Lepidocrocite Titanate–Graphene Composites for Sodium-Ion Batteries

Barim, Gözde; Yin, Wei; Lin, Jason; Song, Chengyu; Kuykendall, Tevye R.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; Marschilok, Amy C.; Doeff, Marca M.

doi:10.1021/acs.jpcc.2c06180

Lepidocrocite Titanate–Graphene Composites for Sodium-Ion Batteries

Journal Article · Wed Nov 02 00:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c06180· OSTI ID:1992079

Barim, Gözde ^[1]; Yin, Wei ^[1]; Lin, Jason ^[1]; Song, Chengyu ^[2]; Kuykendall, Tevye R. ^[2]; ^[3]; ^[3]; ^[3]; ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Stony Brook Univ., NY (United States). Institute for Electrochemically Stored Energy; Brookhaven National Laboratory (BNL), Upton, NY (United States)

To overcome electronic transport issues of layered titanates in sodium-ion batteries, we have designed and synthesized composites of lepidocrocite titanates with reduced graphene oxide through a solution-based self-assembly approach. The parent lepidocrocite titanate (K_0.8[Ti_1.73Li_0.27]O₄) was exfoliated by a soft-chemical approach and mechanical shaking. Exfoliated layered titania sheets (LTO) were then combined with reduced graphene oxide (rGO) layers to assemble into composites through flocculation. Countercations (i.e., Mg²⁺) were used for the self-assembly of negatively charged titania and rGO nanosheets via flocculation. The carbon content in the composites was tuned from 1 to 17% by changing the ratio of titania and rGO sheets in the mixed colloidal suspensions. Electrodes were processed with as-prepared LTO-rGO composites without any carbon additives and tested in sodium half-cell configurations. Mg⁺-coagulated LTO-rGO composite electrodes deliver higher capacities than electrodes prepared with coagulated titania sheets and 10% acetylene black in sodium half-cells and display good capacity retention after 50 cycles. Electrochemical impedance spectroscopy results indicate lower charge transfer resistance for LTO-14.5%rGO composites than that of coagulated titania sheets with 10% acetylene black. A power law analysis of cells containing the composites indicate a hybrid mechanism consisting of both surface and diffusional processes. A comparison with a similar system, that of dopamine-derived LTO-C heterostructures, reveal significant differences. While capacities showed a strong dependence on carbon content for the dopamine-derived materials, this was not true for the LTO-rGO composites. Instead, the highest capacity was obtained for the 14.5% rGO sample, with a lower value obtained for the 17% rGO sample. A greater proportion of the redox processes were surface rather than diffusional in nature for the LTO-rGO composites as well.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0012673; AC02-76SF00515

OSTI ID:: 1992079

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 45 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Sodium-ion batteries
intercalation anodes
lepidocrocite titanates
reduced graphene oxide
self-assembly

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