@article{Wang2018, author = {Wang, Aiping and Kadam, Sanket and Li, Hong and Shi, Siqi and Qi, Yue}, journal = {npj Computational Materials}, number = {1}, pages = {15}, publisher = {Springer US}, title = {{Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries}}, volume = {4}, year = {2018}, abstract = {}, doiurl = {10.1038/s41524-018-0064-0}, issn = {20573960}, url = {http://dx.doi.org/10.1038/s41524-018-0064-0}, } @article{Yu2020, author = {Yu, Zhiao and others}, journal = {Nature Energy}, number = {7}, pages = {526--533}, publisher = {Springer US}, title = {{Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries}}, volume = {5}, year = {2020}, abstract = {}, doiurl = {10.1038/s41560-020-0634-5}, isbn = {4156002006345}, issn = {20587546}, url = {http://dx.doi.org/10.1038/s41560-020-0634-5}, } @article{Paul-Orecchio2022, author = {Paul-Orecchio, Austin G. and Weeks, Jason A. and Dolocan, Andrei and Mullins, C. Buddie}, journal = {ACS Applied Energy Materials}, number = {8}, pages = {9437--9446}, title = {{High-Stability Lithium Metal Batteries Enabled by a Tetrahydrofuran-Based Electrolyte Mixture}}, volume = {5}, year = {2022}, abstract = {T batteries.}, doiurl = {10.1021/acsaem.2c00993}, issn = {25740962}, } @article{Chekushkin2021, author = {Chekushkin, Petr M. and Merenkov, Ivan S. and Smirnov, Vladimir S. and Kislenko, Sergey A. and Nikitina, Victoria A.}, journal = {Electrochimica Acta}, pages = {137843}, publisher = {Elsevier Ltd}, title = {{The physical origin of the activation barrier in Li-ion intercalation processes: the overestimated role of desolvation}}, volume = {372}, year = {2021}, abstract = {ses.}, doiurl = {10.1016/j.electacta.2021.137843}, issn = {00134686}, } @article{Hou2021, author = {Hou, Singyuk and Ji, Xiao and Gaskell, Karen and Wang, Peng Fei and Wang, Luning and Xu, Jijian and Sun, Ruimin and Borodin, Oleg and Wang, Chunsheng}, journal = {Science}, number = {6564}, pages = {172--178}, title = {{Solvation sheath reorganization enables divalent metal batteries with fast interfacial charge transfer kinetics}}, volume = {374}, year = {2021}, abstract = {.}, doiurl = {10.1126/science.abg3954}, issn = {10959203}, } @article{Meng2022, author = {Meng, Y. Shirley and Srinivasan, Venkat and Xu, Kang}, journal = {Science}, number = {6624}, title = {{Designing better electrolytes}}, volume = {378}, year = {2022}, abstract = {.}, doiurl = {10.1126/science.abq3750}, issn = {10959203}, } @article{Doan2020, author = {Doan, Hieu A. and Agarwal, Garvit and Qian, Hai and Counihan, Michael J. and Rodr{\'{i}}guez-L{\'{o}}pez, Joaqu{\'{i}}n and Moore, Jeffrey S. and Assary, Rajeev S.}, journal = {Chemistry of Materials}, number = {15}, pages = {6338--6346}, title = {{Quantum Chemistry-Informed Active Learning to Accelerate the Design and Discovery of Sustainable Energy Storage Materials}}, volume = {32}, year = {2020}, abstract = {.}, doiurl = {10.1021/acs.chemmater.0c00768}, issn = {15205002}, } @article{Cheng2015, author = {Cheng, Lei and Assary, Rajeev S. and Qu, Xiaohui and Jain, Anubhav and Ong, Shyue Ping and Rajput, Nav Nidhi and Persson, Kristin and Curtiss, Larry A.}, journal = {Journal of Physical Chemistry Letters}, number = {2}, pages = {283--291}, title = {{Accelerating Electrolyte Discovery for Energy Storage with High-Throughput Screening}}, volume = {6}, year = {2015}, abstract = {.}, doiurl = {10.1021/jz502319n}, issn = {19487185}, } @article{Qu2015, author = {Qu, Xiaohui and Jain, Anubhav and Rajput, Nav Nidhi and Cheng, Lei and Zhang, Yong and Ong, Shyue Ping and Brafman, Miriam and Maginn, Edward and Curtiss, Larry A. and Persson, Kristin A.}, journal = {Computational Materials Science}, pages = {56--67}, publisher = {Elsevier B.V.