1.

INTRODUCTION:
Several techniques have been devised to improve the capacity and efficiency of the LiIon batteries, among which is the use of 3D transition metal oxides. Amongst the 3D transition metal oxides cobalt oxides (Co3O4, CoO) have shown the highest capacity and the best cyclic performance compared to nickel oxides and iron oxides. However efforts have been made to replace Co3O4 partially by environment friendly and less expensive metal oxides to lower the toxicity and reduce the cost. For this reason ternary cobalt based metal oxide particles like ZnCo2O4, which are larger than Co3O4 particles, have been used as an anode material of Li-Ion batteries. For improving the electrochemical performance one dimensional nanostructured materials have been developed because of their high surface to volume ratio and excellent electronic transport property. ZnCo2O4 1D nanostructure have not been obtained until now because of its spinel structure. The main topic of research carried out by the author is synthesis of ZnCo2O4 nanowires from a microemulsion of ZnCo2 (C2O4)3. The reversible capacity of ZnCo2O4 nanowires is much higher than ZnCo2O4 nanoparticles. The ZnCo2O4 nanowires are obtained from ZnCo2 (C2O4)3 under annelating conditions. Here ZnCo2O4 acts as a sacrificial template for the synthesis of ZnCo2O4. The as- synthesized porus ZnCo2O4 nanowires were applied as anode materials of LiIon batteries, which showed superior capacities and cycling performance. (a) Experimental section: Chemical reagents: a. CTAB (Cetyltrimethylammonium bromide) b. c. d. e. Cyclohexane n-Pentanol 1 M H2C2O4 aqueous solution Mixture of 0.05M Zn(NO3) and 0.1 M Co(NO3)2

(b) Preparation of sacrificial template: One gram of (a) was dissolved in a mixture of 35ml of (b) and 1.5 mL of (c) and stirred for 30 minutes to form a microemulsion. Then, 2mL of reagent (d) was added to the microemulsion and the whole mixture was again stirred for an addition one hour. Finally 1.25 mL of an aqueous solution of reagent (e) was added to the above microemulsion and stirred for 2 hours at room temperature. The precipitates (pink) were obtained by centrifugation and dried in air at 80oC. The precipitates were heated at 500-700oC for 3 hours to obtain the final product (dark grey) (c) Sample characterization: The final product was characterized by using X-ray diffraction (XRD) with monochromized Cu K radiations ( = 1.54178 Angstrom units). The morphology and structure of the samples were examined by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM) with an energy-dispersive X-ray spectrometer (EDX). The BET surface area and pore volume were tested using a Beckman Coulter Omnisorp 100cx.

2. IMPORTANT FEATURES OF THE PAPER:

1. The paper mainly concentrates on production of 1D nanowires via a sacrificial template using microemulsion based technique. 2. A microemulsion based method was developed for synthesizing 1D nanostructures with well controlled dimensions. 3. The porous one dimensional nanostructures and large surface area were found responsible for superior performance. 4. The surface of the nanowires was found to be smooth and no isolated nanoparticles were detected.

5. The reversible capacities of ZnCo2O4 nanowires were found to be much higher than that of ZnCo2O4 nanoparticles. 6. The initial Coulombic efficiency for porous ZnCo2O4 nanowires was found to be 82% which was due to the formation of a Solid electrolyte interphase film and some undecomposed Li2O phase. 7. The porous ZnCo2O4 nanowires synthesized at 500oC showed larger capacity and better cycling performance than prepared at 700oC because of higher porosity and larger surface area.

3. LITERATURE SURVEY:
It is known that rechargeable Li-Ion batteries are the key components for portable equipments. The major hurdle in such batteries is to overcome their disintegrity over many discharge and recharge cycles. So the electrodes made of nanoparticles of transition metal oxides of Ni, Co or Fe was developed. The advantages of metal oxide based Li ion cells over commercially used LiCoO2/C cells are that metal oxides have twice the capacity of Carbon per unit mass and three times its density and six times capacity of carbon per unit volume. [1] Spinel LiMn2O4 is a promising candidate to replace layered Ni or Co oxide materials as cathode in lithium ion batteries because of its intrinsic low-cost, environmental friendliness, high abundance, and better safety. [2] The timing of the reaction controls the products dimensions. Shorter reaction times at optimal cube conditions reduce the nanocube edge lengths to ~70 nm; longer reaction times lead to nanocubes with edges of up to ~175 nm, in a well-controlled manner. [3] There are potential advantages and disadvantages associated with the development of nano electrodes for Lithium batteries.

