbon. Adv. Energy Mater. 6, 1501588 (2016).
doi: 10.1002/aenm.201501588
Xiao, B. et al. Hard carbon as sodium-ion battery anodes: progress and challenges. ChemSusChem 12, 133–144 (2019).
pubmed: 30350453
doi: 10.1002/cssc.201801879
Chen, D. et al. Hard carbon for sodium storage: mechanism and optimization strategies toward commercialization. Energy Environ. Sci. 14, 2244–2262 (2021).
doi: 10.1039/D0EE03916K
Xie, F., Xu, Z., Guo, Z. & Titirici, M. M. Hard carbons for sodium-ion batteries and beyond. Prog. Energy 2, 042002 (2020).
doi: 10.1088/2516-1083/aba5f5
Stevens, D. A. & Dahn, J. R. An in situ small-angle x-ray scattering study of sodium insertion into a nanoporous carbon anode material within an operating electrochemical cell. J. Electrochem. Soc. 147, 4428 (2000).
doi: 10.1149/1.1394081
Anji Reddy, M. et al. Insight into sodium insertion and the storage mechanism in hard carbon. ACS Energy Lett. 3, 2851–2857 (2018).
doi: 10.1021/acsenergylett.8b01761
Qiu, S. et al. Manipulating adsorption–insertion mechanisms in nanostructured carbon materials for high-efficiency sodium ion storage. Adv. Energy Mater. 7, 1700403 (2017).
doi: 10.1002/aenm.201700403
Li, Z. et al. Mechanism of Na-ion storage in hard carbon anodes revealed by heteroatom doping. Adv. Energy Mater. 7, 1602894 (2017).
doi: 10.1002/aenm.201602894
Morikawa, Y. et al. Mechanism of sodium storage in hard carbon: an X-ray scattering analysis. Adv. Energy Mater. 10, 1903176 (2020).
doi: 10.1002/aenm.201903176
Bommier, C., Surta, T. W., Dolgos, M. & Ji, X. New mechanistic insights on Na-ion storage in nongraphitizable carbon. Nano Lett. 15, 5888–5892 (2015).
pubmed: 26241159
doi: 10.1021/acs.nanolett.5b01969
Alvin, S. et al. Revealing the intercalation mechanisms of lithium, sodium, and potassium in hard carbon. Adv. Energy Mater. 10, 2000283 (2020).
doi: 10.1002/aenm.202000283
Au, H. et al. A revised mechanistic model for sodium insertion in hard carbons. Energy Environ. Sci. 13, 3469–3479 (2020).
doi: 10.1039/D0EE01363C
Fitzpatrick, J. R., Costa, S. I. R. & Tapia-Ruiz, N. Sodium-ion batteries: current understanding of the sodium storage mechanism in hard carbons: optimising properties to speed commercialisation. Johns. Matthey Technol. Rev. 66, 44–60 (2022).
doi: 10.1595/205651322X16250408525547
Stevens, D. A. & Dahn, J. R. The mechanisms of lithium and sodium insertion in carbon materials. J. Electrochem. Soc. 148, A803 (2001).
doi: 10.1149/1.1379565
Komaba, S. et al. Electrochemical Na insertion and solid electrolyte interphase for hard-carbon electrodes and application to Na-ion batteries. Adv. Funct. Mater. 21, 3859–3867 (2011).
doi: 10.1002/adfm.201100854
Cao, Y. et al. Sodium ion insertion in hollow carbon nanowires for battery applications. Nano Lett. 12, 3783–3787 (2012).
pubmed: 22686335
doi: 10.1021/nl3016957
Ding, J. et al. Carbon nanosheet frameworks derived from peat moss as high performance sodium ion battery anodes. ACS Nano 7, 11004–11015 (2013).
pubmed: 24191681
doi: 10.1021/nn404640c
Xiao, L. et al. Low-defect and low-porosity hard carbon with high coulombic efficiency and high capacity for practical sodium ion battery anode. Adv. Energy Mater. 8, 1703238 (2018).
doi: 10.1002/aenm.201703238
Bin, D. S. et al. Structural engineering of multishelled hollow carbon nanostructures for high-performance Na-ion battery anode. Adv. Energy Mater. 8, 1800855 (2018).
