Ecuación 8. Estimación del factor de proyección de tránsito
7. RESULTADOS Y DISCUSIÓN
7.2 AFOROS VEHICULARES
As a first step of studying ligand-exchange rates (see 4.2) and desolvation (see 4.1) by the method outlined in section 3.3 the force distributions on the elec- trolyte solvents in the first and second cation solvation shells are computed (Figure 4.2). CPMD was employed to a system consisting of LiPF6in ACN and
for three salt concentrations (solvent to salt ratios): 20:1, 10:1, and 5:1. After the systems were equilibrated for ca. 1-2 ps, production runs of a few ps were performed. The trajectories of the production runs were subsequently anal- ysed in order to retrieve the radial force distributions on the solvents, which broadened with increasing salt concentration (lower ratio). Furthermore, the area between the first and second solvation shell becomes more populated as the salt concentration increases, indicating either more structural disorder or an increasing ligand-exchange, i.e. dynamic disorder, or both. Finally, the distance between the first and second solvation shell shortens as the salt con- centration increases, and hence the interactions between the shells increase, which we tentatively interpret also as a destabilized first solvation shells.
Figure 4.2: The colors indicate probability of having a certain radial force at a certain distance from a cation, with red indicating high probability and dark blue low probability. (Left) At low concentrations the distribution is very sharp within the first solvation shell. (Middle) Increasing the concentration broadens the distribution. (Right) The broadening continues upon increasing the concentration further.
Chapter 5
Conclusions and Outlook
Na+displays a larger solvation shell than Li+, promoting highly concentrated
behaviour at lower solvent to salt ratios than Li+. The structure of the first
solvation shell grows disordered with increasing concentration, showing that the first solvation shell grows unstable, with implications for the transport mechanism of the electrolyte, along with promoting a larger liquid range and faster kinetics. Furthermore, the correlation is more pronounced for Na+than
Li+, and more so for PC than ACN, again indicating that highly concentrated
behaviour is seen at lower solvent to salt ratios for Na+ than Li+ based elec-
trolytes.
The solubility of O2 in a DMSO based electrolyte was dependent on the
salt concentration, and the anion used. The interaction energy between O2
and ClO−4, Tf and TFSI, agreed with the experimentally observed solubility trends, showing that TFSI promotes O2solubility. This is of interest for Li-air
batteries where the O2 solubility determines the capacity.
The distribution of radial forces on solvent molecules further indicates that the solvation shell grows disordered with increasing concentration. The distributions further indicates that the ligand exchange rate increases with concentrations. In the future, a direct way of computing the ligand-exchange rate from the force distributions will be investigated. Moreover, using AIMD data a comprehensive structure analysis of the first and second solvation shell, in LIB and SIB electrolytes, will be carried out, with an emphasis on how the structures interact with one another.
Chapter 6
Acknowledgments
First of all I would like to thank my funders: The Swedish Energy Agency and EU H2020 NAIADES.
I thank my supervisor Patrik Johansson for giving me the freedom and resources to pursue my ideas as well as giving me the opportunity to work on several interesting projects.
To all past and present members of KMF, thank you for creating a good work environment! In particular I like to thank Steffen Jeschke, Rasmus An- dersson, Piotr Jankowski, Rafael Barros Neves de Ara´ujo, Johan Scheers, and Fabian ˚Ar´en for fruitful discussions on modelling. I like to thank Matthew Sadd, Muhammad Abdelhamid, Yajing “Jenny” Yan, Simon Lindberg and Adriana Navarro S´uarez for trying to teach me how batteries work, in addi- tion to some electrochemistry. I want to thank Joakim Zaar for making the office extra fun the last 6 months. Huge thank you to my office mate Simon Lindberg for (almost) always being cheerful, for all the fun and necessary chats, and for putting up with me!
Finally, I want to thank my family and friends, whom I never see nearly enough. Thank you for all the support and for always being there!
References
(1) Li, M.; Lu, J.; Chen, Z.; Amine, K. Advanced Materials 2018, 1800561, 1800561.
(2) Davis, S. J.; Caldeira, K.; Matthews, H. D. Science 2010, 329, 1330– 1333.
(3) International Energy Agency, CO2 Emissions from Fuel Combustion
2017 ; OECD: 2017; Vol. 1, pp 1–162.
