Роль исследования ландшафта потенциальной энергии в разработке новых электролитных растворов

Разработка новых электролитных растворов с улучшенными характеристиками является ключевой задачей для создания высокоэффективных аккумуляторов, топливных элементов, суперконденсаторов и других электрохимических устройств. Исследование ландшафта потенциальной энергии (ЛПЭ) играет важную роль в этом процессе, предоставляя информацию о взаимодействиях между компонентами раствора на молекулярном уровне. В данной работе рассмотрена практика применения методов исследования ЛПЭ, основанных на классических и квантово-химических алгоритмах, для анализа структуры, динамики и термодинамических свойств электролитных растворов. Подробно рассматриваются межмолекулярные и ион-молекулярные взаимодействия на микроскопическом уровне, определяющие макроскопические свойства электролитного раствора. Подчеркнута важность идентификации стабильных конфигураций ионов и их сольватов. Анализ ЛПЭ позволяет систематически определять наиболее вероятные структуры и комплексы, образующиеся в растворе, что важно для понимания механизмов ионного транспорта. Исследование ЛПЭ позволяет определить энергетические барьеры, которые необходимо преодолеть для миграции ионов, что связано с проводимостью электролита. Применение методов исследования ЛПЭ в сочетании с экспериментальными данными открывает новые возможности для рационального дизайна электролитных растворов с требуемыми физико-химическими свойствами. 

1. Zittlau P, Mross S, Gond D, Kohns M. Molecular modeling and simulation of organic electrolyte solutions for lithium ion batteries. The Journal of Chemical Physics. 2024;161(12):124118. DOI:10.1063/5.0228158

2. Shi N, Wang G, Mu T, Li H, et al. Long sidechain imidazolium functionalized poly(vinyl chloride) membranes with low cost and high performance for vanadium redox flow batteries. Journal of Molecular Liquids. 2023;376:121401. DOI:10.1016/j.molliq.2023.121401

3. Deb D, Bhattacharya S. Imidazolium-based ionanofluid electrolytes with viscosity decoupled ion transport properties for lithium-ion batteries. Journal of Molecular Liquids. 2023;379:121645. DOI:10.1016/j.molliq.2023.121645

4. Wu Z, Tian Y, Chen H, Wang L, et al. Evolving aprotic Li–air batteries. Chemical Society Reviews. 2022;51(18):8045-8101. DOI:10.1039/D2CS00003B

5. Habibi P, Polat HM, Blazquez S, Vega C, et al. Accurate free energies of aqueous electrolyte solutions from molecular simulations with non-polarizable force fields. The Journal of Physical Chemistry Letters. 2024;15(16):4477-4485. DOI:10.1021/acs.jpclett.4c00428

6. Lu GW, Li CX, Wang WC, Wang ZH. A MonteCarlo simulation on structure and thermodynamics of potassium nitrate electrolyte solution. Molecular Physics. 2005;103(5):599-610. DOI:10.1080/00268970410001683834

7. Parida R, Yong Lee J. Boron based podand molecule as an anion receptor additive in Li-ion battery electrolytes: a combined density functional theory and molecular dynamics study. Journal of Molecular Liquids. 2023;384:122236. DOI:10.1016/j.molliq.2023.122236

8. Kartha TR, Mallik BS. Revisiting LiClO4 as an electrolyte for Li-ion battery: effect of aggregation behavior on ion-pairing dynamics and conductance. Journal of Molecular Liquids. 2020;302:112536. DOI:10.1016/j.molliq.2020.112536

9. Jiang H, Zhang Q, Zhang Y, Sui L, et al. Li-ion solvation in propylene carbonate electrolytes determined by molecular rotational measurements. Physical Chemistry Chemical Physics. 2019;21(20):10417-10422. DOI:10.1039/C8CP07552B

10. Chaban VV, Andreeva NA. Shorter-chained trialkylsulfonium cations are preferable as admixtures to lithium-ion and sodium-ion electrolytes in acetonitrile. Journal of Molecular Liquids. 2023;385:122399. DOI:10.1016/j.molliq.2023.122399

11. Haghani H, Behrouz M, Chaban VV. Triethylsulfonium-based ionic liquids enforce lithium salt electrolytes. Physical Chemistry Chemical Physics. 2022;24(16):9418-9431. DOI:10.1039/D2CP00275B

12. Chaban VV, Andreeva NA. Magnesium-based electrolytes with ionic liquids chloride additives: quantum chemical stationary point analysis. Journal of Molecular Liquids. 2024;402:124804. DOI:10.1016/j.molliq.2024.124804