doi: 10.1002/aenm.201800855
Li, Y., Hu, Y. S., Titirici, M. M., Chen, L. & Huang, X. Hard carbon microtubes made from renewable cotton as high-performance anode material for sodium-ion batteries. Adv. Energy Mater. 6, 1600659 (2016).
doi: 10.1002/aenm.201600659
Sun, N. et al. Extended “adsorption–insertion” model: a new insight into the sodium storage mechanism of hard carbons. Adv. Energy Mater. 9, 1901351 (2019).
doi: 10.1002/aenm.201901351
Wang, Z. et al. Probing the energy storage mechanism of quasi-metallic na in hard carbon for sodium-ion batteries. Adv. Energy Mater. 11, 2003854 (2021).
doi: 10.1002/aenm.202003854
Alptekin, H. et al. Sodium storage mechanism investigations through structural changes in hard carbons. ACS Appl. Energy Mater. 3, 9918–9927 (2020).
doi: 10.1021/acsaem.0c01614
Li, Y. et al. Regulating pore structure of hierarchical porous waste cork-derived hard carbon anode for enhanced Na storage performance. Adv. Energy Mater. 9, 1902852 (2019).
doi: 10.1002/aenm.201902852
Gomez-Martin, A. et al. Correlation of structure and performance of hard carbons as anodes for sodium ion batteries. Chem. Mater. 31, 7288–7299 (2019).
doi: 10.1021/acs.chemmater.9b01768
Stratford, J. M., Allan, P. K., Pecher, O., Chater, P. A. & Grey, C. P. Mechanistic insights into sodium storage in hard carbon anodes using local structure probes. Chem. Commun. 52, 12430–12433 (2016).
doi: 10.1039/C6CC06990H
Ilic, I. K., Schutjajew, K., Zhang, W. & Oschatz, M. Changes of porosity of hard carbons during mechanical treatment and the relevance for sodium-ion anodes. Carbon 186, 55–63 (2022).
doi: 10.1016/j.carbon.2021.09.063
Lu, H. et al. Exploring sodium-ion storage mechanism in hard carbons with different microstructure prepared by ball-milling method. Small 14, 1802694 (2018).
doi: 10.1002/smll.201802694
Dou, X. et al. Hard carbons for sodium-ion batteries: Structure, analysis, sustainability, and electrochemistry. Mater. Today 23, 87–104 (2019).
doi: 10.1016/j.mattod.2018.12.040
Kawamura, K. Electron spin resonance behavior of pitch-based carbons in the heat treatment temperature range of 1100–2000 °C. Carbon 36, 1227–1230 (1998).
doi: 10.1016/S0008-6223(98)00103-1
Zhecheva, E. et al. EPR study on petroleum cokes annealed at different temperatures and used in lithium and sodium batteries. Carbon 40, 2301–2306 (2002).
doi: 10.1016/S0008-6223(02)00121-5
Singer, L. S. & Wagoner, G. Electron spin resonance in polycrystalline graphite. J. Chem. Phys. 37, 1812–1817 (1962).
doi: 10.1063/1.1733373
Emmerich, F. G., Rettori, C. & Luengo, C. A. ESR in heat treated carbons from the endocarp of babassu coconut. Carbon 29, 305–311 (1991).
doi: 10.1016/0008-6223(91)90198-R
Ottaviani, M. F. & Mazzeo, R. EPR characterization of graphitized and activated micro- and meso-porous carbons. Microporous Mesoporous Mater. 141, 61–68 (2011).
doi: 10.1016/j.micromeso.2010.10.049
Barbon, A. EPR spectroscopy in the study of 2D graphene-based nanomaterials and nanographites. In Electron Paramagnetic Resonance. (eds Chechik, V. & Murphy, D. M.) Vol. 26, 38–65 (The Royal Society of Chemistry, 2018).