}, title = {{The Electrolyte Genome project: A big data approach in battery materials discovery}}, volume = {103}, year = {2015}, abstract = {We present a high-throughput infrastructure for the automated calculation of molecular properties with a focus on battery electrolytes. The infrastructure is largely open-source and handles both practical aspects (input file generation, output file parsing, and information management) as well as more complex problems (structure matching, salt complex generation, and failure recovery). Using this infrastructure, we have computed the ionization potential (IP) and electron affinities (EA) of 4830 molecules relevant to battery electrolytes (encompassing almost 55,000 quantum mechanics calculations) at the B3LYP/6-31+G∗level. We describe automated workflows for computing redox potential, dissociation constant, and salt-molecule binding complex structure generation. We present routines for automatic recovery from calculation errors, which brings the failure rate from 9.2% to 0.8% for the QChem DFT code. Automated algorithms to check duplication between two arbitrary molecules and structures are described. We present benchmark data on basis sets and functionals on the G2-97 test set; one finding is that a IP/EA calculation method that combines PBE geometry optimization and B3LYP energy evaluation requires less computational cost and yields nearly identical results as compared to a full B3LYP calculation, and could be suitable for the calculation of large molecules. Our data indicates that among the 8 functionals tested, XYGJ-OS and B3LYP are the two best functionals to predict IP/EA with an RMSE of 0.12 and 0.27 eV, respectively. Application of our automated workflow to a large set of quinoxaline derivative molecules shows that functional group effect and substitution position effect can be separated for IP/EA of quinoxaline derivatives, and the most sensitive position is different for IP and EA.}, doiurl = {10.1016/j.commatsci.2015.02.050}, issn = {09270256}, url = {http://dx.doi.org/10.1016/j.commatsci.2015.02.050}, } @article{Korth2014, author = {Korth, Martin}, journal = {Physical Chemistry Chemical Physics}, number = {17}, pages = {7919--7926}, title = {{Large-scale virtual high-throughput screening for the identification of new battery electrolyte solvents: Evaluation of electronic structure theory methods}}, volume = {16}, year = {2014}, abstract = {The performance of semi-empirical quantum mechanical (SQM), density functional theory (DFT) and wave function theory (WFT) methods is evaluated for the purpose of screening a large number of molecular structures with respect to their electrochemical stability to identify new battery electrolyte solvents. Starting from 100000 database entries and based on more than 46000 DFT calculations, 83 candidate molecules are identified and then used for benchmarking lower-level computational models (SQM, DFT) with respect to higher-level WFT reference data. A combination of SQM and WFT methods is suggested as a screening strategy at the electronic structure theory level. Using a subset of over 11000 typical organic molecules and based on over 22000 high-level WFT calculations, several simple models are tested for the prediction of ionization potentials (IPs) and electron affinities (EAs). Reference data are made available for the development of more sophisticated QSPR models. {\textcopyright} 2014 the Partner Organisations.}, doiurl = {10.1039/c4cp00547c}, issn = {14639076}, } @article{Borodin2015, author = {Borodin, Oleg and Olguin, Marco and Spear, Carrie E. and Leiter, Kenneth W. and Knap, Jaroslaw}, journal = {Nanotechnology}, number = {35}, pages = {354003}, publisher = {IOP Publishing}, title = {{Towards high throughput screening of electrochemical stability of battery electrolytes}}, volume = {26}, year = {2015}, abstract = {High throughput screening of solvents and additives with potential applications in lithium batteries is reported. The initial test set is limited to carbonate and phosphate-based compounds and focused on their electrochemical properties. Solvent stability towards first and second reduction and oxidation is reported from density functional theory (DFT) calculations performed on isolated solvents surrounded by implicit solvent. The reorganization energy is estimated from the difference between vertical and adiabatic redox energies and found to be especially important for the accurate prediction of reduction stability. A majority of tested compounds had the second reduction potential higher than the first reduction potential indicating that the second reduction reaction might play an important