A critical review presentation

on

Porous ZnCo2O4 Nanowires Synthesis via Sacrificial Templates: High Performance Anode Materials of Li-Ion Batteries Liby

Anita G Sharma
Under Guidance of

Prof. G.D.Yadav

Introduction:
Li-Ion battery: Need for improvement in capacity and efficiency y Use of transition metal oxides y Development of environmental friendly metal oxides y Development of one dimensional nanostructured metal oxides for improvement in electrochemical performance.
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Experiment:
Development of a microemulsion based technique by using reagents CTAB (1 gram) (Cetyltrimethylammonium bromide) Cyclohexane (35 mL) n-Pentanol (1.5 mL) 1 M H2C2O4 (2mL) aqueous solution Mixture of 0.05M Zn(NO3) and 0.1 M Co(NO3)2 (1.25mL) y Template obtained: ZnCo2 (C2O4)3 y Precipitates heated at 500-700 oC for three hours to obtain final product.
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Important features of the paper

Production of 1D nanowires via a sacrificial template using microemulsion technique with well controlled dimensions. y Porous 1D nanowires with large surface area were responsible for superior performance. y Surface of nanowires formed were smooth with no isolated nanoparticles. y Reversible capacities of nanowires were higher than nanoparticles
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Porous nanowires synthesized at 500oC showed larger capacity and better cycling performance than at 700oC because of larger surface area and high porosity. y Initial coulombic efficiency was 82% which was due to formation of Solid electrolyte interphase film
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Literature survey
Replacement of carbon anodes with transition metal oxides. y Need for organizing nanomaterial on a template. y Different oxides that can be used as anode material for Li-ion batteries(e.g. silicon oxide, manganese oxide, iron oxide, cobalt oxide & nickel oxide) y Nanotubes one of the promising structures for Li-Ion batteries but initial Coulombic efficiency of around 70%. y Spinel structure for nanowires used as they act as efficient catalysts.
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ZnCo2O4 as an attractive material for anode material of Li-Ion batteries. y Chemical Reactions: ZnCo2O4 + 8Li++8e Zn+ 2Co + 4 Li2O Zn + Li++e LiZn Zn + Li2O ZnO+ 2Li++2e 2Co + 2Li2O 2CoO+ 4Li++4e 2CoO+ 2/3Li2O 2/3Co3O4 + 4/3Li++ 4/3e
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Originality
Work done is modification and extension to the other researches carried out. y Modification is the synthesis of ZnCo2O4 nanowires at different annealing temperatures.
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Assumptions
Large surface area of 1D nanowires responsible for good performance and high capacity. y Higher surface area at 500oC due to smaller diameters and larger quantities of nanocrystals and nanopores. y ZnCo2O4 nanowires give superior performance in comparison to ZnCo2O4 nanoparticles
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Technical correctness
Microemulsion technique with advantage of Biocompatibility and biodegradability. y No fact supporting the statement that ZnCo2O4 nanowires have better capacity compared to ZnCo2O4 nanoparticles. y Effect of temperature on morphology is discussed but effect of time is not discussed. y Some typographical errors like Colombic efficiency instead of Coulombic efficiency. y Difficulty in synthesizing Spinel structure. y Aging and annealing of precipitates formed by microemulsion.
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The apparatus used is not mentioned. y Substrate used not mentioned. y No sample treatment done with variation of aging times and different CTAB concentration.
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Typographica l errors

Irrelevant reference

Wrong reference citing

Bibliography

Wrong year of publication Wrong information about the references

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Not citing references where needed

Title/abstract
Abstract same as that of conclusions. y Title inappropriate as it does clearly define the process y Title mentions the use of sacrificial templates but the use of only one template is made. y Suitable title suggested ZnCo2O4 synthesis by annealing ZnCo2 (C2O4)3 template; used as anode in Li-Ion batteries.
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Illustrations and tables

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Too many figures when things can be made clear by a few figures.

Figure showing XRD pattern of product prepared by calcination of ZnCo2 (C2O4)3 . The x-axis of the graph does not specify units used

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The graph depicts voltammogram curves of electrodes made from ZnCo2O4. Herein the x-axis of the graph is not defined which makes the validity of the plot unsure.
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Above is a plot of capacity versus cycle number for porous ZnCo2O4 synthesized at 500 & 700 oC. There is a slight increase in the capacity after 5-6 cycles and then the capacity fairly remains a constant. This slight increase in value is not clarified

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Alternative Interpretations
Comparison of nanowires with nanoparticle but not with nanotubes y Need for further research.
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Conclusions
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Work could not clearly explain as to with what the comparisons where made

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References:
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Poizot P., Laruelle S., Grugeon S., Dupont L., Tarascon J M., Nature Volume 407, 496-499, 2000 Lee H.W., Muralidharan P., Ruffo R., Mari C M., Cui Y., Kim D K., Nano Lett., 3852-3856, 2010. Murphy C J., Science Volume 298, 2139-2141, 2002. Arico A S., Bruce P., Scrosati B., Tarascon J M., Schalkwijk W V., Nature Materials 4, 366-375, 2005. Nam K. T., Kim D. W., Yoo P. J., Chiang C Y., Meethong N. L., Hammond P T., Chiang Y M., Belcher A. M., Science, 312, 885-888, 2006. Cao M., Hu C., Wang E., J Am. Chem. Soc., 11196-11197, 2003. Chan C K., Peng H L., Liu G., Mcilwrath K., Zhang X F., Huggins R. A., Cui Y., Nature Nanotechnology, 3, 31-34, 2008
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y y y

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Yu Y., Chen C H., Shui J L., Xie S., Angew. Chem., Int. Ed. 44,7085-7089,2005 Li W Y., Xu L N., Chen J., Adv. Funct. Mater., 15, 851-856, 2005. Du N., Zhang H., Chen B D., Wu J B., Ma X Y., Liu Z H., Zhang Y. Q., Yang D R., Huang X H., Tu J P., Adv. Mater., 19, 4505-4509, 2007 Wang G., Gao X. P., Shen P W., J. Power Sources, 192, 719-723, 2009. Kang Y M., Kim K T., Kim J H., Kim H S., Lee P S., Lee J Y., Liu H K., Dou S X , J. Power Sources, 133, 252-259, 2004 Chu Y Q., Fu Z W., Qin Q Z., Electrochim. Acta., 49, 4915-4921, 2004. Wei X H., Chen D H., Tang W J., Mater. Chem. Phys., 103, 54-58, 2007 Ai C C., Yin M C., Wang C W., Sun J T., J. Mater. Sci., 39, 10771079, 2004 Fan H J., Knez M., Scholz R., Nielsch K., Pippel E., Hesse D., Zacharias M., Gosele U., Nat. Mater, 5, 627-631, 2006 Shamara Y., Shamara N., Rao., G V S., Chowdari B. V., R. Adv. Funct. Mater., 17, 2855-2861, 2007. Bhushan B., Springer Handbook of nanotechnology,40-115, 2007 20