Advantages include: y Better accommodation of the strain of lithium insertion/removal, improving cycle life
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y y y

New reactions not possible with bulk materials Higher electrode/electrolyte contact area leading to higher charge/discharge rates. Short path lengths for electronic transport (permitting operation with low electronic conductivity or at higher power). Short path lengths for Li+ transport (permitting operation with low Li+ conductivity or higher power).

Disadvantages include: y An increase in undesirable electrode/electrolyte reactions due to high surface area, leading to self-discharge, poor cycling and calendar life. y Inferior packing of particles leading to lower volumetric energy densities unless special compaction methods are developed y Potentially more complex synthesis. [4] Nanostructure material can improve the electrochemical properties of Li-Ion batteries compared to their bulk counterpart but to maximize this potential, organizing nanomaterial on an attractive template is needed. [5] 1D nanostructures have attracted considerable attention because of their potential use in a wide range of advanced applications in the past decade. Studies have shown that the key to fabricating a 1D nanostructure can be focused on the way in which atoms or other building blocks are rationally assembled into structures with nanometer-sized diameters but much higher lengths. 1D nanostructures have attracted considerable attention because of their potential use in a wide range of advanced applications in the past decade. Studies have shown that the key to fabricating a 1D nanostructure can be focused on the way in which atoms or other building blocks are rationally assembled into structures with nanometer-sized diameters but much higher lengths. [6] Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials silicon anodes have limited applications because silicons volume changes by 400% upon insertion and extraction of lithium, which results in pulverization and capacity fading. [7]

It has been found that 3D transition metal oxides such as nickel oxide, cobalt oxide, and iron oxide exhibit reversible capacities about three times larger than those of graphite at a relative low potential. Among them, cobalt oxides (Co3O4 and CoO) have shown the highest capacity (700 mAh g1) and best cycle performance (93.4 % of initial capacity was retained after 100 cycles), compared with nickel oxide (NiO) and iron oxides (Fe2O3 and Fe3O4). [8] Co3O4 nanotubes were developed via thermal decomposition of a sacrificial template which was used as anode material for Li-Ion batteries and also as gas sensors.Co3O4 nanotubes were found to be much better than Co3O4 nanorods or nanoparticles. The improved performance has aroused from the effects of hollow inside and porous surface character of the tubes. [9] Nanotubes have been considered as one of the most promising structures for Li-Ion batteries due to higher surface to volume ratios than other one dimensional nanostructures such as nanowires. But the initial Coulombic efficiency for porous Co3O4 nanotubes was only 70% which was the same for earlier performed research. The TEM image and the XRD pattern of the porous ZnCo3O4 nanotube indicated that morphology and structure have been basically maintained after first charge and discharge process. [8,10] It was reported that nano sized metal oxides exhibited good electrochemical performance on account of larger specific area and higher reaction activity for Li-Ion insertion. For transition metal oxides multi-electron reaction is dominant in the electrochemical reaction processes, leading to higher electrochemical property. [11] The main cause for low initial Coulombic efficiency i.e. large initial irreversible capacity, were solid electrolyte interphase (SEI) film formation and incomplete decomposition of Li2O during first discharge process. Co3O4 specimen exhibited similar properties in terms of capacity and cycle life even when there was a change in synthetic time. [12] Ferrous oxides being environment friendly were combined with Cobalt to form cobalt ferrite which showed superior capacities. But the major drawback of the ferrite for anode materials of Li-Ion batteries is that, there is dramatically decrease in the reversible capacities. [13] Co3O4 produces a cubic inverse spinel structure.
[14]