role in the passivation layer formation. Similarly, the second oxidation potential was smaller for a significant subset of tested molecules than the first oxidation potential. A number of potential sources of errors introduced during screening of the electrolyte electrochemical properties were examined. The formation of lithium fluoride during reduction of semifluorinated solvents such as fluoroethylene carbonate and the H-transfer during oxidation of solvents were found to shift the electrochemical potential by 1.5-2 V and could shrink the electrochemical stability window by as much as 3.5 V when such reactions are included in the screening procedure. The initial oxidation reaction of ethylene carbonate and dimethyl carbonate at the surface of the completely de-lithiated LiNi0.5Mn1.5O4 high voltage spinel cathode was examined using DFT. Depending on the molecular orientation at the cathode surface, a carbonate molecule either exhibited deprotonation or was found bound to the transition metal via its carbonyl oxygen.}, doiurl = {10.1088/0957-4484/26/35/354003}, issn = {13616528}, url = {http://dx.doi.org/10.1088/0957-4484/26/35/354003}, } @article{JCC2023, author = {Orekhov, M A}, journal = {J. Comput. Chem.}, pages = {https://doi.org/10.1002/jcc.27229}, title = {{Correcting charge distribution in reduced Li-molecule pair for computational screening of battery solvents}}, year = {2023}, } @article{Wang2023a, author = {Wang, Da and He, Tingting and Wang, Aiping and Guo, Kai and Avdeev, Maxim and Ouyang, Chuying and Chen, Liquan and Shi, Siqi}, journal = {Advanced Functional Materials}, number = {11}, pages = {2212342}, title = {{A Thermodynamic Cycle-Based Electrochemical Windows Database of 308 Electrolyte Solvents for Rechargeable Batteries}}, volume = {33}, year = {2023}, abstract = {Rational design of wide electrochemical window (ECW) electrolytes to pair with high-voltage cathodes is an emerging trend to push the energy density limits of current rechargeable batteries. Traditional single-electronic/gas-phase approximation-based methods (e.g., highest occupied molecular orbital/lowest unoccupied molecular orbital) are increasingly recognized to have large deviations from experiments when predicting ECWs of electrolytes involving complex solvent interactions. Specifically, by examining available experimental ECWs of 68 electrolyte solvents extracted from ≈140 000 literature sources, which are conventionally divided into five functional-group categories (covering commonly used carbonate-based ethylene carbonate (EC)/propylene carbonate (PC) and ether-based tetrahydrofuran), it is found that mean-absolute-errors (MAE) of traditional methods reach up to 3.25 V. Herein, a thermodynamic cycle-based ECW prediction approach is proposed including two long-term overlooked reorganization-energy and solvation-energy corrections, each of which can be quantified by two geometric descriptors ($\lambda$ and $\Delta$Gsol), reducing MAE below 0.68 V. Following this, a database containing ECWs for 308 electrolyte solvents, obtained by traversing single functional-group substitutions, is established. Furthermore, two omitted solvents with ECWs over 6.00 V and excellent structural stabilities (bond-length change < 0.10 {\AA} during redox process) are retrieved by stepwise screening of structural/electronic parallel properties. This study demonstrates the benefits of improving ECW prediction accuracy and accumulating descriptors to accelerate rapid screening of superior battery electrolytes.}, doiurl = {10.1002/adfm.202212342}, issn = {16163028}, } @article{Agarwal2020, author = {Agarwal, Garvit and Doan, Hieu and Assary, Rajeev S.}, journal = {Journal of The Electrochemical Society}, pages = {100545}, title = {{Molecular Structure and Electron Affinity of Metal-Solvent Complexes: Insights from Density Functional Theory Simulations}}, volume = {167}, year = {2020}, abstract = {For more than sixty years, markets and hierarchies have dominated our thinking about economic organization1. This paper suggests that a third form, the ecosystem organizational form, has now become so important in practice that it should be accorded equal recognition in theory and in policy-making.