13. Zhang W, Hu YH. Material design and performance of carbon monoxide‐fueled solid oxide fuel cells: a review. Energy Science & Engineering. 2023;11(9):3276-3288. DOI:10.1002/ese3.1502

14. Dethan JFN, Swamy V. Mechanical and thermal properties of carbon nanotubes and boron nitride nanotubes for fuel cells and hydrogen storage applications: a comparative review of molecular dynamics studies. International Journal of Hydrogen Energy. 2022; 47(59):24916-24944. DOI:10.1016/j.ijhydene.2022.05.240

15. Pant R, Sengupta S, Lyulin AV, Venkatnathan A. Computational investigation of a protic ionic liquid doped poly-benzimidazole fuel cell electrolyte. Journal of Molecular Liquids. 2020;314:113686. DOI:10.1016/j.molliq.2020.113686

16. Khan HA, Tawalbeh M, Aljawrneh B, Abuwatfa W, et al. A comprehensive review on supercapacitors: their promise to flexibility, high temperature, materials, design, and challenges. Energy. 2024;295:131043. DOI:10.1016/j.energy.2024.131043

17. Varner S, Wang ZG. Effects of dilution in ionic liquid supercapacitors. Physical Chemistry Chemical Physics. 2022;24(44):27362-27374. DOI:10.1039/D2CP03398D

18. Dashti Najafi M, Kowsari E, Reza Naderi H, Sarabadani Tafreshi S, et al. High-performance symmetric supercapacitor based on new functionalized graphene oxide composites with pyrimidine nucleotide and nucleoside. Journal of Molecular Liquids. 2022;348:118381. DOI:10.1016/j.molliq.2021.118381

19. Bakhshandeh A, Dos Santos AP, Levin Y. Efficient simulation method for nano-patterned charged surfaces in an electrolyte solution. Soft Matter. 2018;14(20):4081-4086. DOI:10.1039/C8SM00226F

20. Brkljača Z, Namjesnik D, Lützenkirchen J, Předota M, et al. Quartz/aqueous electrolyte solution interface: molecular dynamic simulation and interfacial potential measurements. The Journal of Physical Chemistry C. 2018;122(42):24025-24036. DOI:10.1021/acs.jpcc.8b04035

21. Di Tommaso D, Prakash M, Lemaire T, Lewerenz M, et al. Molecular dynamics simulations of hydroxyapatite nanopores in contact with electrolyte solutions: the effect of nanoconfinement and solvated ions on the surface reactivity and the structural, dynamical, and vibrational properties of water. Crystals. 2017;7(2):57. DOI:10.3390/cryst7020057

22. Karatrantos AV, Middendorf M, Nosov DR, Cai Q, et al. Diffusion and structure of propylene carbonate–metal salt electrolyte solutions for post-lithiumion batteries: from experiment to simulation. The Journal of Chemical Physics. 2024;161(5):054502. DOI:10.1063/5.0216222

23. Eisenhart AE, Beck TL. Quantum simulations of hydrogen bonding effects in glycerol carbonate electrolyte solutions. The Journal of Physical Chemistry B. 2021;125(8):2157-2166. DOI:10.1021/acs.jpcb.0c10942

24. Friedman R. Simulations of biomolecules in electrolyte solutions. Advanced Theory and Simulations. 2019;2(4):1800163. DOI:10.1002/adts.201800163

25. Chaiyasit P, Tongraar A, Kerdcharoen T. Characteristics of methylammonium ion (CH3NH3+) in aqueous electrolyte solution: an ONIOM-XS md simulation study. Chemical Physics. 2017;493:91-101. DOI:10.1016/j.chemphys.2017.06.012

26. Li Y, Wu F, Li Y, Liu M, et al. Ether-based electrolytes for sodium ion batteries. Chemical Society Reviews. 2022;51(11):4484-4536. DOI:10.1039/D1CS00948F

27. Yang Q, Zhang Z, Sun XG, Hu YS, et al. Ionic liquids and derived materials for lithium and sodium batteries. Chemical Society Reviews. 2018;47(6):2020-2064. DOI:10.1039/C7CS00464H

28. Yang L, Huang K. Electric conductivity in electrolyte solution under external electromagnetic field by nonequilibrium molecular dynamics simulation. The Journal of Physical Chemistry B. 2010;114(25):8449-8452. DOI:10.1021/jp102593m

