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Phosphate Based Cathodes and Reduced Graphene Oxide Composite Anodes for Energy Storage Applications PDF

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Springer Theses Recognizing Outstanding Ph.D. Research Abdulrahman Shahul Hameed Phosphate Based Cathodes and Reduced Graphene Oxide Composite Anodes for Energy Storage Applications Springer Theses Recognizing Outstanding Ph.D. Research Aims and Scope The series “Springer Theses” brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected foritsscientificexcellenceandthehighimpactofitscontentsforthepertinentfield of research. For greater accessibility to non-specialists, the published versions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explainingthespecialrelevanceoftheworkforthefield.Asawhole,theserieswill provide a valuable resource both for newcomers to the research fields described, and for other scientists seeking detailed background information on special questions. Finally, it provides an accredited documentation of the valuable contributions made by today’s younger generation of scientists. Theses are accepted into the series by invited nomination only and must fulfill all of the following criteria (cid:129) They must be written in good English. (cid:129) ThetopicshouldfallwithintheconfinesofChemistry,Physics,EarthSciences, Engineeringandrelatedinterdisciplinary fields such asMaterials,Nanoscience, Chemical Engineering, Complex Systems and Biophysics. (cid:129) The work reported in the thesis must represent a significant scientific advance. (cid:129) Ifthethesisincludespreviouslypublishedmaterial,permissiontoreproducethis must be gained from the respective copyright holder. (cid:129) They must have been examined and passed during the 12 months prior to nomination. (cid:129) Each thesis should include a foreword by the supervisor outlining the signifi- cance of its content. (cid:129) The theses should have a clearly defined structure including an introduction accessible to scientists not expert in that particular field. More information about this series at http://www.springer.com/series/8790 Abdulrahman Shahul Hameed Phosphate Based Cathodes and Reduced Graphene Oxide Composite Anodes for Energy Storage Applications Doctoral Thesis accepted by National University of Singapore, Singapore 123 Author Supervisor Dr. Abdulrahman ShahulHameed Prof. J.J.Vittal DepartmentofChemistryandEarthSciences National University ofSingapore Qatar University Singapore Doha Singapore Qatar ISSN 2190-5053 ISSN 2190-5061 (electronic) SpringerTheses ISBN978-981-10-2301-9 ISBN978-981-10-2302-6 (eBook) DOI 10.1007/978-981-10-2302-6 LibraryofCongressControlNumber:2016947759 ©SpringerScience+BusinessMediaSingapore2016 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authorsortheeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinor foranyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper ThisSpringerimprintispublishedbySpringerNature TheregisteredcompanyisSpringerScience+BusinessMediaSingaporePteLtd. ’ Supervisor s Foreword ItisagreatpleasuretointroducethePh.D.thesisworkofDr.AbdulrahmanShahul HameedwhichwontheSpringerThesisAward2016foroutstandingoriginalwork and accepted for publication within Springer Theses. Shahul ranked second in his B.Sc.