}, } @article{Rulev2020, author = {Rulev, Alexey A. and Frolov, Alexander and Doronin, Sergey and Bezuglov, Iliya and Itkis, Daniil M. and Yashina, Lada V.}, journal = {Physical Chemistry Chemical Physics}, number = {28}, pages = {16184--16192}, title = {{Revising the pathways of the Li reaction with organic carbonates}}, volume = {22}, year = {2020}, abstract = {The metallic lithium electrode has major concerns such as extremely high reactivity and nonuniform needle-like electrodeposition, limiting its wide application as a negative electrode in secondary batteries. Its reactions with the electrolyte leading to solid electrolyte interphase (SEI) formation play an important role, and controlling its composition and properties can help to overcome both difficulties. Even though solid electrolyte interphase chemistry and properties seem to be well known, many surface chemistry experiments reported are not perfect with respect to the purity needed for Li studies and can be interpreted alternatively. Here, we studied reactions between lithium and propylene carbonate and ethylene carbonate in model reactions realized in an ultra-high vacuum. In addition to the already reported reaction pathway yielding lithium carbonate and semicarbonate, our theoretical (DFT) modeling confirms the preference of alternative routes. Along with the most beneficial final lithium carbonates, dilithium 1,2-dialkoxide (DD) can form barrierlessly as a final product by two-electron transfer. Experimental XPS/NEXAFS studies of gas phase and solid-gas model reactions revealed that in both cases DD is the main reaction product. Understanding of the discovered reaction pathway can also be essential for reactions in liquid electrolytes, although the low electric conductivity of the SEI makes it less probable.}, doiurl = {10.1039/d0cp02228d}, issn = {14639076}, } @article{Xu2023, author = {Xu, Jijian and others}, journal = {Nature}, pages = {694}, publisher = {Springer US}, title = {{Electrolyte design for Li-ion batteries under extreme operating conditions}}, volume = {614}, year = {2023}, abstract = {The ideal electrolyte for the widely used LiNi0.8Mn0.1Co0.1O2 (NMC811)||graphite lithium-ion batteries is expected to have the capability of supporting higher voltages (≥4.5 volts), fast charging (≤15 minutes), charging/discharging over a wide temperature range (±60 degrees Celsius) without lithium plating, and non-flammability1–4. No existing electrolyte simultaneously meets all these requirements and electrolyte design is hindered by the absence of an effective guiding principle that addresses the relationships between battery performance, solvation structure and solid-electrolyte-interphase chemistry5. Here we report and validate an electrolyte design strategy based on a group of soft solvents that strikes a balance between weak Li+–solvent interactions, sufficient salt dissociation and desired electrochemistry to fulfil all the aforementioned requirements. Remarkably, the 4.5-volt NMC811||graphite coin cells with areal capacities of more than 2.5 milliampere hours per square centimetre retain 75 per cent (54 per cent) of their room-temperature capacity when these cells are charged and discharged at −50 degrees Celsius (−60 degrees Celsius) at a C rate of 0.1C, and the NMC811||graphite pouch cells with lean electrolyte (2.5 grams per ampere hour) achieve stable cycling with an average Coulombic efficiency of more than 99.9 per cent at −30 degrees Celsius. The comprehensive analysis further reveals an impedance matching between the NMC811 cathode and the graphite anode owing to the formation of similar lithium-fluoride-rich interphases, thus effectively avoiding lithium plating at low temperatures. This electrolyte design principle can be extended to other alkali-metal-ion batteries operating under extreme conditions.