Journal Pre-proof V2O5 nanoparticles as cathode for lithium-ion battery applications: Fabricated via microwave-assisted green synthesis using A paniculata leaf extract K Karthik, Anukorn Phuruangrat, Zaira Zaman Chowdhury, K Pradeeswari, R Mohan Kumar PII: S2468-2179(19)30221-7 DOI: https://doi.org/10.1016/j.jsamd.2019.09.003 Reference: JSAMD 252 To appear in: Journal of Science: Advanced Materials and Devices Received Date: May 2019 Revised Date: September 2019 Accepted Date: September 2019 Please cite this article as: K Karthik, A Phuruangrat, Z.Z Chowdhury, K Pradeeswari, R.M Kumar, V2O5 nanoparticles as cathode for lithium-ion battery applications: Fabricated via microwave-assisted green synthesis using A paniculata leaf extract, Journal of Science: Advanced Materials and Devices, https://doi.org/10.1016/j.jsamd.2019.09.003 This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain © 2019 Publishing services by Elsevier B.V on behalf of Vietnam National University, Hanoi V2O5 nanoparticles as cathode for lithium-ion battery applications: Fabricated via microwave-assisted green synthesis using A paniculata leaf extract K Karthik1*, Anukorn Phuruangrat2, Zaira Zaman Chowdhury3, K Pradeeswari 4, R Mohan Kumar4 Department of Physics, Bharathidasan University, Tiruchirappalli – 620 024, India Department of Materials Science and Technology, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand Nanotechnology and Catalysis Research Center (NANOCAT), University of Malaya, Kuala Lumpur 50603, Malaysia Department of Physics, Presidency College, Chennai - 600 005, Tamil Nadu, India *E-mail : astrokarthik8@gmail.com V2O5 nanoparticles as cathode for lithium-ion battery applications: Fabricated via microwave-assisted green synthesis using A paniculata leaf extract Abstract: Vanadium pentoxide (V2O5) cathode was fabricated via a facile simple and microwave-assisted method by the utilization of Andrographis paniculata leaf extract as fuel and optimizes the electrochemical applications Structural and surface morphology of V2O5 nanoparticles was analyzed by various spectroscopic techniques like SEM and TEM The PXRD exhibits an orthorhombic crystal structure with an average crystallite size (32 nm) The band at 497 cm-1 is attributed to V-O-V stretching vibration through FTIR analysis The electrochemical characterization of synthesized V2O5 nanoparticles was studied towards the lithium-ion battery applications Various parameters like Charge-Discharge, Cyclic Voltammogram (CV) Columbic efficiency have performed The V2O5 exhibits a reversible capacity of 225mAhg-1 after 50 cycles The enhanced performance of the lithium-ion batteries is due to green synthesized V2O5 nanoparticles Keywords: Andrographis paniculata, microwave-assisted method, V2O5, Li-ion battery Introduction In general, electrical energy storage and portable electronic devices were made from Lithium-ion batteries (LIBs), which can offer the best energy to weight performance Lots of efforts were made to develop several anode, cathode and electrolyte materials, the huge response for LIBs is capable of producing high energy density along with good and stable cyclability continuously needs to synthesize high efficacy electrode materials At the same time, developing applications are directing the research for LIBs to a new trend, i.e successful enhancement of battery performances by nanostructured electrodes Primary versions of these nanomaterials are already in the marketplace, especially in the applications of portable power devices In recent times, lithium-ion batteries are also visible in blade electric vehicles (BEVs) and plug-in hybrid electric vehicles (PHEVs) on automotive applications Surviving applications like portable electronics, where lithium-ion technology is entirely deep rooted for the implementation of nanomaterials electrodes to provide extraordinary performance at a preferred power level with constant cycle life The improvement of novel material with good battery performance is an important matter; capacity and retaining of active materials like metals, metal oxides, metal sulfides, and metal alloys are being considered Metal oxides are motivating among these materials, because of their related reactions and repetitive insertion conversion process, permitting the supply of greater capacity Hollow and porous structures of metal oxide semiconductors gained much attention because of their distinct structure dependent properties that enhance them in a wide range of applications like conversion and storage, catalysis and biomedicine [1-6] Anode and cathode of battery materials directly participate or indirectly help for catalytic action in an electrochemical conversion process Even promote to get enhanced properties to achieve high capacity, high columbic efficiency, and low toxicity, mainly to avoid unwanted additives Here we emphasized on powder form of metal oxides, which exhibits unique novel physical and chemical properties due to density, the surface to volume ratio and spatial confinement Specialized local and collective features are produced among the transition metal oxide for the diverse potential electrochemical devices to mitigate the energy crisis Among numerous electrode materials, V2O5 is an ensuring cathode material