3-D vertically aligned few-layered graphene (FLGs) nanoflakes synthesised using microwave plasma enhanced chemical vapour deposition are melt-impregnated with partially reduced graphene oxide-sulfur (PrGO-S) nanocomposites for use in lithium–sulfur batteries. The aligned structure and the presence of interconnected micro voids/channels in the 3-D FLG/PrGO-S electrodes serves as template not only for the high sulfur loading (up to 80 wt%, areal loading of 1.2 mg cm−2) but also compensates for the volume changes occurring during charge–discharge cycles. The inter-connectivity of the electrode system further facilitates fast electronic and ionic transport pathways. Consequently, the binder-free 3-D FLG/PrGO-S electrodes display a high first-cycle capacity (1320 mA h g−1 at C/20), along with excellent rate capability of ∼830 mA h g−1 and 700 mA h g−1 at 2C and 5C rates, respectively. The residual functional groups of PrGO (–OH, –C–O–C– and –COOH) facilitate fast and reversible capture of Li+ ions while confining the polysulfide shuttles, thus, contributing to excellent cycling capability and retention capacity. The 3D electrodes demonstrate excellent capacity retention of ∼80% (1040 mA h g−1 at C/10) over 350 charge–discharge cycles. Comparatively, the 2-D planar PrGO-S electrodes displayed poor electronic conductivity and can only provide 560 mA h g−1 after 150 cycles, thereby further highlighting the vital role of the electrode morphology in improving the electrochemical performance of Li–S batteries.@en

One of the main goals in lithium ion battery electrode design is to increase the power density. This requires insight in the relation between the complex heterogeneous microstructure existing of active material, conductive additive and electrolyte providing the required electronic and Li-ion transport. FIB-SEM is used to determine the three phase 3D morphology, and Li-ion concentration profiles obtained with Neutron Depth Profiling (NDP) are compared for two cases, conventional LiFePO₄ electrodes and better performing carbonate templated LiFePO₄ electrodes. This provides detailed understanding of the impact of key parameters such as the tortuosity for electron and Li-ion transport though the electrodes. The created hierarchical pore network of the templated electrodes, containing micron sized pores, appears to be effective only at high rate charge where electrolyte depletion is hindering fast discharge. Surprisingly the carbonate templating method results in a better electronic conductive CB network, enhancing the activity of LiFePO₄ near the electrolyte-electrode interface as directly observed with NDP, which in a large part is responsible for the improved rate performance both during charge and discharge. The results demonstrate that standard electrodes have a far from optimal charge transport network and that significantly improved electrode performance should be possible by engineering the microstructure.

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