(2004–2007)fromCalicutUniversity,India.Later,hewasadmittedtoIndian InstituteofTechnology—Delhi,oneoftheprestigiousinstitutes inIndia througha highly competitive national-level Joint Admission Test to do M.Sc. (2008–2010) before joining National University of Singapore for his Ph.D. degree. Shahul completed Ph.D. doctoral work under my supervision in the Department of ChemistryduringtheperiodAugust2010–August2014,defendedhisPh.D.thesis, and received his Ph.D. degree in January 2015. Shahul’s thesis work deals with developing novel cathode and anode materials for lithium-ion battery applications. This includes synthesizing novel nanomateri- als, characterizing the as-synthesized materials and fabrication of the electrodes, and assembling the lithium-ion battery in glove box. Shahul had carried out his research independently. Shahulreceivedseveralawardsforthiswork.Heobtainedtravelgranttoattend AsianCrystallographyAssociation(AsCA)toattendAsCA’13conferenceinHong Kongin2013.Hewasawarded“RisingStarAward”atthesameconferenceforhis presentation.HealsowontheBestPosterAwardatthe8thSingaporeInternational Chemistry Conference (SICC-8) in December 2014. Shahul also obtained travel grant from the department to attend the International School on “Materials for Renewable Energy” in Erice, Italy, in 2014. Shahul published 8 international papers from his research work, one submitted for publication and one more to be written for publication. Li-ion batteries (LIBs) are considered as one of the best available technologies for the production of eco-friendly electric vehicles (EVs). High cost of LIBs is mainly responsible for commercializationoftheLIBsinconventionalvehicles.Shahultriedtoaddressthis toproducecheaperhigh-performancecathodematerialsforLIBs;anrGO/MOPOF (reduced graphene oxide/Metal Organophosphate Open Framework) nanocom- posite with *4 V of operation has been developed by a cost-effective room v vi Supervisor’sForeword temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H . Enhanced lithium cycling has been witnessed 2 with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks toincreasedelectronicconductivityandenhancedLidiffusivity.Thisworkhasthe potential for commercialization due to cheap and easy synthesis of the cathode materials (Scientific Reports, 2015). Shahul showed how to improve good rever- sible capacity and better capacity retention of ZnFe O material by Mg(II) and Cu 2 4 (II)dopingusingsolgel-assistedcombustionmethod.Thereversiblecapacityofthe samples was improved by annealing at higher temperature. However, there is still capacityfadingduringtheinitialfewcycleswhichcanbeminimizedwiththehelp of carbon coating or by preparing graphene-Mg Cu Zn Fe O composites 0.2 0.2 0.62 1.98 4 (ACS Applied Materials & Interfaces, 2015). Newer synthetic methods are also very important in material synthesis as the performance depends on the synthetic methods and easy access to large amount of materials in pure phase. Shahul dis- covered a new method of synthesizing Li V (PO ) by thermal decomposition of 3 2 4 3 another cathode material Li (VO) (HPO ) (C O )(cid:1)6H O. Carbon coating of 2 2 4 2 2 4 2 Li V (PO ) has also achieved by mixing the precursor with sucrose and subse- 3 2 4 3 quent decomposition in argon atmosphere to improve its performance (Electrochimica Acta, 2014). Shahul synthesized a new lithium containing hybrid inorganic-organic open frameworkmaterial,Li (VO) (HPO ) (C O )(cid:1)6H O,whichwasdifficulttoachieve 2 2 4 2 2 4 2 before inour laboratory.The presenceof extractablelithium ions intheinter-layer space together with the feasibility of V4+/5+ redox couple make this compound suitable for cathode applications in 4-V Li-ion batteries. The material exhibits excellent reversible lithium insertion/extraction during cycling (J. Mater. Chem., 2013). The higher redox potential (*4 V) of LiVOPO blended with its good 4 theoreticalcapacityof166mAhg−1makesitsenergydensityhigherthanLiFePO 4 and projects to be a potential high-voltage cathode material for LIBs. So far, researchhasmainlybeenfocusedonstudying