Kubota, K. et al. Structural analysis of sucrose-derived hard carbon and correlation with the electrochemical properties for lithium, sodium, and potassium insertion. Chem. Mater. 32, 2961–2977 (2020).
doi: 10.1021/acs.chemmater.9b05235
Yu, Z. E. et al. Hard carbon micro-nano tubes derived from kapok fiber as anode materials for sodium-ion batteries and the sodium-ion storage mechanism. Chem. Commun. 56, 778–781 (2020).
doi: 10.1039/C9CC08221B
Alcántara, R. et al. EPR, NMR, and electrochemical studies of surface-modified carbon microbeads. Chem. Mater. 18, 2293–2301 (2006).
doi: 10.1021/cm060060p
Gan, Q. et al. Extra sodiation sites in hard carbon for high performance sodium ion batteries. Small Methods 5, 2100580 (2021).
doi: 10.1002/smtd.202100580
Zhou, X., Zhuang, L. & Lu, J. Deducing the density of electronic states at the fermi level for lithiated carbons using comWanged electrochemical and electron spin resonance measurements. J. Phys. Chem. B 107, 7783–7787 (2003).
doi: 10.1021/jp034342d
Feher, G. & Kip, A. F. Electron spin resonance absorption in metals. I. Experimental. Phys. Rev. 98, 337–348 (1955).
doi: 10.1103/PhysRev.98.337
Wang, K. et al. Low-cost and high-performance hard carbon anode materials for sodium-ion batteries. ACS Omega 2, 1687–1695 (2017).
pubmed: 31457533
pmcid: 6641066
doi: 10.1021/acsomega.7b00259
Zhen, Y. et al. Ultrafast synthesis of hard carbon anodes for sodium-ion batteries. Proc. Natl. Acad. Sci. USA 118, e2111119118 (2021).
pubmed: 34663702
pmcid: 8545444
doi: 10.1073/pnas.2111119118
Tuinstra, F. & Koenig, J. L. Raman spectrum of graphite. J. Chem. Phys. 53, 1126–1130 (1970).
doi: 10.1063/1.1674108
He, X. X. et al. Soft-carbon-coated, free-standing, low-defect, hard-carbon anode to achieve a 94% initial coulombic efficiency for sodium-ion batteries. ACS Appl. Mater. Interfaces 13, 44358–44368 (2021).
pubmed: 34506123
doi: 10.1021/acsami.1c12171
Sadezky, A., Muckenhuber, H., Grothe, H., Niessner, R. & Pöschl, U. Raman microspectroscopy of soot and related carbonaceous materials: spectral analysis and structural information. Carbon 43, 1731–1742 (2005).
doi: 10.1016/j.carbon.2005.02.018
Goodman, P. A. et al. Preparation and characterization of high surface area, high porosity carbon monoliths from pyrolyzed bovine bone and their performance as supercapacitor electrodes. Carbon 55, 291–298 (2013).
doi: 10.1016/j.carbon.2012.12.066
Jawhari, T., Roid, A. & Casado, J. Raman spectroscopic characterization of some commercially available carbon black materials. Carbon 33, 1561–1565 (1995).
doi: 10.1016/0008-6223(95)00117-V
Nemanich, R. J. & Solin, S. A. First- and second-order Raman scattering from finite-size crystals of graphite. Phys. Rev. B 20, 392–401 (1979).
doi: 10.1103/PhysRevB.20.392
Wang, K. et al. Sodium storage in hard carbon with curved graphene platelets as the basic structural units. J. Mater. Chem. A 7, 3327–3335 (2019).
doi: 10.1039/C8TA11510A
Badaczewski, F. et al. Peering into the structural evolution of glass-like carbons derived from phenolic resin by combining small-angle neutron scattering with an advanced evaluation method for wide-angle X-ray scattering. Carbon 141, 169–181 (2019).
doi: 10.1016/j.carbon.2018.09.025
Saurel, D. et al. A SAXS outlook on disordered carbonaceous materials for electrochemical energy storage. Energy Storage Mater. 21, 162–173 (2019).
doi: 10.1016/j.ensm.2019.05.007
Irisarri, E. et al. Optimization of large scale produced hard carbon performance in na-ion batteries: effect of precursor, temperature and processing conditions. J. Electrochem. Soc. 165, A4058 (2018).
