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New Conducting Salts for Rechargeable Lithium-Ion Batteries New Conducting Salts for Rechargeable Lithium-Ion Bateries INAUGURALDISSERTATION zur Erlangung des Doktorgrads der Fakultät für Chemie und Pharmazie der Albert-Ludwigs-Universität Freiburg im Breisgau vorgelegt von Michael Rohde aus Freiburg im Breisgau 2014 Vorsitzender des Promotionsausschusses: Prof. Dr. Torsten Koslowski Referent: Prof. Dr. Ingo Krossing Korreferent: Prof. Dr. Caroline Röhr Datum der mündlichen Prüfung: 30.03.2014 Diese Arbeit wurde im Zeitraum von Oktober 2010 bis Februar 2014 am Freiburger Materialforschungszentrum der Albert-Ludwigs-Universität in Freiburg im Breis- gau unter Anleitung von Prof. Dr. Ingo Krossing angefertigt. Teile dieser Arbeit enthalten Ergebnisse, die im Rahmen von Bachelorarbeiten (Alexander Norow 08.2011, Verena Leppert 08.2012, Lutz Miensopust 05.2013 und Marcel Schorpp 07.2013) im Arbeitskreis von Prof. Krossing unter meiner Anleitung angefertigt wurden. „achtzehn?“ „weg.“ „weg!“ „Karo.“ „Kontra!“ VII Danksagung Ich danke allerherzlichst meinem Doktorvater Prof. Ingo Krossing für das Bereitstellen des spannenden Temas innerhalb dieser Industriekooperation, seine ausgezeichnete Betreuung über all die Jahre, seine Motivationsfähigkeit und die bei dieser Arbeit ge- lassenen Freiheiten. Ich möchte mich sehr herzlich bedanken bei der Korreferentin Prof. Caroline Röhr für die Übernahme der Zweitkorrektur dieser Arbeit, dem Dritprüfer Prof. Michael Fiederle, meinen Laborkollegen Michel Panzer und Christoph Schulz für die geniale Zeit, dem Gruppenleiter Philipp Eiden für seine Geduld bei meinen vielen Fragen, den Bachelorstudenten Alexander Norow, Verena Leppert, Lutz Miensopust und Marcel Schorpp für die Unterstützung im Labor, den Partnern von der BASF Dr. Michael Schmidt, Dr. Arnd Garsuch und Dr. Günter Semrau für die produktiven Projektrefen und angenehme Zusammenarbeit, Stefanie Kuhl für Hilfe bei allen organisatorischen Dingen, die tolle Zeit auf den Sci- ence-Days und die Zeit im FMF oder auch außerhalb. Ich danke allen anderen Mitgliedern der Arbeitsgruppe Krossing für die Unterstützung in jedweger Art: Dr. Anke Hofmann, Dr. Alexander Higelin, Alexander Rupp, Dr. Anne Kraf, Benedikt Burgenmeister, Brigite Jörger, Boumahdi Benkmil, Carola Sturm, Dr. Daniel Himmel, Dr. Daniel Kratzert, Dr. Elias Frei, Fadime Bitgül, Florian Kirschenmann, Florian Stahl, Franziska Scholz, Hannes Böhrer, Dr. Harald Scherer, Jennifer Beck, Dr. Julia Schäfer, Josephine Possart, Katharina Pütz, Dr. Lucia Alvarez Hernandez, Dr. Mara Bürchner, Maribel Sierra, Dr. Marina Artamonova, Mario Sander, Martin Lichtenthaler, Martin Lieder, Dr. Mathias Hill, Mathias Kamp, Dr. Mathias Keßler, Melanie Sanchez, Michael Hog, Mira Schulz, Miriam Schwab, Dr. Nils Trapp, Olaf Petersen, Pengcheng Zhang, Petra Klose, Philippe Weis, Dr. Przemek Malinowski, Dr. Safak Bulut, Sarah Keller, Dr. Sascha Goll, Stefanie Reininger, Tobias Engesser, Valentin Dybbert, Dr. Valentin Radtke, Vera Brucksch, Dr. Werner Deck. Ein besonderes Dankeschön an Dr. Philipp Eiden und Dr. Daniel Himmel bei der Unterstützung von quanten- chemischen Rechnungen, Dr. Harald Scherer für die Hilfe bei der Auswertung von NMR Spektren, Fadime Bitgül, Hannes Böhrer, Dr. Harald Scherer, Dr. Mara Bürchner und Dr. Mathias Keßler für das Messen der unzähligen NMR Spektren, den Glasbläsern Tim Lecke und Martin Walter für ihre Spitzenleistung, den Mitarbeitern der Chemikalienausgabe mit Frau Völker, Herrn Jerg und Herrn Lenhard, VIII dem Werkstatteam um Herrn Melder für die vielen Reparaturen und Installationen im BASF Labor, der Verwaltung des FMF mit Frau Dr. Stefanie Meisen, Stefanie Kuhl, Nicola Weis, Daniel Frauzem, Assiyear Joers, Beate Gloderer, Leonhard Falk, Klaus Hasis und Elena König für die wunderbare Organisation und die unermüdliche Hilfsbereitschaf, meinen Beachvolleyballfreunden Burkhart Pössel, Nils Blumenthal, Jan Krause, Marc Neininger, Valentin Radtke, Tim Rabaschus und Leander Poocza. meinen Freundinnen und Freunden Marlene, Nikolas, Micha, Jonathan, Anthea, Burk- hart, Katrin, Christoph, Daniel, Liza, Laura, Teresa, Bar, Johanna, Marc, Sto, Martin, Rafael, Lisa, Nathalie, Dounia, Franzi und Tim für die spaßige Zeit jenseits der Uni. Der aller größte Dank geht an meine Familie, Nicole, Alisha, Florian, Nadine, Mat- thias, Rike, Henry, Marie-Luise, Opa Werner und Oma Lore, meine Eltern, Donna, Kurt, Marlene und ihrer Familie. IX Contents 1/INTRODUCTION .............................................. 1 1.1/Outline ........................................................ 1 1.2/Principles of Operation ........................................... 2 1.3/Termodynamics ................................................ 3 1.3.1.!Cell voltage ...........................................3 1.3.2.!Teoretical specifc charge capacity ........................ 