Research ArticleELECTROPLATING

Electroplating lithium transition metal oxides

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Science Advances  12 May 2017:
Vol. 3, no. 5, e1602427
DOI: 10.1126/sciadv.1602427
  • Fig. 1 Cyclic voltammetric and electrochemical modeling of KOH-LiOH-CoO eutectic systems.

    (A) CVs of CNF in pure and CoO-containing LiOH-KOH melts. (B) CVs of Co and Pt foils in pure LiOH-KOH melt. (C) CVs of Ni foil in pure and CoO-containing LiOH-KOH melts. (D) Potential-pH2O diagram of the LiOH-KOH-CoO eutectic system. (E) Schematic illustration of electrodeposition process. All the CV measurements start from an oxidative scan.

  • Fig. 2 Characterizations of electroplated LiCoO2.

    (A) Diffraction patterns collected from the edge (1) and center (2) of an as-prepared LiCoO2 flake and (B) its transmission electron microscopy (TEM) image. Diffraction mapping of (C) non-O3 (intensity multiplied by a factor of 20) and (D) O3 phases. a.u., arbitrary units. (E) Diffraction patterns of spots from the edge (1) and the center (2) of an annealed LiCoO2 flake and (F) its TEM image. Diffraction patterns of (G) non-O3 (intensity multiplied by a factor of 20) and (H) O3 phases after annealing. XRD (I) and Raman spectroscopy (J) of the LiCoO2 electrode. (K) Charge/discharge voltage profiles. Inset: |dQ/dV| of the LiCoO2 cathode (electroplated on an Al foil) versus a lithium electrode. (L) Cycling of the electrodeposited LiCoO2 cathode versus a Li electrode at 1 C.

  • Fig. 3 Morphology of LiCoO2 electroplated on various substrates.

    (A) SEM images of planar LiCoO2 films (~20% porosity) electroplated on both sides of an Al foil. (B) Higher-magnification view of the LiCoO2 coating. (C) Optical images of LiCoO2 electroplated on the Al foil and this electrode rolled into a 5-mm-diameter tube (inset). SEM images of the open-cell carbon foam (D) and the LiCoO2/carbon foam electrode (E). (F) Lower-magnification view of a ~0.5-mm-thick LiCoO2/carbon foam electrode, with LiCoO2 plated uniformly throughout the foam. SEM images of the 3D CNF scaffold (G) and the LiCoO2 electrodes electroplated on this scaffold with ~1 mA·hour cm−2 loading (H) and ~3 mA·hour cm−2 loading (I).

  • Fig. 4 Electrochemical and flexural properties of LiCoO2 electrodes.

    Electrochemical performance of a full pouch cell consisting of a LiCoO2/Al foil cathode and a conventional anode: (A) capacity retentions of the full cell at varied discharge rates and (B) cycling of the full cell at 1 C. (C) Capacity retentions of a ~20 mA·hour cm−2 LiCoO2/carbon foam electrodes at varied discharge rates. (D) Capacity retentions of a ~1.1 mA·hour cm−2 LiCoO2/CNF electrodes at varied discharge rates. (E) Capacity retention of the LiCoO2/CNF-based and LiCoO2 slurry–based full cells after cyclic bending of 180° to an ~5-mm radius. (F) Energy density and flexural performance of our and other flexible batteries. LCO, lithium cobalt oxide; PMTA, pyromellitic dianhydride-tris(2-aminoethyl)amine; LTO, lithium titanium oxide; LMO, lithium manganese oxide; LFP, lithium iron phosphate.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/5/e1602427/DC1

    section SI. Plating bath and solubility of transition metal oxides.

    section SII. Mesoporous carbon foam.

    section SIII. Flexible carbon scaffold.

    section SIV. Quasi-reference electrode.

    section SV. Thermodynamic modeling.

    section SVI. Crystallography of LiCoO2.

    section SVII. Scanning electron nanobeam diffraction.

    section SVIII. Flexible battery.

    section SIX. Electrodeposition of spinel LiMn2O4.

    section SX. Electroplating of Al-doped lithium cobalt oxide.

    section SXI. Calculation of energy density of flexible batteries.