for energy storage systems, outstanding to its easy synthesis, abundance, and large theoretical capacity Vanadium pentoxide to act as cathode towards lithiation/de-lithiation among the currently available cathode materials LiCoO2, LiMn2O4, LiFePO4, and LiNi1-x-yCoxMnyO2, Moreover, vanadium pentoxide has special properties such as high coefficient of thermal resistance, abundant sources, better safety and well-studied intercalation compound due to its large surface area and easy transportation of charge [7] Various methods have been suggested for the synthesis of V2O5 namely hydrothermal, combustion, sol-gel, precipitation, electrodepositing, droplet emulsion, etc Table showed the comparison of present work with V2O5 reported work (synthesis method, morphology, and applications) In the present study reports the V2O5 nanoparticles by the microwave-assisted green method using Andrographis paniculata (chelating agent) It is a facile, simple, cost-free and less time-consuming combustion method to obtain the single phased of V2O5 NPs These structures lead to increase the diffusion co-efficient As a substitute of common fuels for carbon sources such as glycitric acid, urea, etc., Microwave-assisted green V2O5 nanoparticles are employed as anode material for lithium-ion battery Table Different application V2O5 nanoparticles using different methods Materials Synthesis method Morphology Applications Ref V2O5 Green route (Saccharomyces cerevisiae) Nanoparticles Optical devices and oxidation catalysis [8] Vanadium Green method (Moringa oleifera) Nanoparticles Antimicrobial activity [9] V2O5 Sol-gel Nanoparticles Photocatalytic degradation of Rhodamine B dye [10] V2O5 Chemical precipitation Nanoparticles Photocatalytic degradation of Phenol [11] V2O5 Ultrasoundassisted method Nanoparticles Photocatalytic degradation of Rose Bengal dye and antibacterial activity (foodborne pathogens) [12] V2O5/ZnO nanocomposite Thermal decomposition Nanorods Photodegradation of Methylene blue [13] V2O5 Microwaveassisted hydrothermal synthesis Nanorods Li-ion battery [14] V2O5 Microwaveassisted green route (Andrographis paniculata) Nanoparticles Li-ion battery Present study Experimental Fresh leaves of A paniculata were collected from surrounding of Bharathidasan University campus, were washed with DD water and heat to get extract as shown in the procedure reported by Karthik et al [15-16] V2O5 nanoparticles were prepared by the microwave-assisted biogenic method Stoichiometric amounts of Ammonium metavanadate were homogeneously stirred with 100 mL of A paniculata extract solution for about h at RT A domestic microwave oven (800 W, 2.45 GHz) was used for the synthesis The reaction mixture was placed inside the microwave oven and in the convection mode irradiated for 20 The obtained product was subjected to calcination at 500°C for h The XRD analysis was operated on Rikagu Mini Flexll Desktop, with Cu-Kα radiation (λ=1.5418 Å) at 40 KV, 25 mA The structural interpretation was recorded in the form FTIR spectrum in JASCO 460 PLUS FTIR spectrometer Surface morphologies of green synthesized V2O5 nanoparticles were investigated by SEM (VEGA TESCAN SEM) and TEM (JEOL-JEM 2100F) Electrochemical measurements done by fabrication of required electrodes as reported by Saji et al Active material V2O5 nanopowder (80 wt %), Carbon black (15%) and polyvinylidene fluoride binder (PVDF wt %) were vital for the construction of electrode Charge-discharge profile was examined between 0.01V and 3V vs lithiation and delithiation, by utilizing CHI 660D Austin USA, to the Biologic BCS-80 Battery testing unit [17] Results and Discussion 3.1 Structural Characterization by XRD and FTIR The resulting products (V2O5 NPs) prepared by microwave-assisted biogenic method was characterized by PXRD to identify the crystallite structure and the diffraction pattern presented in Fig.1 The XRD pattern corresponds to the orthorhombic phase of V2O5 and it is in good agreement with the peaks and also matches with JCPDS card no 41-1426 It consisted strong (0 1), (1 0), and (4 0) peaks at the diffracted angles 20.19, 26.18 and 31.04 respectively Which were signified the strong and narrow peaks of as prepared products i.e V2O5 NPs illustrate the high crystallinity and lattice parameters were a= 11.51, b= 3.65 and c= 4.38 Å [18] Also, there are no obvious impurity peaks can be noticed, representing the obtained V2O5 phase with high purity and the complete form of V2O5 during heat-treatment The average crystallite size of the V2O5 nanoparticles was found to be 32 nm according to Debye-Scherrer’s equation as reported earlier [19] D=kλ/β cosθ -(1) There is also one more parameter, which is Dislocation density (δ) is found to be 9.765 × 1014 lines/m2 calculated by using equation [20-22] δ = 1/D2 - (2) Fig XRD pattern of microwave-assisted green synthesis V2O5 nanoparticles Figure shows the FTIR spectrum of V2O5 nanoparticles It displayed that the characteristic peaks of vanadium oxide for V2O5 NPs appeared at The band at 497 cm-1 is attributed to (V-O-V) stretching vibration of terminal oxygen bonds and those around 988 cm-1 is attributed to (V=O) the vibration of doubly coordinated oxygen bonds stretching, and the band at 1615 and 3222 cm-1 were ascribed to bending