Spinel-type ZnCo2O4 has long been

used as pigments or dying material and also in use as a catalyst for some reactions. Spinel
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compounds have a general formula MY2O4, in which M is a divalent metal and Y is a trivalent one. Spinels (involve ZnCo2O4) containing transition metal ions can act as efficient catalysts in a number of heterogeneous chemical processes. [15] ZnCo2O4 was also used as an anode material and demonstrated high energy density. The initial discharge capacity is high but irreversible capacity is low due to the formation of solid electrolyte interface (SEI) and the irreversible reaction of lithium with oxygen atoms in the active material. [16] Poizot et.al; have proposed that mechanism of lithium storage in the cobalt oxide materials is due to the reversible oxidation and reduction of cobalt oxides. ZnCo2O4 is an attractive material for evaluation as anode for Lithium Ion batteries. It is a normal spinel with the bivalent Zn-ions occupying the tetrahedral sites in the cubic spinel structure and the trivalent Co-ions occupying the octahedral sites. Both Zn and Co are electrochemically active metals with respect to Li-metal. Traditional spinel-formation reactions usually occur at planar interfaces, or in a powder form at high sintering temperatures (>1,000 C). [17] When nano-size particles of ZnCo2O4 are electrochemically discharged with Li-metal, the crystal structure destruction occurs followed by the formation of Zn- and Co-metal nanoparticles and Li2O, as per the Equation 1. Upon deep discharge, Zn can reversibly react with Li to form Li-Zn alloy (1:1) at potentials below 1.0 V to contribute to the anodic capacity, as shown in Equation 2. In addition, at potentials above 1.0 V during charge-reaction, both Zn- and Cometal nano-particles can reversibly react with Li2O by the displacement reaction forming the respective nano-size metal oxides (Equations. 3 and 4). In the most favourable case, the bivalent Co2+ ions in CoO can further react reversibly with Li2O to form some trivalent Co3+ ions to give Co3O4 as in Equation 5.

ZnCo2O4 + 8Li++8e Zn + Li++e LiZn

Zn+ 2Co + 4 Li2O

(1) (2) (3)

Zn + Li2O ZnO+ 2Li++2e

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2Co + 2Li2O 2CoO+ 4Li++4e 2CoO+ 2/3Li2O 2/3Co3O4 + 4/3Li+ + 4/3e

(4) (5)

ZnCo2O4 gives high and stable capacities only under deep discharge-charge conditions that enabled the formation and decomposition of the beneficial polymeric gel-type layer. During the first-discharge reaction, the crystal structure of the starting material was destroyed followed by the reduction of metal ions to metal nanoparticles. [18]

4. CRITICAL ANALYSIS 4.1 ORIGINALITY:

The work done by the author/ authors is the modification and extension to the other researches carried out in the field. The ZnCo2O4 nanowire synthesis was already carried out by the other researchers and the same work has been modified by synthesizing the material at different annealing temperatures. The references which mention this work are 10th, 11th, 22nd, 25th, and 26th. Assumptions: 1. The large surface area and unique porous 1 D nanostructure may be responsible for good performance and higher capacity. 2. The higher surface area at 500 oC is due to smaller diameters and larger quantities of nanocrystals and nanopores. 3. ZnCo2O4 nanowires give superior performance in comparison to ZnCo2O4 nanoparticles

4.2 TECHNICAL CORRECTNESS:

1. The assumptions made are technically sound and reasonable. The microemulsion technique used is one of the common techniques employed for nanowire synthesis as the advantage of the method is biocompatibility and biodegradability. [18] 2. The author says that reversible capacity of ZnCo2O4 nanowires is much higher than that of ZnCo2O4 nanoparticles but there are no facts supporting the statement as in 11th reference it is mentioned that the reversible capacities of ZnCo2O4 nanoparticles were

98% over 60 cycles but the paper mentions that initial Coulombic efficiency was 82% in case of ZnCo2O4 nanowires. Some of the other discrepancies observed were as follows; a. The effect of temperature is discussed but variation of the product property with respect to time is not discussed. b. The thermal conductivity of the material and its variation with temperature is not discussed. c. There are some typographical errors existing in the paper like Coulombic efficiency being cited as Colombic efficiency. d. Why the synthesis of ZnCO2O4 spinel structure is difficult is not mentioned in any of the references cited. e. The chemical name of ZnCO2O4 and name of the substrate used has not been mentioned anywhere in the paper. f. The initial Coulombic efficiency is mentioned but the average efficiency after 20 cycles is not mentioned. g. Whether the precipitates formed after microemulsion were aged and then annealed or whether they were directly annealed after preparation is not clearly understood. h. The apparatus in which the products obtained were prepared or stored is not mentioned. i. Results with samples prepared with different aging times as well as at different CTAB concentrations were not compared.