theperformance oftwowell-known phases of LiVOPO , namely the triclinic a-LiVOPO and the orthorhombic 4 4 b-LiVOPO . In addition to these phases, a new phase a-LiVOPO was observed 4 I 4 duringlithiuminsertionofa-anda -VOPO .Theoreticalstudiesonthisphasehas I II 4 shownthepossibilityofa2Dlithiumionmigrationandexpectedtoexhibitabetter lithium storage performance than a and b phases. However, a detailed electro- chemicalstudyofthisphaseisstilllacking.Shahuldiscoveredaconvenientmethod to synthesize LiVOPO (cid:1)2H O in bulk. He was able to achieve a direct chemical 4 2 synthesis of the tetragonal a-LiVOPO by an easier and a cost-effective route. I 4 Electrochemical studies reveal that a-LiVOPO exhibits highly reversible lithium I 4 insertionandextractionwithanegligiblecapacityfadingduringcycling(J.Mater. Chem., 2012). Overall, Shahul focussed on the vanadium phosphates, a battery materialinhisPh.D.thesis.HisPh.D.workgeneratedlotsofattentionandinterest among the battery community which you may realize while reading his thesis. Singapore Prof. J.J. Vittal June 2016 Parts of this thesis have been published in the following journal articles: A. Shahul Hameed, M. V. Reddy, Jeremiah L. T. Chen, B. V. R. Chowdari and JagadeseJ.Vittal,“RGO/StibniteNanocompositeasaDualAnodeforLithiumand Sodium Ion Batteries”, ACS Sustainable Chem. Eng., 2016, 4, 2479–2486. A.ShahulHameed,M.V.Reddy,M.Nagarathinam,TomčeRunčevski,RobertE Dinnebier, Stefan Adams, B. V. R. Chowdari and Jagadese J. Vittal, “Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries”, Sci. Rep., 2015, 5, 16270. A. Shahul Hameed, M. V. Reddy, B. V. R. Chowdari and Jagadese J. Vittal, “PreparationofrGO-wrappedmagnetitenanocompositesandtheirenergystorage properties”, RSC Adv., 2014, 4, 64142–64150. A. Shahul Hameed, M. V. Reddy, B. V. R. Chowdari and Jagadese J. Vittal, “Carbon coated Li V (PO ) from the single-source precursor, Li (VO) (HPO ) 3 2 4 3 2 2 4 2 (C O )(cid:1)6H O as cathode and anode materials for Lithium ion batteries”, 2 4 2 Electrochim. Acta, 2014, 128, 184–191. A. Shahul Hameed, M. Nagarathinam, Martin Schreyer, M. V. Reddy, B. V. R. Chowdari and Jagadese J. Vittal, “A layered oxalatophosphate frame- work as a cathode material for Li-ion batteries”, J. Mater. Chem. A, 2013, 1, 5721–5726. A. Shahul Hameed, M. Nagarathinam, M. V. Reddy, B. V. R. Chowdari and Jagadese J. Vittal, “Synthesis and electrochemical studies of layer-structured metastable a-LiVOPO ”, J. Mater. Chem., 2012, 22, 7206–7213. I 4 vii Contents 1 Introduction to Li-ion Batteries. .... .... .... .... .... ..... .... 1 1.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 1 1.2 Definition and Classification of Batteries ... .... .... ..... .... 2 1.2.1 Primary Batteries.... .... .... .... .... .... ..... .... 3 1.2.2 Secondary Batteries.. .... .... .... .... .... ..... .... 3 1.2.3 Comparison of Secondary Batteries.. .... .... ..... .... 3 1.3 Principle of Operation of LIBs... .... .... .... .... ..... .... 4 1.4 Applications of LIBs: State of the Art and Future .... ..... .... 6 1.5 Research Trend on LIB Materials. .... .... .... .... ..... .... 6 1.5.1 Cathode Materials... .... .... .... .... .... ..... .... 7 1.5.2 Anode Materials .... .... .... .... .... .... ..... .... 16 1.5.3 Electrolyte Materials. .... .... .... .... .... ..... .... 22 1.6 Aims of the Present Study .. .... .... .... .... .... ..... .... 24 1.7 Thesis Outline .. .... ..... .... .... .... .... .... ..... .... 25 References.. .... .... .... ..... .... .... .... .... .... ..... .... 25 2 Physicochemical and Electrochemical Characterization.. ..... .... 31 2.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 31 2.2 Synthesis of Electrode Materials.. .... .... .... .... ..... .... 