3 1.3.3.!Teoretical specifc energy or energy density . .3 1.4/Lithium Ion Bateries ............................................ 4 1.4.1.!General characteristics and performance . .4 1.4.2.!Anode materials .......................................5 1.4.3.!Cathode materials ...................................... 6 1.4.4.!Separators ............................................6 1.5/Liquid Nonaqueous Electrolytes ................................... 7 1.5.1.!General requirements ...................................7 1.5.2.!Conducting salts .......................................8 1.5.3.!Solvents ..............................................9 1.5.4.!Additives ............................................10 1.6/Lithium Sulfur Bateries ......................................... 10 1.6.1.!Introduction, fundamental chemistry and their problems . 10 1.6.2.!Solutions ............................................12 1.7/ References .................................................... 13 2/MOTIVATION ............................................... 17 2.1/References ..................................................... 18 3/LITHIUM BOROXINATES ..................................... 19 3.1/Introduction and Overview ...................................... 19 3.2/Syntheses from fuoroalkyl borates and boron oxide . 21 3.3/Syntheses of fuoroalkoxy boroxines from alkoxy boroxine . 24 3.4/Fluorination of trimethoxyboroxine ............................... 25 3.5/Conclusion and Summary ....................................... 25 3.6/Experimental Section ........................................... 27 3.6.1.!Chemicals ...........................................27 3.6.2.!Synthesis of fuoroalkyl borates .......................... 27 3.6.3.!Syntheses of fuoroalkyl boroxine ........................29 3.6.4.!Substitutions at alkyl boroxines .......................... 31 X 3.6.5.!Fluorination of trimethoxy boroxine ......................33 3.7/References ..................................................... 35 4/LITHIUM BIS(TRIFLUOROACETYL)PHOSPHATE . 37 4.1/Introduction and Overview ...................................... 37 4.2/Syntheses from phosphorus pentoxide ............................. 39 4.2.1.!NMR characterisation .................................. 39 4.3/Syntheses from phosphoryl chloride .............................. 41 4.3.1.!Overview and thermodynamic considerations . .41 4.3.2.!Syntheses from POCl3 with LiOAcF in dimethyl carbonate . .43 4.3.3.!Syntheses in acetonitrile and tetrahydrofuran . .51 4.3.4.!Summary ............................................ 55 4.4/Syntheses from lithium dihydrogenphosphate ...................... 55 4.4.1.!NMR characterization .................................56 4.4.2.!IR characterisation ....................................57 4.4.3.!Purifcation of the product ..............................59 4.4.4.!Stability and purity considerations of the product . 59 4.4.5.!Conclusion ........................................... 62 4.5/Synthesis from lithium difuorophosphate ......................... 62 4.6/Summary. 63 4.7/Experimental Section ........................................... 65 4.7.1.!Chemicals ...........................................65 4.7.2.!Syntheses from P4O10 ..................................65 4.7.3.!Syntheses from POCl3 .................................. 67 4.7.4.!Syntheses from LiH2PO4 ................................77 4.7.5.!Synthesis from Li[PO2F2] ...............................89 4.8/References ..................................................... 91 5/LITHIUM TETRAKIS(TRIFLUOROETHOXY)BORATE . 93 5.1/Introduction and Overview ...................................... 93 5.2/Synthesis and Characterisation ................................... 94 5.2.1.!Synthesis ............................................94 5.2.2.!NMR characterisation .................................. 95 5.2.3.!Vibrational spectroscopic characterization . .98 5.3/Ionic Conductivity ............................................. 103 5.4/Termal stability .............................................. 105 5.5/Electrochemical analysis ........................................ 106 5.5.1.!Cyclic voltammetry. .106 XI 5.5.2.!Electrochemical cycling ...............................108 5.6/Summary. 109 5.7/Experimental Section .......................................... 110 5.7.1.!Chemicals ..........................................110 5.7.2.!Preliminary remark ..................................110 5.7.3.!Syntheses in toluene ..................................111 5.7.4.!Synthesis in 1,2-dimethoxyethane .......................113 5.7.5.!Synthesis in toluene with 4 eq. 1,2-dimethoxyethane . 114 5.7.6.!Synthesis in toluene with 2 eq. 1,2-dimethoxyethane . 115 5.8/References .................................................... 116 6/SUMMARY
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