(4) Cann, O. These are the top 10 emerging technologies of 2016., https:// www.weforum.org/agenda/2016/06/top-10-emerging-technologies- 2016/.
(5) Carbeck, J. These next-generation batteries could end energy poverty., https : / / www . weforum . org / agenda / 2016 / 06 / next - generation - batteries.
(6) Tan, S.; Ji, Y. J.; Zhang, Z. R.; Yang, Y. ChemPhysChem 2014, 15, 1956–1969.
(7) Berg, H., Batteries for Electric Vehicles - Materials and Electrochem-
istry; Cambridge University Press: 2015.
(8) Tarascon, J.-M.; Armand, M. Nature 2001, 414, 359–367. (9) Reddy, T. B., Linden’s handbook of batteries; McGraw-Hill: 2011. (10) B. Schott A. P¨uttner, M. M. In Advances in Battery Technology for
Electrical Vehicles; Woodhead Publisher: 2015.
(11) Ohzuku, T.; Ueda, A.; Yamamoto, N. Journal of The Electrochemical
Society 1995, 142, 1431–1435.
(12) Ferg, E.; Gummow, R. J.; Kock, A.; Thackeray, M. M. Journal of The
Electrochemical Society 1994, 141, L147.
(13) Colbow, K.; Dahn, J.; Haering, R. Journal of Power Sources 1989, 26, 397–402.
(14) Ozawa, K. Solid State Ionics 1994, 69, 212–221.
(15) Sawai, K.; Iwakoshi, Y.; Ohzuku, T. Solid State Ionics 1994, 69, 273– 283.
(16) Peled, E.; Menkin, S. Journal of The Electrochemical Society 2017, 164, A1703–A1719.
(17) Peled, E. Journal of The Electrochemical Society 1979, 126, 2047. (18) Verma, P.; Maire, P.; Nov´ak, P. Electrochimica Acta 2010, 55, 6332–
6341.
(19) Zubi, G.; Dufo-L´opez, R.; Carvalho, M.; Pasaoglu, G. Renewable and
Sustainable Energy Reviews 2018, 89, 292–308.
(20) Frankel, T. C. The Cobalt Pipeline., https://www.washingtonpost. com / graphics / business / batteries / congo - cobalt - mining - for - lithium-ion-battery/??noredirect=on.
(21) Suo, L.; Borodin, O.; Gao, T.; Olguin, M.; Ho, J.; Fan, X.; Luo, C.; Wang, C.; Xu, K. Science 2015, 350, 938–943.
(22) Xu, K. Chemical Reviews 2004, 104, 4303–4418.
(23) Jeong, S. K.; Inaba, M.; Iriyama, Y.; Abe, T.; Ogumi, Z. Journal of
Power Sources 2008, 175, 540–546.
(24) Yamada, Y.; Yamada, A. Journal of the Electrochemical Society 2015,
162, A2406–A2423.
(25) Yamada, Y.; Furukawa, K.; Sodeyama, K.; Kikuchi, K.; Yaegashi, M.; Tateyama, Y.; Yamada, A. Journal of the American Chemical Society
2014, 136, 5039–5046.
(26) Yamada, Y.; Usui, K.; Chiang, C. H.; Kikuchi, K.; Furukawa, K.; Ya- mada, A. ACS Applied Materials & Interfaces 2014, 6, 10892–10899. (27) Suo, L.; Hu, Y.-S.; Li, H.; Armand, M.; Chen, L. Nature Communica-
tions 2013, 4, 1481.
(28) Yamada, Y.; Yaegashi, M.; Abe, T.; Yamada, A. Chem. Commun. 2013,
49, 11194–11196.
(29) Abe, T.; Fukuda, H.; Iriyama, Y.; Ogumi, Z. Journal of The Electro-
chemical Society 2004, 151, A1120–A1123.
(30) Xu, K.; von Wald Cresce, A. Journal of Materials Research 2012, 27, 2327–2341.
(31) Forsyth, M.; Yoon, H.; Chen, F.; Zhu, H.; MacFarlane, D. R.; Armand, M.; Howlett, P. C. The Journal of Physical Chemistry C 2016, 120, 4276–4286.