doi: 10.1149/2.1171816jes
Chen, X. et al. High-performance sodium-ion batteries with a hard carbon anode: transition from the half-cell to full-cell perspective. Nanoscale 11, 22196–22205 (2019).
pubmed: 31742294
doi: 10.1039/C9NR07545C
Conder, J. & Villevieille, C. How reliable is the Na metal as a counter electrode in Na-ion half cells? Chem. Commun. 55, 1275–1278 (2019).
doi: 10.1039/C8CC07852A
Li, Z. et al. Hard carbon anodes of sodium-ion batteries: undervalued rate capability. Chem. Commun. 53, 2610–2613 (2017).
doi: 10.1039/C7CC00301C
Stratford, J. M. et al. Correlating local structure and sodium storage in hard carbon anodes: insights from pair distribution function analysis and solid-state NMR. J. Am. Chem. Soc. 143, 14274–14286 (2021).
pubmed: 34431677
doi: 10.1021/jacs.1c06058
Zhang, Y. et al. Lithium and sodium storage in highly ordered mesoporous nitrogen-doped carbons derived from honey. J. Power Sour. 335, 20–30 (2016).
doi: 10.1016/j.jpowsour.2016.08.096
Li, D. et al. Potassium gluconate-derived N/S Co-doped carbon nanosheets as superior electrode materials for supercapacitors and sodium-ion batteries. J. Power Sour. 414, 308–316 (2019).
doi: 10.1016/j.jpowsour.2018.12.091
Li, Z. et al. Defective hard carbon anode for Na-ion batteries. Chem. Mater. 30, 4536–4542 (2018).
doi: 10.1021/acs.chemmater.8b00645
Li, Y., Lu, Y., Adelhelm, P., Titirici, M. M. & Hu, Y. S. Intercalation chemistry of graphite: alkali metal ions and beyond. Chem. Soc. Rev. 48, 4655–4687 (2019).
pubmed: 31294739
doi: 10.1039/C9CS00162J
Schutjajew, K., Pampel, J., Zhang, W., Antonietti, M. & Oschatz, M. Influence of pore architecture and chemical structure on the sodium storage in nitrogen-doped hard carbons. Small 17, 2006767 (2021).
doi: 10.1002/smll.202006767
Zhao, H. et al. Insights into the surface oxygen functional group-driven fast and stable sodium adsorption on carbon. ACS Appl. Mater. Interfaces 12, 6991–7000 (2020).
pubmed: 31957428
doi: 10.1021/acsami.9b11627
Guo, R. et al. Effect of intrinsic defects of carbon materials on the sodium storage performance. Adv. Energy Mater. 10, 1903652 (2020).
doi: 10.1002/aenm.201903652
Wang, H. et al. Oxygen functional group modification of cellulose-derived hard carbon for enhanced sodium ion storage. ACS Sustain. Chem. Eng. 7, 18554–18565 (2019).
doi: 10.1021/acssuschemeng.9b04676
Matthews, M. J. et al. Electron spin resonance of polyparaphenylene‐based carbons. Appl. Phys. Lett. 69, 2042–2044 (1996).
doi: 10.1063/1.116873
Tomita, S., Sakurai, T., Ohta, H., Fujii, M. & Hayashi, S. Structure and electronic properties of carbon onions. J. Chem. Phys. 114, 7477–7482 (2001).
doi: 10.1063/1.1360197
Wang, B., Le Fevre, L. W., Brookfield, A., McInnes, E. J. L. & Dryfe, R. A. W. Resolution of lithium deposition versus intercalation of graphite anodes in lithium ion batteries: an in situ electron paramagnetic resonance study. Angew. Chem. Int. Ed. 60, 21860–21867 (2021).
doi: 10.1002/anie.202106178
Wagoner, G. Spin Resonance of charge carriers in graphite. Phys. Rev. 118, 647–653 (1960).
doi: 10.1103/PhysRev.118.647
Di Vittorio, S. L. et al. ESR study of activated carbon fibers: preliminary results. J. Mater. Res. 8, 2282–2287 (1993).
doi: 10.1557/JMR.1993.2282
Nakayama, A. et al. Magnetic properties of activated carbon fibers. Synth. Met. 57, 3736–3741 (1993).