}, doiurl = {10.1038/s41586-022-05627-8}, issn = {14764687}, } @article{Delp2016, author = {Delp, Samuel A. and Borodin, Oleg and Olguin, Marco and Eisner, Claire G. and Allen, Joshua L. and Jow, T. Richard}, journal = {Electrochimica Acta}, pages = {498--510}, publisher = {Elsevier Ltd}, title = {{Importance of Reduction and Oxidation Stability of High Voltage Electrolytes and Additives}}, volume = {209}, year = {2016}, abstract = {The electrolyte is a critical component for rechargeable Li-ion batteries, especially batteries containing high voltage cathodes. A series of electrolyte salts, solvents and additives was investigated via cyclic voltammetry (CV) on glassy carbon (GC) electrodes. Quantum chemistry (QC) calculations were used for prediction of oxidation and reduction stability of electrolyte components such as ethylene carbonate (EC), dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), tris(trimethylsilyl) phosphate (TMSP), 1,3-propane sultone (PS), tris(hexafluoroisopropyl) phosphate (HFiPP) and lithium salts such as LiPF6, LiBF4, lithium difluoro(oxalato)borate (LiDFOB), lithium 4,5-dicyano-2-trifluoromethyl-imidazolide (LiTDI), and lithium bis(trifluoromethanesulfonimide) (LiTFSI). QC calculations predicted that defluorination of LiPF6 and LiTFSI aggregates coupled with electron transfer significantly increased their reduction potential, while H-transfer upon oxidation lowered oxidation potential for many solvents. The composition of the Li+ cation solvation shell was estimated from the binding energies for the Li+–solvent complexes using cluster-continuum calculations and was used to provide insight into the experimental data on electrolyte reduction. Full coin cell data was acquired using LiNi0.5Mn1.5O4 (LNMO) cathodes with graphite anodes at 25 °C and 55 °C. Differential capacity plots (dQ/dE vs. E) and electrochemical impedance spectroscopy (EIS) results. The electrolyte with the most desirable performance was 1 M LiPF6 in 3:7 EC:EMC (wt%) with 1 wt% TMSP. Oxidative CV experiments show that the TMSP containing electrolyte has a slightly lower oxidation stability compared to the baseline, which is consistent with the order of oxidation stability of electrolyte components from QC calculations. The EIS measurements showed that the TMSP containing electrolyte had the lowest impedance after cycling and the dQ/dE plots show that the redox reactions retained their peak shape and area more so than an electrolyte without TMSP, indicating a greater capacity retention. Density functional theory calculations of TMSP oxidation on the LNMO surface were performed in order to provide insight into the additive role in improving cell performance.}, doiurl = {10.1016/j.electacta.2016.05.100}, issn = {00134686}, url = {http://dx.doi.org/10.1016/j.electacta.2016.05.100}, } @article{Leung2013, author = {Leung, Kevin}, journal = {Chemical Physics Letters}, pages = {1--8}, publisher = {Elsevier B.V.}, title = {{Two-electron reduction of ethylene carbonate: A quantum chemistry re-examination of mechanisms}}, volume = {568-569}, year = {2013}, abstract = {Passivating solid-electrolyte interphase (SEI) films arising from electrolyte decomposition on low-voltage lithium ion battery anode surfaces are critical for battery operations. We review the recent theoretical literature on electrolyte decomposition and emphasize the modeling work on two-electron reduction of ethylene carbonate (EC, a key battery organic solvent). One of the two-electron pathways, which releases CO gas, is re-examined using simple quantum chemistry calculations. Excess electrons are shown to preferentially attack EC in the order (broken EC-) > (intact EC-) > EC. This confirms the viability of two electron processes and emphasizes that they need to be considered when interpreting SEI experiments. A speculative estimate of the crossover between one- and two-electron regimes under a homogeneous reaction zone approximation is proposed. {\textcopyright} 2013 Elsevier B.V. All rights reserved.}, doiurl = {10.1016/j.cplett.2012.08.022}, issn = {00092614}, url = {http://dx.doi.org/10.1016/j.cplett.2012.08.022}, } @article{Kim2023, author = {Kim, Sunghwan and Chen, Jie and Cheng, Tiejun and Gindulyte, Asta and He, Jia and He, Siqian and Li, Qingliang and Shoemaker, Benjamin A. and Thiessen, Paul A. and Yu, Bo and Zaslavsky, Leonid and Zhang, Jian and Bolton, Evan E.