Manoj K. Jangid

Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance.

Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal structure, band gap and micro structure of the CZTS thin films are affected by the substitution of anion/cations. Moreover, secondary phases are not observed and grain sizes are enhanced significantly with selenium doping (grain size ~1 μm). The earth-abundant Cu2MSnS4/Se4 (M = Zn, Mn and Fe) nanoparticles have band gaps in the range of 1.04–1.51 eV with high optical-absorption coefficients (~104 cm−1) in the visible region. The power conversion efficiency of a CZTS solar cell is enhanced significantly, from 0.4% to 7.4% with selenium doping, within an active area of 1.1 ± 0.1 cm2. The observed changes in the device performance parameters might be ascribed to the variation of optical band gap and microstructure of the thin films. The performance of the device is at par with sputtered fabricated films, at similar scales.

Understanding the Li-storage in few layers graphene with respect to bulk graphite: experimental, analytical and computational study

In order to understand, clarify and provide confirmations in the contexts of the prevalent confusions concerning Li-storage in graphenic carbon (viz. the reduced dimensional scale of graphitic carbon), electrochemical lithiation/delithiation has been performed with CVD-grown fairly pristine well-ordered few-layer graphene films (FLG; ∼7 layers; as a model material). Chronopotentiograms and cyclic voltammograms recorded with the FLG present distinct features corresponding to the transformation between different Li-GICs (i.e., ‘staging’) below 0.3 V against Li/Li+, thus confirming that ‘classical’ Li-intercalation does occur even at such reduced dimensional (nano)scale. Nevertheless, even in this lower potential window (our main focus here), Li-storage in FLG involves contributions from both diffusion- and surface-controlled mechanisms. The Li-capacities recorded with FLG just within this lower potential window, and also upon subtracting any possible contribution from the Cu current collector, were still ∼3–4 times greater than those obtained with similarly grown thicker bulk graphite films (TBG: ∼450 nm; Li-capacity recorded: ∼380 mA h g−1). Contrary to the usual belief, the excess Li-capacity of FLG cannot be explained by the presence of extrinsic/intrinsic defects, which are nearly negligible in the FLG films under consideration. Simulation of Li-storage in graphene via DFT indicated that the excess capacity (after formation of the LiC6 configuration) is associated with additional stable Li-storage on the outer graphene surfaces in the forms of more than one Li-layer (but different from Li-plating) and segregation close to the ‘stepped’ (exposed) edges of the inner graphene layers (but not exactly at the edge sites). Overall, such predicted Li-storage mechanisms are in agreement with the experimentally observed contributions from both ‘classical’ Li-intercalation and surface-controlled processes (even at potentials below 0.3 V), which primarily account for the excess Li-capacities recorded with graphenic carbon.

Optimization of lithium content in LiFePO4 for superior electrochemical performance: the role of impurities

Carbon coated LixFePO4 samples with systematically varying Li-content (x = 1, 1.02, 1.05, 1.10) have been synthesized via a sol–gel route. The Li : Fe ratios for the as-synthesized samples is found to vary from ∼0.96 : 1 to 1.16 : 1 as determined by the proton induced gamma emission (PIGE) technique (for Li) and ICP-OES (for Fe). According to Mossbauer spectroscopy, sample Li1.05FePO4 has the highest content (i.e., ∼91.5%) of the actual electroactive phase (viz., crystalline LiFePO4), followed by samples Li1.02FePO4, Li1.1FePO4 and LiFePO4; with the remaining content being primarily Fe-containing impurities, including a conducting FeP phase in samples Li1.02FePO4 and Li1.05FePO4. Electrodes based on sample Li1.05FePO4 show the best electrochemical performance in all aspects, retaining ∼150 mA h g−1 after 100 charge/discharge cycles at C/2, followed by sample Li1.02FePO4 (∼140 mA h g−1), LiFePO4 (∼120 mA h g−1) and Li1.10FePO4 (∼115 mA h g−1). Furthermore, the electrodes based on sample Li1.05FePO4 retain ∼107 mA h g−1 even at a high current density of 5C. Impedance spectra indicate that electrodes based on sample Li1.05FePO4 possess the least charge transfer resistance, plausibly having influence from the compositional aspects. This low charge transfer resistance is partially responsible for the superior electrochemical behavior of that specific composition.

Crystalline core/amorphous shell structured silicon nanowires offer size and structure dependent reversible Na-storage

One of the major bottlenecks towards the development of the Na-ion battery system is that graphitic carbon (the commonly used anode material for the Li-ion system) is not suitable for use in Na-ion system. Accordingly, in the pursuit to identify and develop a suitable anode material for the upcoming Na-ion battery system, we report here the feasibility of reversible electrochemical Na-alloying in core/shell-structured Si nanowires having crystalline (c-Si) core and amorphous (a-Si) shell. Vapor–liquid–solid mechanism during nanowire growth allowed systematic variations of the a-Si shell thickness around the c-Si core of constant diameter (∼25 nm; as per the size of Sn catalyst-cum-‘nano-template’ particles). This allowed the development of four different sets of nanowires having overall diameters varying between ∼40 (SiNW-40) and ∼460 nm (SiNW-460); thus providing platforms also for investigating the influences of the dimensional scale and structure of Si (viz., amorphous vs. crystalline) towards Na-storage. While negligible reversible Na-capacity could be recorded with the thickest nanowire set, significantly greater Na-capacities could be recorded upon reduction in the overall diameter; leading to a reversible Na-capacity of ∼390 mA h g−1 for the thinnest nanowire set (i.e., SiNW-40), which is also the highest reported to-date for ‘stand-alone’ Si-based electrodes. Shortened Na-transport distance through the a-Si shell and increased influence of the more conductive c-Si core towards the lowering of charge transfer resistance, with reduced nanowire thickness, are the causes for such a remarkable dimensional effect. Experimental evidences and analytical computational studies indicate that Na-capacity gets contributed primarily by the ‘bulk’ of the amorphous Si shell, but (interestingly) not by the crystalline Si core.

Li metal battery, heal thyself

Intermittent high-current pulses prevent battery failure In the 1970s, scientists first developed a promising class of rechargeable batteries in which lithium (Li) metal served as the anode and compounds that could reversibly host Li ions inside the lattice formed the cathode (1). Because Li is the lightest and most electropositive metal, this setup allows very high energy and power densities. However, repeated discharge-charge cycles cause growth of Li dendrites from the anode toward the cathode. Such dendrites can eventually penetrate the separator (placed to prevent contact between the electrodes) and touch the cathode, causing short circuiting of the cell and potentially leading to safety hazards (2–5). On page 1513 of this issue, Li et al. (6) show that Li dendrite growth can be suppressed by applying short, intermittent high-current pulses during battery use. These pulses lead to self-healing of the dendrites.