doi: 10.1016/0379-6779(93)90506-R
Escher, I., A. Ferrero, G., Goktas, M. & Adelhelmm, P. In situ (operando) electrochemical dilatometry as a method to distinguish charge storage mechanisms and metal plating processes for sodium and lithium ions in hard carbon battery electrodes. Adv. Mater. Interfaces 9, 2100596 (2022).
doi: 10.1002/admi.202100596
Li, Q. et al. Unraveling the key atomic interactions in determining the varying li/na/k storage mechanism of hard carbon anodes. Adv. Energy Mater. 12, 2201734 (2022).
doi: 10.1002/aenm.202201734
Wang, B., Fielding, A. J. & Dryfe, R. A. W. In situ electrochemical electron paramagnetic resonance spectroscopy as a tool to probe electrical double layer capacitance. Chem. Commun. 54, 3827–3830 (2018).
doi: 10.1039/C8CC00450A
Wandt, J., Jakes, P., Granwehr, J., Eichel, R. A. & Gasteiger, H. A. Quantitative and time-resolved detection of lithium plating on graphite anodes in lithium ion batteries. Mater. Today 21, 231–240 (2018).
doi: 10.1016/j.mattod.2017.11.001
Tommasini, M., Castiglioni, C., Zerbi, G., Barbon, A. & Brustolon, M. A joint Raman and EPR spectroscopic study on ball-milled nanographites. Chem. Phys. Lett. 516, 220–224 (2011).
doi: 10.1016/j.cplett.2011.09.094
Barbon, A. & Brustolon, M. An EPR study on nanographites. Appl. Mag. Res. 42, 197–210 (2012).
doi: 10.1007/s00723-011-0285-6
Smith, C. I. et al. Electron spin resonance investigation of hydrogen absorption in ball-milled graphite. J. Phys. Chem. C. 113, 5409–5416 (2009).
doi: 10.1021/jp809902r
Wang, B., Fielding, A. J. & Dryfe, R. A. W. Electron paramagnetic resonance investigation of the structure of graphene oxide: pH-dependence of the spectroscopic response. ACS Appl. Nano Mater. 2, 19–27 (2019).
doi: 10.1021/acsanm.8b01329
Ćirić, L. et al. Defects and localization in chemically-derived graphene. Phys. Rev. B 86, 195139 (2012).
doi: 10.1103/PhysRevB.86.195139
Diamantopoulou, Α, Glenis, S., Zolnierkiwicz, G., Guskos, N. & Likodimos, V. Magnetism in pristine and chemically reduced graphene oxide. J. Appl. Phys. 121, 043906 (2017).
doi: 10.1063/1.4974364
Wang, B., Likodimos, V., Fielding, A. J. & Dryfe, R. A. W. In situ electron paramagnetic resonance spectroelectrochemical study of graphene-based supercapacitors: comparison between chemically reduced graphene oxide and nitrogen-doped reduced graphene oxide. Carbon 160, 236–246 (2020).
doi: 10.1016/j.carbon.2019.12.045
Origin(Pro), Version 2023 (OriginLab Corporation, Northampton, MA, 2022).
Yamamoto, T. et al. Structural and electrochemical properties of hard carbon negative electrodes for sodium secondary batteries using the Na[FSA]–[C3C1pyrr][FSA] ionic liquid electrolyte. Electrochemistry 85, 391–396 (2017).
doi: 10.5796/electrochemistry.85.391
Walton, J., Wincott, P., Fairley, N. & Carrick. A. Peak Fitting with CasaXPS: A Casa Pocket Book (Accolyte Science, 2010).
Archibald, R. K. et al. Classifying and analyzing small-angle scattering data using weighted k nearest neighbors machine learning techniques. J. Appl. Crystallogr. 53, 326–334 (2020).
doi: 10.1107/S1600576720000552
Sitaram, V., Sharma, A., Bhat, S. V., Mizoguchi, K. & Menon, R. Electron spin resonance studies in the doped polyaniline PANI-AMPSA: evidence for local ordering from linewidth features. Phys. Rev. B 72, 035209 (2005).
doi: 10.1103/PhysRevB.72.035209