vibrations of water molecules, other bands at 1425 cm-1was assigned with carbonate appearing due to the contact of the product with atmosphere Principally, the discernible peaks assigned as shown in Fig were unique bands for V2O5, which is quite reliable with previously reported results [23-26] Fig FTIR spectrum of microwave-assisted green synthesis V2O5 nanoparticles 3.2 Morphological Characterization by SEM and TEM All the V2O5 NPs powder samples were prepared by microwave-assisted green synthesis with subsequent heat treatment Surface morphology and shape of microwaveassisted green synthesis V2O5 nanoparticles were studied by SEM and TEM SEM analysis confirmed the particle sizes and micro-surface morphologies of the resultant V2O5 NPs were influenced by agglomeration i.e irregular bunch of particles were spread out in the nanometre range shown in Fig 3a From TEM, can observe that the particles appeared spherical shape and size was in the range of 23 nm (Fig 3b) Fig (a) SEM and (b) TEM images of microwave-assisted green synthesis V2O5 nanoparticles 3.3 Electrochemical performance To emphasize the advantages of the suggested structure, the electrochemical performance of V2O5 as LIB cathode was thoroughly assessed to verify the significant effects The CV studies of V2O5 are shown in Fig 4, which gives evidence for the redox couple and structural phase transition during electrochemical intercalation reaction Fig suggests the CVs of V2O5 nanomaterials at a scan rate (0.1 mV s−1) in the potential range of 1.5–4 V vs Li+/Li possess peaks at 3.65, 2.16 in the first cathodic scan is assignable to lithium insertion (lithiation) process From the second cycle, the intensity of the peak was observed In the anodic part of the scan cycle, the peak at 2.37, 3.11 and 3.81 V assigns to the delithiation process Charging existed for the reverse phase transformation due to deintercalation from γ-LiV2O5 to ε-LiV2O5 (3.11 V) and α-V2O5 (3.81 V) Incomplete redox reactions were responsible for lower cyclic stability [27-29] The insertion/extraction behavior of lithium ions in V2O5 electrode V2O5 + 0.5 Li+ + 0.5 e- ↔ Li0.5V2O5 (3) Li0.5V2O5 + 0.5 Li+ + 0.5 e- ↔ LiV2O5 (4) LiV2O5 + Li+ +1e- ↔ Li2V2O5 (5) Fig CV curves at a scanning rate of 0.1 mVs-1 in the voltage range of 1.5-4.0 V Galvanostatic charge-discharge profile of the V2O5 electrode for the 1st charge, 1, 10th, 30th and 50th charge-discharge cycles at C/10 current rate in the potential range of 1.5–4.0 V vs Li/Li+ (Fig 5) Galvanostatic cycling studies reveal the performance of the battery The initial charge capacities acquired from these data is 333 mAhg-1 The discharge capacity maintains to decrease up to 50 cycles and the charge capacity obtained at the end of 50 cycles is 222 mAhg-1 Fig Galvanostatic charge-discharge profiles at a current rate of C/10 Fig shows the columbic efficiency of 50 cycles at a constant current rate of C/10, which depicts the remarkable performance of V2O5 nanomaterials as the anode in LIBs The initial lithiation capacity of V2O5 was 335 mAhg-1, later eventually reached 225 mAhg-1 at 50th cycle Gradually capacity maintained the stabilization; it retained 95% at its 50th cycle and faded only 5% related to the 30th cycle Table A comparison of battery performance of other reported works and present work First specific Specific capacity capacity after 50th cycle (mAhg-1) (mAhg-1) 250 230 [30] 273 189 [31] 275 175 [14] 310 230 [32] 294 188 [33] Facial sol-gel method 230 213 [34] V2O5 Microwave-assisted 335 225 nanoparticles green route Materials Synthesis method V2O5 Rice husk carbon nanoparticles mediated calcinations V2O5 hollow Solvothermal structures treatment V2O5 nanorods Microwave-assisted Ref hydrothermal method V2O5 sheets Organics-assisted pyrolysis method V2O5 Gel-combustion (Bio nanoparticles fuel: (Manihot esculenta) V-V2O5 nanosheets (Andrographis paniculata) Present work Fig Cycling performance and columbic efficiency at a current rate of C/10 Battery performance of the prepared V2O5 compared to previously published literature (Table 2) In this regard, it is important to notify that the synthesis method is simple, cost-effective, less time consuming (green method) over-complicated chemical methods for large scale synthesis of V2O5 nanoparticles for lithium-ion batteries Conclusion V2O5 nanoparticles have been synthesized via the microwave-assisted green route (Andrographis paniculata as a green fuel), which is very simple and economically cheap The prepared V2O5 nanoparticles showed the orthorhombic phase through XRD analysis and in good agreement with JCPDS data The characteristic band at 497 cm-1 was due to the V-O-V stretching from the FTIR TEM indicated that the particles seemed spherical and size was 23 nm approximately Electrochemical studies of V2O5 nanoparticles showed 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A paniculata leaf extract Abstract: Vanadium pentoxide (V2O5) cathode was fabricated via a facile simple and microwave- assisted method by the utilization of Andrographis paniculata leaf extract. .. Chennai - 600 005, Tamil Nadu, India *E-mail : astrokarthik8@gmail.com V2O5 nanoparticles as cathode for lithium- ion battery applications: Fabricated via microwave- assisted green synthesis using A