Department of Chemistry

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http://presiuniv.ndl.gov.in:4009/handle/123456789/2304

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Browsing Department of Chemistry by Author "Biswas, Biplab"

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    Developments of Low-Cost Aqueous Sodium-Ion Batteries with Prussian Blue Analogue Positive Electrodes for Solar Energy Storage Applications
    Biswas, Biplab; Banerjee, Anjan
    In this thesis, different aqueous sodium ion batteries are presented with various combinations of positive electrode, negative electrode and electrolyte, whereas the target application is the solar energy storage. Several Prussian blue analogues (PBAs) with multiple transition metal substitutions are utilized as positive electrodes, while diverse classes of redox active materials, namely functionalized carbons, vanadium based polyoxometalates, metal oxides, metal phosphates etc. are screened for negative electrodes. Herein, low-cost stainless steel current collectors are utilized, while optimized corrosion protective coatings are applied. The sodium ion prototype cells and devices with multiple electrode couples are assembled in both flooded and starved electrolyte configurations. The exploitation of hydrogels as electrolyte media is vividly emphasized in this thesis. However, all the developed prototype cells/devices are laboratory tested through specific capacity, Faradaic efficiency, rate capability, energy density, power density and cycle life at a wide range of working temperatures. Moreover, the prototype devices are also performance tested through the custom-built solar charging module as part of the feasibility assessments for solar energy storage applications. However, this thesis comprises eight chapters, and brief descriptions of each chapter are following. Chapter 1 elaborates the basic concepts of battery applications in renewable energy storage sectors. This chapter starts with the fundamental ideas of energy storage devices, namely batteries and supercapacitors, while their significances in our daily life are greatly discussed. The limitations of present battery technologies for solar energy storage are addressed, and the lacuna could be filled by the introduction of aqueous sodium ion batteries. The middle part of this chapter deals with the sodium ion electrochemistry and relevant active material screening. However, this chapter culminates with the wise selection of PBAs as positive electrode materials in sodium ion systems. Chapter 2 describes hybrid sodium ion batteries, wherewith Na2NiFe(CN)6 (Ni-PBA) positive electrode couples with functionalized carbon negative electrodes in starved electrolyte configuration. A 1 M Na2SO4 (aq.) solution is used as electrolyte, which is socked in porous adsorbent glass mat (AGM) separator. Chapter 3 demonstrates Na2CoFe(CN)6//NaV3O8 (Co-PBA//NVO) couple for successful sodium ion cells under pouch and prismatic cell configurations, whereas respective Na2SO4-AGM and Na2SO4- SiO2-hydrogel electrolytes are employed. Chapter 4 depicts the sodium ion cell with Na2MnFe(CN)6 (Mn-PBA) positive and commercial Fe2O3 negative electrodes in Na2SO4-SiO2-hydrogel electrolyte. This cell chemistry does not sustain well due to multiple performance limiting issues arising from both positive and negative electrodes. Chapter 5 emphasis on the limitations of Mn-PBA//Fe2O3 couple, and the legitimate solutions are addressed. Herein, Ni incorporation in Mn-PBA and Na-doping in Fe2O3 appreciably mitigate the problems of Mn-PBA//Fe2O3 couple. Therefore, a successful sodium ion cell is reported by coupling Na2Mn0.5Ni0.5Fe(CN)6 (MnNi-PBA) as positive and Na-doped Fe2O3 (NaxFe2O3) as negative electrodes in a novel hydrogel comprising carboxymethyl cellulose (CMC) and SiO2 in 1 M Na2SO4 (aq.). Chapter 6 demonstrates the performance studies of Na2Co0.5Ni0.5Fe(CN)6//Na3Ti2(PO4)3 (CoNiPBA//NTP) sodium ion cell in 1 M (aq.) Na2SO4-SiO2 hydrogel electrolyte. Chapter 7 represents the optimization studies of Ni/Co/Mn ratio in Na2NixCoyMnzFe(CN)6 system, while, Na2Ni0.33Co0.33Mn0.33Fe(CN)6 demonstrates augmented electrochemical performances. A sodium ion full cell is assembled with Na2Ni0.33Co0.33Mn0.33Fe(CN)6 positive and hydrogen Vanadate negative electrodes in Na2SO4-CMC-SiO2 hydrogel electrolyte. Chapter 8 introduces the high entropy PBAs (HE-PBAs: Na1.3Mn0.2Fe0.2Co0.2Ni0.2Cu0.2[Fe(CN)6]0.82‧2.2H2O and Na1.7Mn0.2Fe0.2Co0.2Ni0.2Zn0.2[Fe(CN)6]0.93‧1.4H2O) as positive electrodes in aqueous sodium ion cells. The Na2Mn0.2Fe0.2Co0.2Ni0.2Cu0.2Fe(CN)6 shows better charge storage performances, and is coupled with Na-incorporated CuFeO, derived from Na2CuFe(CN)6, in Na2SO4-CMC-SiO2 hydrogel electrolyte. However, the thesis is culminated with a concise description of future directions for PBAs based advanced sodium ion batteries for solar energy storage towards sustainable developments.
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    Synthesis and Characterization of Metal Organic Framework Based on 3d and 4f Metals
    Biswas, Biplab
    This thesis covers the broader section of the chemistry and the material sciences of our daily needs. The main objective of our work was to design different 3d and 3d-4f hetero bimetallic Metal Organic Framework (MOF) using different clickable Schiff base ligand having N,N,O donor sites. We have further used co-ligand such as azide, thiocyanate, 4-tert-butyl-benzoic acid to increase the nuclearity of the metal complex. Careful design of these complexes has allowed us to isolate these complexes with versatile structural motif and application in the field of data storage, luminescence and sensing. We have explored the sensing study for the detection of the hazardous analytes such as sulfide (S2-) and Ag+ , Cu2+, Fe3+ by Metal Organic Framework. We have also studied the anti-cancer activity towards the breast cancer cells Zn azido and Zn perchloato complex where we have found that a 0.5 mM dose of the Zn-azido and Zn-perchlorato complex could kill the 81% and 72% of the breast cancer cells respectively. However Zn-azido complex affects the normal cell as well although Zn-perchlorato complex does not affect the normal cells. Hence Znperchlorato complex has potential biological activity and may be used for the therapeutic purposes. We have also synthesised 3d-4f metal complexes which could be used as fluorescence biomarker and could be used as data storage. This thesis covers a broader sector of material science in corroboration of biological studies in few cases.