}, journal = {Nucleic Acids Research}, number = {D1}, pages = {D1373--D1380}, title = {{PubChem 2023 update}}, volume = {51}, year = {2023}, abstract = {PubChem (https://pubchem.ncbi.nlm.nih.gov) is a popular chemical information resource that serves a wide range of use cases. In the past two years, a number of changes were made to PubChem. Data from more than 120 data sources was added to PubChem. Some major highlights include: the integration of Google Patents data into PubChem, which greatly expanded the coverage of the PubChem Patent data collection; the creation of the Cell Line and Taxonomy data collections, which provide quick and easy access to chemical information for a given cell line and taxon, respectively; and the update of the bioassay data model. In addition, new functionalities were added to the PubChem programmatic access protocols, PUG-REST and PUG-View, including support for target-centric data download for a given protein, gene, pathway, cell line, and taxon and the addition of the 'standardize' option to PUG-REST, which returns the standardized form of an input chemical structure. A significant update was also made to PubChemRDF. The present paper provides an overview of these changes.}, doiurl = {10.1093/nar/gkac956}, issn = {13624962}, } @article{Wu2005, author = {Wu, Qin and {Van Voorhis}, Troy}, journal = {Physical Review A - Atomic, Molecular, and Optical Physics}, number = {2}, pages = {7--10}, title = {{Direct optimization method to study constrained systems within density-functional theory}}, volume = {72}, year = {2005}, abstract = {Consider a system with an arbitrary constraint on its electron density (e.g., that there are N charges on a certain group of atoms). We show that in Kohn-Sham density functional theory, the minimum energy state consistent with the constraint is actually a maximum with respect to the constraint potential, and that this solution is unique. This leads us to an efficient algorithm for calculations on constrained systems. Illustrative studies are shown for charge transfer in the zincbacteriochlorin-bacteriochlorin complex, polyene and alkane chains. {\textcopyright} 2005 The American Physical Society.}, doiurl = {10.1103/PhysRevA.72.024502}, issn = {10502947}, } @article{Valiev2010, author = {Valiev, M. and Bylaska, E. J. and Govind, N. and Kowalski, K. and Straatsma, T. P. and {Van Dam}, H. J.J. and Wang, D. and Nieplocha, J. and Apra, E. and Windus, T. L. and {De Jong}, W. A.}, journal = {Computer Physics Communications}, number = {9}, pages = {1477--1489}, publisher = {Elsevier B.V.}, title = {{NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations}}, volume = {181}, year = {2010}, abstract = {The latest release of NWChem delivers an open-source computational chemistry package with extensive capabilities for large scale simulations of chemical and biological systems. Utilizing a common computational framework, diverse theoretical descriptions can be used to provide the best solution for a given scientific problem. Scalable parallel implementations and modular software design enable efficient utilization of current computational architectures. This paper provides an overview of NWChem focusing primarily on the core theoretical modules provided by the code and their parallel performance. {\textcopyright} 2010 Elsevier B.V.}, doiurl = {10.1016/j.cpc.2010.04.018}, issn = {00104655}, url = {http://dx.doi.org/10.1016/j.cpc.2010.04.018}, } @article{Zhao2006, author = {Zhao, Yan and Schultz, Nathan E. and Truhlar, Donald G.}, journal = {Journal of Chemical Theory and Computation}, number = {2}, pages = {364--382}, title = {{Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions}}, volume = {2}, year = {2006}, abstract = {By incorporating kinetic-energy density in a balanced way in the exchange and correlational functionals and removing self-correlation effects, we have designed a density functional that is broadly applicable to organometallic, inorganometallic, and nonmetallic bonding, thermochemistry, thermochemical kinetics, and noncovalent interactions as well as satisfying the uniform electron gas limit. The average error is reduced by a factor of 1.3 compared with the best previously available functionals, but even more significantly, we find a functional that has a high accuracy for all four categories of interaction.