    fig. S1. Schematic illustration of a flexible CNF.

    fig. S2. High-resolution TEM images of the CNF.

    fig. S3. High-resolution TEM image and electron diffraction pattern of an electroplated LiCoO2 crystal flake.

    fig. S4. Crystallographic structures of O3-, O2-, and spinel-phase lithium cobalt oxides and two superstructures with lithium staging and 2 × 2 periods.

    fig. S5. Illustration of the SEND technique.

    fig. S6. Cross-sectional SEM image of ~200-μm-thick LiCoO2 electroplated on an Al foil.

    fig. S7. Charge/discharge voltage profiles of the CNF anode.

    fig. S8. Charge/discharge curves of a LiCoO2/CNF flexible battery.

    fig. S9. Optical images of bending tests.

    fig. S10. Schematic illustrations of the structure difference between traditional and electroplated flexible batteries.

    fig. S11. SEM images of a LiCoO2/CNF cathode before and after 1000 bending cycles.

    fig. S12. Materials and electrochemical characterization of the electroplated LiMn2O4/CNF battery.

    fig. S13. The Gibbs free energy of the formation from the elements for LiMnO2.

    fig. S14. The Gibbs free energy of LiMnO2.

    fig. S15. The potential-pH2O diagram of the LiOH-KOH-MnO-H2O melt system.

    fig. S16. Materials and electrochemical characterization of the electroplated Al-doped LiCoO2.

    table S1. Thermodynamic data used for the LiOH-KOH-CoO system at 260°C.

    table S2. Thermodynamic data of the LiOH-KOH-MnO system at 25°C.

    table S3. Thermodynamic data of the LiOH-KOH-MnO system at 300°C.

    References (4282)

  • Supplementary Materials

    This PDF file includes:

    • section SI. Plating bath and solubility of transition metal oxides.
    • section SII. Mesoporous carbon foam.
    • section SIII. Flexible carbon scaffold.
    • section SIV. Quasi-reference electrode.
    • section SV. Thermodynamic modeling.
    • section SVI. Crystallography of LiCoO2.
    • section SVII. Scanning electron nanobeam diffraction.
    • section SVIII. Flexible battery.
    • section SIX. Electrodeposition of spinel LiMn2O4.
    • section SX. Electroplating of Al-doped lithium cobalt oxide.
    • section SXI. Calculation of energy density of flexible batteries.
    • fig. S1. Schematic illustration of a flexible CNF.
    • fig. S2. High-resolution TEM images of the CNF.
    • fig. S3. High-resolution TEM image and electron diffraction pattern of an electroplated LiCoO2 crystal flake.
    • fig. S4. Crystallographic structures of O3-, O2-, and spinel-phase lithium cobalt oxides and two superstructures with lithium staging and 2 × 2 periods.
    • fig. S5. Illustration of the SEND technique.
    • fig. S6. Cross-sectional SEM image of ~200-μm-thick LiCoO2 electroplated on an Al foil.
    • fig. S7. Charge/discharge voltage profiles of the CNF anode.
    • fig. S8. Charge/discharge curves of a LiCoO2/CNF flexible battery.
    • fig. S9. Optical images of bending tests.
    • fig. S10. Schematic illustrations of the structure difference between traditional and electroplated flexible batteries.
    • fig. S11. SEM images of a LiCoO2/CNF cathode before and after 1000 bending cycles.
    • fig. S12. Materials and electrochemical characterization of the electroplated LiMn2O4/CNF battery.
    • fig. S13. The Gibbs free energy of the formation from the elements for LiMnO2.
    • fig. S14. The Gibbs free energy of LiMnO2.
    • fig. S15. The potential-pH2O diagram of the LiOH-KOH-MnO-H2O melt system.
    • fig. S16. Materials and electrochemical characterization of the electroplated Al-doped LiCoO2.
    • table S1. Thermodynamic data used for the LiOH-KOH-CoO system at 260°C.
    • table S2. Thermodynamic data of the LiOH-KOH-MnO system at 25°C.
    • table S3. Thermodynamic data of the LiOH-KOH-MnO system at 300°C.
    • References (42–82)

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