(32) Chen, F.; Forsyth, M. Phys. Chem. Chem. Phys. 2016, 18, 19336– 19344.
(33) Matsumoto, K.; Okamoto, Y.; Nohira, T.; Hagiwara, R. The Journal of
Physical Chemistry C 2015, 119, 7648–7655.
(34) Bauer, A.; Song, J.; Vail, S.; Pan, W.; Barker, J.; Lu, Y. Advanced
Energy Materials 2018, 8, 1–13.
(35) Larcher, D.; Tarascon, J.-M. Nature Chemistry 2015, 7, 19–29. (36) Jaskula, B. W. 2014 Minerals Yearbook., http://minerals.usgs.gov/
minerals/pubs/commodity/lithium/myb1-2014-lithi.pdf.
(37) Bolen, B. W. P. 2015 Minerals Yearbook., http : / / minerals . usgs . gov/minerals/pubs/commodity/soda_ash/myb1-2015-sodaa.pdf. (38) Ponrouch, A.; Dedryv`ere, R.; Monti, D.; Demet, A. E.; Ateba Mba,
J. M.; Croguennec, L.; Masquelier, C.; Johansson, P.; Palac´ın, M. R.
Energy & Environmental Science 2013, 6, 2361–2369.
(39) Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Advanced Functional
Materials 2013, 23, 947–958.
(40) Pan, H.; Hu, Y.-S.; Chen, L. Energy & Environmental Science 2013, 6, 2338.
(41) Kubota, K.; Komaba, S. Journal of The Electrochemical Society 2015,
162, A2538–A2550.
(42) Liu, Y.; Fan, F.; Wang, J.; Liu, Y.; Chen, H.; Jungjohann, K. L.; Xu, Y.; Zhu, Y.; Bigio, D.; Zhu, T.; Wang, C. Nano Letters 2014, 14, 3445– 3452.
(43) Hong, S. Y.; Kim, Y.; Park, Y.; Choi, A.; Choi, N.-S.; Lee, K. T. Energy
& Environmental Science 2013, 6, 2067–2081.
(44) Senguttuvan, P.; Rousse, G.; Seznec, V.; Tarascon, J. M.; Palac´ın, M. R.
Chemistry of Materials 2011, 23, 4109–4111.
(45) Stevens, D. A.; Dahn, J. R. Journal of The Electrochemical Society
2000, 147, 1271.
(46) Barker, J.; Saidi, M. Y.; Swoyer, J. L. Electrochemical and Solid-State
Letters 2003, 6, A1.
(47) Gover, R.; Bryan, A.; Burns, P.; Barker, J. Solid State Ionics 2006, 177, 1495–1500.
(48) Ponrouch, A.; Monti, D.; Boschin, A.; Steen, B.; Johansson, P.; Palac´ın, M. R. J. Mater. Chem. A 2015, 3, 22–42.
(49) Krachkovskiy, S. A.; Bazak, J. D.; Fraser, S.; Halalay, I. C.; Goward, G. R. Journal of The Electrochemical Society 2017, 164, A912–A916.
(50) Cresce, A. V.; Russell, S. M.; Borodin, O.; Allen, J. A.; Schroeder, M. A.; Dai, M.; Peng, J.; Gobet, M. P.; Greenbaum, S. G.; Rogers, R. E.; Xu, K. Phys. Chem. Chem. Phys. 2017, 19, 574–586.
(51) Seo, D. M.; Borodin, O.; Balogh, D.; O’Connell, M.; Ly, Q.; Han, S.-D.; Passerini, S.; Henderson, W. A. Journal of the Electrochemical Society
2013, 160, A1061–A1070.
(52) Wahlers, J.; Fulfer, K. D.; Harding, D. P.; Kuroda, D. G.; Kumar, R.; Jorn, R. The Journal of Physical Chemistry C 2016, 120, 17949–17959. (53) Xu, K.; Lam, Y.; Zhang, S. S.; Jow, T. R.; Curtis, T. B. Journal of
Physical Chemistry C 2007, 111, 7411–7421.
(54) Xu, K. Journal of The Electrochemical Society 2007, 154, A162. (55) Nielsen, M. A.; Chung, I. I., Quantum Computation and Quantum In-
formation; Cambridge University Press: 2010.