4.3 CLARITY:
The paper presented is an extension to the other researches that were carried out in the same field. The work was already carried out as per the references 10th, 11th, 22nd, 23rd, 25th, 26th. The paper is prepared taken into consideration that the reader is very well aware of the basic aspect relative to the subject. For a beginner the paper is very tedious to understand and interpret its contents.

4.4 BIBLIOGRAPHY:
1. The references are not fully cited and unnecessary semicolons are used for separating two names. 2. As per the 1st reference which is cited, the author mentions that it gives information about efforts made for the improvement of cyclic performance, Coulombic efficiency and capacity. But such things are not at all mentioned in the 1st reference but the given information is found in 6th reference. 3. At some places information is taken from the references but the references are not cited as in; the low Coulombic efficiency was due to the formation of solid electrolyte interphase film and incomplete decomposition of Li2O during the discharge process is taken from 11th reference but was not cited. 4. Some of the references are not cited in a proper manner as in; reference 8th the year is cited incorrectly (cited 2009 instead of 2007)., reference 7th the page number is cited incorrectly. 5. The author states that reversible capacities of ZnCo2O4 nanowires are much higher than that of ZnCo2O4 nanoparticles as per cited in references 10th and 11th. But both the references describe the nanoparticles of ZnCo2O4 and no comparison between the nanoparticles and nanowires is being made 6. 15th reference does not clarify any significant details about the study of research relative to the given paper.

4.5 TITLE/ABSTRACT:
1. The abstract contains the same content as that of conclusions. 2. The title Porous ZnCO2O4 nanowires synthesis via Sacrificial Templates: High Performance Anode materials of Li-Ion Batteries it mentions use of templates but the work contains the use of only a single template. The title is somewhat inappropriate as it does not clearly define the process. The title suitable would be ZnCo2O4 nanowire synthesis by annealing ZnCo2 (C2O4)3 template; used as anode in Li-Ion batteries.

4.6 ILLUSTRATIONS AND TABLES:

There are too many figures or illustrations depicted in the paper. The illustrations are quite clear but one of the figures given in the abstract is not at all the part of the paper. .

Figure 1: XRD pattern of ZnCo2O4 at 500 oC The figure given below is a XRD pattern of the product prepared by calcinations of ZnCo2 (C2O4)3 nanowires at 500oC. The x-axis of the graph does not signify the units used whether the 2 is in degrees or radians.

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Figure 2: (b) EDX pattern (c) SEM image, (d, e) TEM images, (f) HRTEM image, of ZnCo2O4 nanowires For the above figures the author has wrongly mentioned figure (b) and (c) to be SEM images but b is an EDX pattern of ZnCo2O4 at 500oC.

Figure 3: Cyclic voltammogram curves of electrodes made from ZnCo2O4 In the above figure the x-axis title is defined and it is mentioned that these curves are voltammogram curves of the electrodes made from ZnCo2O4 nanowires at a scan rate of 0.5 mVs-1.

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Figure 4: Discharge capacity versus cycle number for electrodes made from ZnCo2O4 nanowires synthesized at 500oC and 700oC Figure 4 compares the discharge capacity of versus cycle number for porous ZnCo2O4 nanowires synthesized at 500 oC and 700 oC. The reversible capacity of nanowires synthesized at 500 oC was maintained at 1197.9 mA h/g while that synthesized at 700 oC exhibits a value of 957mAh/g. This was due to the larger surface area of the nanowires obtained at 500 oC than at 700 oC. If a clear observation is made, it is seen that there is a slight increase in the capacity after 5-6 cycles and then the capacity remains fairly constant. This slight increase in the value is not clarified.

4.7 ALTERNATIVE INTERPRETATION:

The research concludes with the comparison of nanowires with nanoparticles but does not compare nanowires with nanotubes. Also the comparison made is not on a firm base as no references cited clearly mention the facts that are stated. Some of the research papers mentioned in the references state that nanotube is more efficient than nanowire. The author could have carried out further research on synthesis of nanotubes under different annealing conditions and testing its Coulombic efficiency, cycling performance and capacity.

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5. CONCLUSIONS:
On basis of the critical analysis performed on the given research paper and on the basis of my understanding I conclude that the author/authors tried to synthesize the product by microemulsion technique by modification according to the need. But the work could not clearly explain whether the comparision made was between ZnCo2O4 nanowires synthesized at different annealing temperatures or between ZnCo2O4 nanoparticles or nanowires or various other metal oxides with ZnCo2O4.

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