DOI: 10.1063/1.1556092. The first <i>in situ</i> Li7 nuclear magnetic resonance study of lithium insertion in hard-carbon anode materials for Li-ion batteries

The first in situ Li7 nuclear magnetic resonance study of lithium insertion in hard-carbon anode materials for Li-ion batteries

10.1063/1.1556092

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We show the first continuous in situ static Li7 nuclear magnetic resonance (NMR) experiment on a plastic lithium/carbon cell. The electrochemical cycling was successfully performed inside the magnet. We particularly studied the insertion/extraction of lithium in a material designed to be used as negative electrode in a secondary battery; hard carbon fibers treated to reduce the irreversible capacity (x=0.5). The reversible capacity is x=1.5 (in LixC6), higher than with graphite for which the saturating composition corresponds to the first stage intercalation compound LiC6 (x=1). Ex situ quantitative transmission electron microscopy gives a statistical description of the fibers; a core made of disorganized carbon coated by better organized pyrocarbon. Crossed with the values of capacity given by the current generator, in situ NMR indicates the chronology of the insertion. From the observed data, we propose that a Li–C metallic alloy is formed. By comparing the Knight shift with that of metal (Li0), we estimate the charge transfer from Li to C. Amongst the two types of lithium found, the first might be assigned to Li intercalating (Li+0.66) into the smallest spaces between the graphene layers. The second represents most of the reversible lithium and is assigned to be quasimetallic (Li+0.1). Its longitudinal relaxation time T1 is also near-metallic. The quality of this carbon comes from its ability to host such a species.

Bibliography

Letellier, M., Chevallier, F., Clinard, C., Frackowiak, E., Rouzaud, J.-N., BÃ©guin, F., Morcrette, M., & Tarascon, J.-M. (2003). The first in situâLi7 nuclear magnetic resonance study of lithium insertion in hard-carbon anode materials for Li-ion batteries. The Journal of Chemical Physics, 118(13), 6038â6045.

Authors 8

Michel Letellier (first)
Frédéric Chevallier (additional)
Christian Clinard (additional)
Elzbieta Frackowiak (additional)
Jean-Noël Rouzaud (additional)
François Béguin (additional)
Mathieu Morcrette (additional)
Jean-Marie Tarascon (additional)

References 32 Referenced 111

10.1016/S0013-4686(00)00333-9 / Electrochim. Acta (2000)
10.1016/S0013-4686(99)00198-X / Electrochim. Acta (1999)
10.1149/1.2131244 / J. Electrochem. Soc. (1978)
10.1139/p82-040 / Can. J. Phys. (1982)
10.1149/1.2043869 / J. Electrochem. Soc. (1995)
10.1016/0378-7753(94)02035-2 / J. Power Sources (1995)
10.1016/0022-0728(89)80122-6 / J. Electroanal. Chem. Interfacial Electrochem. (1989)
10.1016/S0022-0728(97)00296-9 / J. Electroanal. Chem. (1997)
10.1016/S0167-2738(98)00411-1 / Solid State Ionics (1999)
10.1016/S0022-0728(00)00197-2 / J. Electroanal. Chem. (2000)
10.1016/S0378-7753(00)00435-3 / J. Power Sources (2000)
{'key': '2024020706293907100_r12'}
10.1016/0025-5416(77)90032-5 / Mater. Sci. Eng. (1977)
10.1149/1.1392009 / J. Electrochem. Soc. (1999)
10.1016/S0378-7753(00)00591-7 / J. Power Sources (2001)
10.1016/S0167-2738(97)00520-1 / Solid State Ionics (1998)
10.1080/10587259408051661 / Mol. Cryst. Liq. Cryst. (1994)
10.1016/0378-7753(95)80036-G / J. Power Sources (1995)
{'key': '2024020706293907100_r19', 'first-page': '165', 'volume': '97–98', 'year': '2001', 'journal-title': 'J. Power Sources'} / J. Power Sources (2001)
{'key': '2024020706293907100_r20', 'first-page': '317', 'volume': '81–82', 'year': '1999', 'journal-title': 'J. Power Sources'} / J. Power Sources (1999)
10.1016/S0378-7753(96)02560-8 / J. Power Sources (1997)
10.1016/S0167-2738(99)00290-8 / Solid State Ionics (2000)
10.1016/S0022-2860(97)00296-2 / J. Mol. Struct. (1998)
10.1021/jp000892p / J. Phys. Chem. A (2001)
{'key': '2024020706293907100_r25', 'first-page': '143', 'volume': '97–98', 'year': '2001', 'journal-title': 'J. Power Sources'} / J. Power Sources (2001)
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{'key': '2024020706293907100_r27', 'first-page': '49', 'volume': '86–88', 'year': '1996', 'journal-title': 'Solid State Ionics'} / Solid State Ionics (1996)
{'key': '2024020706293907100_r28'}
{'key': '2024020706293907100_r29', 'first-page': '229', 'volume': '77–78', 'year': '2002', 'journal-title': 'Fuel Process. Technol.'} / Fuel Process. Technol. (2002)
{'key': '2024020706293907100_r30'}
10.1016/0025-5416(77)90036-2 / Mater. Sci. Eng. (1977)
{'key': '2024020706293907100_r32'}

Dates

Type	When
Created	22 years, 5 months ago (March 20, 2003, 6:17 p.m.)
Deposited	1 year, 6 months ago (Feb. 7, 2024, 5:49 a.m.)
Indexed	2 months, 2 weeks ago (June 18, 2025, 5:24 a.m.)
Issued	22 years, 5 months ago (April 1, 2003)
Published	22 years, 5 months ago (April 1, 2003)
Published Print	22 years, 5 months ago (April 1, 2003)

Funders 0

None

BibTeX

@article{Letellier_2003, title={The first in situ Li7 nuclear magnetic resonance study of lithium insertion in hard-carbon anode materials for Li-ion batteries}, volume={118}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1556092}, DOI={10.1063/1.1556092}, number={13}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Letellier, Michel and Chevallier, Frédéric and Clinard, Christian and Frackowiak, Elzbieta and Rouzaud, Jean-Noël and Béguin, François and Morcrette, Mathieu and Tarascon, Jean-Marie}, year={2003}, month=apr, pages={6038–6045} }

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