32 2.2.1 Hydrothermal Synthesis .. .... .... .... .... ..... .... 32 2.2.2 Single Source Precursor Approach .. .... .... ..... .... 32 2.2.3 Sonochemical Reaction... .... .... .... .... ..... .... 33 2.3 Structural Characterization .. .... .... .... .... .... ..... .... 33 2.3.1 Powder X-Ray Diffraction. .... .... .... .... ..... .... 33 2.3.2 In Situ X-Ray Diffraction . .... .... .... .... ..... .... 35 2.3.3 Rietveld Refinement . .... .... .... .... .... ..... .... 36 2.3.4 Single Crystal X-Ray Diffraction ... .... .... ..... .... 36 2.3.5 Elemental Analysis (EA).. .... .... .... .... ..... .... 37 2.3.6 Thermogravimetric Analysis... .... .... .... ..... .... 37 ix x Contents 2.4 Morphological Characterization .. .... .... .... .... ..... .... 38 2.4.1 Scanning Electron Microscopy . .... .... .... ..... .... 38 2.4.2 Transmission Electron Microscopy .. .... .... ..... .... 39 2.5 Coin Cell Fabrication. ..... .... .... .... .... .... ..... .... 40 2.5.1 Electrode Fabrication. .... .... .... .... .... ..... .... 40 2.5.2 Coin Cell Assembly . .... .... .... .... .... ..... .... 41 2.6 Electrochemical Characterization . .... .... .... .... ..... .... 42 2.6.1 Galvanostatic Cycling.... .... .... .... .... ..... .... 42 2.6.2 Cyclic Voltammetry . .... .... .... .... .... ..... .... 43 2.6.3 Electrochemical Impedance Spectroscopy (EIS) ..... .... 44 References.. .... .... .... ..... .... .... .... .... .... ..... .... 45 3 Synthesis and Electrochemical Studies of a Novel MOPOF Cathode Material, [Li (VO) (C O )(HPO ) ]... .... .... ..... .... 47 2 2 2 4 4 2 3.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 47 3.2 Experimental Section . ..... .... .... .... .... .... ..... .... 49 3.2.1 Synthesis of [Li (VO) (HPO ) (C O )](cid:1)6H O.. ..... .... 49 2 2 4 2 2 4 2 3.2.2 Synthesis of [Li (VO) (HPO ) (C O )]... .... ..... .... 49 2 2 4 2 2 4 3.2.3 X-Ray Data Collection and Structure Determination.. .... 50 3.3 Results and Discussion..... .... .... .... .... .... ..... .... 50 3.3.1 ControlledSynthesisof[Li (VO) (HPO ) (C O )](cid:1)6H O ... 50 2 2 4 2 2 4 2 3.3.2 TGA.... .... ..... .... .... .... .... .... ..... .... 51 3.3.3 In Situ PXRD. ..... .... .... .... .... .... ..... .... 52 3.3.4 Ab Initio Structure Determination... .... .... ..... .... 53 3.3.5 Structure Description. .... .... .... .... .... ..... .... 54 3.3.6 Galvanostatic Cycling Studies.. .... .... .... ..... .... 55 3.3.7 Cyclic Voltammetry . .... .... .... .... .... ..... .... 59 3.3.8 Electrochemical Impedance Spectroscopy (EIS) ..... .... 61 3.3.9 Ex Situ XRD Studies .... .... .... .... .... ..... .... 62 3.4 Conclusions .... .... ..... .... .... .... .... .... ..... .... 64 References.. .... .... .... ..... .... .... .... .... .... ..... .... 64 4 Room Temperature Synthesis of rGO/[K (VO) (C O )(HPO ) ] 2 2 2 4 4 2 for Greener and Cheaper Lithium Ion Batteries ... .... ..... .... 67 4.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 67 4.2 Experimental Section . ..... .... .... .... .... .... ..... .... 68 4.2.1 Preparation of Graphene Oxide. .... .... .... ..... .... 68 4.2.2 Synthesis of [K (VO) (HPO ) (C O )] ... .... ..... .... 69 2 2 4 2 2 4 4.2.3 Synthesis of rGO/[K (VO) (HPO ) (C O )] ... ..... .... 69 2 2 4 2 2 4 4.2.4 Structural and Electrochemical Characterization ..... .... 70 4.3 Results and Discussion..... .... .... .... .... .... ..... .... 70 4.3.1 Structural Analysis .. .... .... .... .... .... ..... .... 70 4.3.2 In Situ PXRD. ..... .... .... .... .... .... ..... .... 71 4.3.3 TGA.... .... ..... .... .... .... .... .... ..... .... 73

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