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Synchrotron crystal and local structures, microstructure, and electrical characterization of Cu-doped LiFePO4/C via dissolution method with ironstone as Fe source

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Abstract

Powders of lithium iron phosphate (LFP) with Cu doping and carbon coating were prepared by a dissolution method using Fe sourced from natural ironstone. Two dopant amounts were used, 2 and 3 at.% while the carbon coating used carbonization with 9 wt.% citric acid. Synchrotron X-ray diffraction (XRD), Fe K-edge X-ray absorption spectroscopy (XAS), and scanning electron microscopy (SEM) were used to reveal the crystal and local structures and grain morphology of the formed phase. Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and charge–discharge (CD) measurements were carried out to determine the electrical properties of the samples. According to the XRD and XAS data, LFP was the main phase in all samples with Fe coordination number 6 and an oxidation number of 2+. Small amounts of hematite were detected in the doped and carbonized samples. SEM images of the 2 and 3 at.% Cu-doped samples showed a spherical morphology with clear grain boundaries, whereas carbonization resulted in smaller grain sizes. XAS analysis showed that Cu doping increased the distance between Fe as the absorbing atom and its nearest-neighbor atoms, while carbon coating reduced it. The EIS and CD tests showed that Cu doping and carbonization increased the conductivity up to 10 times and the specific capacity up to 50 times for the undoped and uncarbonized samples. The CV curves showed that Cu doping and carbonization provided better intercalation, deintercalation, and reversibility properties of LFP as shown by the smallest potential difference at a value as low as 0.2 V. The changes in the electrical properties are explained in terms of the LFP structures.

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Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors thank the Ministry of Education, Culture, Research and Technology (KEMDIKBUDRISTEK) and the ITS Research and Community Service Institute (DRPM) who have funded this research in the PMDSU program No. 820/PKS/ITS/2018 which was given to CL under the supervision of SP. We would also thank the SLRI Thailand and its staff at BL 1.1W and BL 8 for providing XRD and XAS facilities through Beam Time Project Numbers 6447 and 2618. We also thank the late Dr. Bambang Prihandoko from the Research Center for Physics—National Research and Innovation Agency, who provided supervision in the manufacture of coin cell batteries and testing their electrical properties.

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Authors and Affiliations

  1. Department of Physics, Institut Teknologi Sepuluh Nopember, Surabaya, 60111, Indonesia

    Chaironi Latif, Amalia Firdausi, Nihlatunnur Nihlatunnur, Mochamad Zainuri & Suminar Pratapa

  2. Department of Electrical Engineering, Institut Teknologi Telkom Surabaya, Surabaya, 60234, Indonesia

    Chaironi Latif

  3. Synchrotron Light Research Institute (Public Organization), Nakhon Ratchasima, 30000, Thailand

    Chatree Saiyasombat & Wantana Klysubun

  4. Research Center for Physics - National Research and Innovation Agency, Puspiptek Serpong Gd. 442 South Tangerang, Banten, 15314, Indonesia

    Achmad Subhan

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Contributions

Conceptualization and methodology: CL, MZ, SP; formal analysis: CL, CS, SP; investigation: CL, AF, NN, CS, WK, AS, SP; writing—original draft: CL; resources: CL, AF, NN, CS, WK, AS; data curation: CL, AF, NN: writing—review and editing: CS, SP; supervision: MZ, SP; funding acquisition: CL, SP; project administration: SP.

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Latif, C., Firdausi, A., Nihlatunnur, N. et al. Synchrotron crystal and local structures, microstructure, and electrical characterization of Cu-doped LiFePO4/C via dissolution method with ironstone as Fe source. J Mater Sci: Mater Electron 33, 17722–17732 (2022). https://doi.org/10.1007/s10854-022-08635-6

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