(56) J. M. Thijssen, Computational Physics, Second Edi; Cambridge Univer- sity Press: 2007.
(57) Foresman, J. B.; Firsch, Æ., Exploring Chemistry with Electronic Struc-
ture Methods, Third Edit; Gaussian Inc: 2015.
(58) Stewart, J. J. P. Journal of Molecular Modeling 2013, 19, 1–32. (59) Pople, J. A.; Santry, D. P.; Segal, G. A. The Journal of Chemical Physics
1965, 43, S129–S135.
(60) Hohenberg, P.; Kohn, W. Physical Review 1964, 136, B864–B871. (61) Kohn, W.; Sham, L. J. Physical Review 1965, 140, A1133–A1138. (62) Perdew, J. P. AIP Conference Proceedings 2001, 577, 1–20.
(63) Schlegel, H. B. Wiley Interdisciplinary Reviews: Computational Molec-
ular Science 2011, 1, 790–809.
(64) Schlegel, H. B. Adv. Chem. Phys. 1987, 67, 249.
(65) Ochterski, J. W.; Ph, D. Gaussian Inc Pittsburgh PA 2000, 264, 1–19. (66) Car, R.; Parrinello, M. Physical Review Letters 1985, 55, 2471–2474. (67) Okoshi, M.; Yamada, Y.; Yamada, A.; Nakai, H. Journal of the Electro-
chemical Society 2013, 160, A2160–A2165.
(68) Okoshi, M.; Yamada, Y.; Komaba, S.; Yamada, A.; Nakai, H. Journal
of The Electrochemical Society 2017, 164, A54–A60.
(69) Foresman, J. B.; Firsch, Æ., Exploring Chemistry with Electronic Struc-
(70) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Pe- tersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Jr.; Peralta, J. E.; Ogliaro, F.; Bearkpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Starovero, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Barkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Guassian 09, Revision B.01, 2010.
(71) J´onsson, E.; Johansson, P. Physical Chemistry Chemical Physics 2012,
14, 10774.
(72) Chen, S.; Ishii, J.; Horiuchi, S.; Yoshizawa-Fujita, M.; Izgorodina, E. I.
Phys. Chem. Chem. Phys. 2017, 19, 17366–17372.
(73) De, S.; Boda, A.; Ali, S. M. Journal of Molecular Structure: THEOCHEM
2010, 941, 90–101.
(74) Klamt, A.; Sch¨u¨urmann, G. J. Chem. Soc., Perkin Trans. 2 1993, 799– 805.
(75) Seo, D. M.; Borodin, O.; Han, S.-D.; Boyle, P. D.; Henderson, W. A.
Journal of the Electrochemical Society 2012, 159, A1489–A1500.
(76) Borodin, O.; Suo, L.; Gobet, M.; Ren, X.; Wang, F.; Faraone, A.; Peng, J.; Olguin, M.; Schroeder, M.; Ding, M. S.; Gobrogge, E.; Von Wald Cresce, A.; Munoz, S.; Dura, J. A.; Greenbaum, S.; Wang, C.; Xu, K.
ACS Nano 2017, 11, 10462–10471.
(77) Borodin, O.; Olguin, M.; Ganesh, P.; Kent, P. R.; Allen, J. L.; Hender- son, W. A. Physical Chemistry Chemical Physics 2016, 18, 164–175. (78) Blint, R. J. Journal of The Electrochemical Society 1995, 142, 696–702. (79) Sp˚angberg, D.; Hermansson, K. Chemical Physics 2004, 300, 165–176.
(80) Kamath, G.; Cutler, R. W.; Deshmukh, S. A.; Shakourian-Fard, M.; Parrish, R.; Huether, J.; Butt, D. P.; Xiong, H.; Sankaranarayanan, S. K. R. S. The Journal of Physical Chemistry C 2014, 118, 13406– 13416.
(81) He, M.; Lau, K. C.; Ren, X.; Xiao, N.; McCulloch, W. D.; Curtiss, L. A.; Wu, Y. Angewandte Chemie International Edition 2016, 55, 15310– 15314.
(82) Okoshi, M.; Chou, C.-P.; Nakai, H. The Journal of Physical Chemistry