}, issn = {1549-9618}, url = {http://pubs.acs.org/doi/abs/10.1021/ct0502763}, } @article{Dodda2017, author = {Dodda, Leela S. and {De Vaca}, Israel Cabeza and Tirado-Rives, Julian and Jorgensen, William L.}, journal = {Nucleic Acids Research}, number = {W1}, pages = {W331--W336}, title = {{LigParGen web server: An automatic OPLS-AA parameter generator for organic ligands}}, volume = {45}, year = {2017}, abstract = {The accurate calculation of protein/nucleic acid-ligand interactions or condensed phase properties by force field-based methods require a precise description of the energetics of intermolecular interactions. Despite the progress made in force fields, small molecule parameterization remains an open problem due to the magnitude of the chemical space; the most critical issue is the estimation of a balanced set of atomic charges with the ability to reproduce experimental properties. The LigParGen web server provides an intuitive interface for generating OPLS-AA/1.14∗CM1A(-LBCC) force field parameters for organic ligands, in the formats of commonly used molecular dynamics and Monte Carlo simulation packages. This server has high value for researchers interested in studying any phenomena based on intermolecular interactions with ligands via molecular mechanics simulations. It is free and open to all at jorgensenresearch.com/ligpargen, and has no login requirements.}, doiurl = {10.1093/nar/gkx312}, issn = {13624962}, } @article{Wang2001, author = {Wang, Y. and Nakamura, S. and Ue, M. and Balbuena, P. B.}, journal = {Journal of the American Chemical Society}, number = {47}, pages = {11708--11718}, title = {{Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: Reduction mechanisms of ethylene carbonate}}, volume = {123}, year = {2001}, abstract = {Reductive decomposition mechanisms for ethylene carbonate (EC) molecule in electrolyte solutions for lithium-ion batteries are comprehensively investigated using density functional theory. In gas phase the reduction of EC is thermodynamically forbidden, whereas in bulk solvent it is likely to undergo one- as well as two-electron reduction processes. The presence of Li cation considerably stabilizes the EC reduction intermediates. The adiabatic electron affinities of the supermolecule Li+(EC)n (n = 1-4) successively decrease with the number of EC molecules, independently of EC or Li+ being reduced. Regarding the reductive decomposition mechanism, Li+(EC)n is initially reduced to an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approximately 11.0 kcal/mol barrier, bringing up a radical anion coordinated with Li+. Among the possible termination pathways of the radical anion, thermodynamically the most favorable is the formation of lithium butylene dicarbonate, (CH2CH2OCO2Li)2, followed by the formation of one O-Li bond compound containing an ester group, LiO(CH2)2CO2(CH2)2 OCO2Li, then two very competitive reactions of the further reduction of the radical anion and the formation of lithium ethylene dicarbonate, (CH2OCO2Li)2, and the least favorable is the formation of a C-Li bond compound (Li carbides), Li(CH2)2OCO2Li. The products show a weak EC concentration dependence as has also been revealed for the reactions of LiCO3- with Li+(EC)n; that is, the formation of Li2CO3 is slightly more favorable at low EC concentrations, whereas (CH2OCO2Li)2 is favored at high EC concentrations. On the basis of the results presented here, in line with some experimental findings, we find that a two-electron reduction process indeed takes place by a stepwise path. Regarding the composition of the surface films resulting from solvent reduction, for which experiments usually indicate that (CH2OCO2Li)2 is a dominant component, we conclude that they comprise two leading lithium alkyl bicarbonates, (CH2CH2OCO2Li)2 and (CH2OCO2Li)2, together with LiO(CH2)2CO2(CH2)2 OCO2Li, Li(CH2)2OCO2Li and Li2CO3.}, doiurl = {10.1021/ja0164529}, issn = {00027863}, } @book{Atkin2006, author = {Atkin, Peter and Paula, Julio}, pages = {1072}, publisher = {Oxford University Press}, title = {{Physical chemistry}}, year = {2006}, doiurl = {10.1039/C1CS15191F}, isbn = {978-0716787594}, issn = {0306-0012}, }