29. Kumar P, Yashonath S. Ionic conductivity in aqueous electrolyte solutions: insights from computer simulations. Journal of Molecular Liquids. 2019;277:506-515. DOI:10.1016/j.molliq.2018.12.090

30. Liu Y, Zhu W, Li B, Yang L. Simulation study on the flow behaviors of weak electrolyte solutions in nanosized and micron-sized pores considering electric double layer interactions. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects. 2022;44(2):3532-3543. DOI:10.1080/15567036.2022.2067266

31. Guàrdia E, Martí J, Padró JA. Ion solvation in aqueous supercritical electrolyte solutions at finite concentrations: a computer simulation study. Theoretical Chemistry Accounts. 2006;115(2-3):161-169. DOI:10.1007/s00214-005-0055-3

32. Balbuena PB, Johnston KP, Rossky PJ. Molecular dynamics simulation of electrolyte solutions in ambient and supercritical water. 1. Ion solvation. The Journal of Physical Chemistry. 1996;100(7):2706-2715. DOI: 10.1021/jp952194o

33. Bosen A, Roth M. Simulation of a distillation column on an IBM PC, accounting for real behaviour of electrolyte solutions. Chemical Engineering & Technology. 1991;14(5):295-300. DOI:10.1002/ceat.270140502

34. Neria E, Nitzan A. Numerical simulations of solvation dynamics in electrolyte solutions. The Journal of Chemical Physics. 1994;100(5):3855-3868. DOI:10.1063/1.466374

35. Padró JA, Trullàs J, Giró A. Langevin dynamics simulations of electrolyte solutions. Influence of friction and random forces. Journal of the Chemical Society, Faraday Transactions. 1990;86(12):2139-2143. DOI: 10.1039/FT9908602139

36. Spohr E, Heinzinger K. Computer simulations of water and aqueous electrolyte solutions at interfaces. Electrochimica Acta. 1988;33(9):1211-1222. DOI: 10.1016/0013-4686(88)80151-8

37. Feng HJ, Zhou J, Lu XH. Molecular dynamics simulations on the interfacial structures of electrolyte solutions. Acta Chimica Sinica. 2009;67(21):2407-2412.

38. Neilson GW. The structure of aqueous electrolyte solutions: comparison of computer simulation and experiment. Zeitschrift für Naturforschung A. 1991;46(1-2): 100-106. DOI:10.1515/zna-1991-1-216

39. Lee LL, Llano-Restrepo M, Chapman WG, Shukla KP. Improved MSA theory for concentrated electrolyte solutions based on Monte-Carlo simulation at high ionic strengths. Journal of the Chinese Institute of Chemical Engineers. 1996;27(4).

40. Malekzadeh Moghani M, Khomami B. Flexible polyelectrolyte chain in a strong electrolyte solution: insight into equilibrium properties and force-extension behavior from mesoscale simulation. The Journal of Chemical Physics. 2016;144(2):024903. DOI:10.1063/1.4939720

41. Kohns M, Reiser S, Horsch M, Hasse H. Solvent activity in electrolyte solutions from molecular simulation of the osmotic pressure. The Journal of Chemical Physics. 2016;144(8):084112. DOI:10.1063/1.4942500

42. Yi L, Liang D, Zhou X, Li D, et al. Molecular dynamics simulations of carbon dioxide hydrate growth in electrolyte solutions of NaCl and MgCl2. Molecular Physics. 2014;112(24):3127-3137. DOI:10.1080/00268976.2014.932454

43. Fiates J, Ratochinski RH, Lourenço TC, Da Silva JLF, et al. Fluoroalkoxyaluminate-based ionic liquids as electrolytes for sodium-ion batteries. Journal of Molecular Liquids. 2023;369:120919. DOI:10.1016/j.molliq.2022.120919

44. Xu X, Su L, Lu F, Yin Z, et al. Unraveling anion effect on lithium ion dynamics and interactions in concentrated ionic liquid electrolyte. Journal of Molecular Liquids. 2022;361:119629. DOI:10.1016/j.molliq.2022.119629

45. Khudozhitkov AE, Stange P, Stepanov AG, Kolokolov DI, et al. Structure, hydrogen bond dynamics and phase transition in a model ionic liquid electrolyte. Physical Chemistry Chemical Physics. 2022;24(10):6064-6071. DOI:10.1039/D2CP00452F

46. Calero C, Faraudo J, Aguilella-Arzo M. Molecular dynamics simulations of concentrated aqueous electrolyte solutions. Molecular Simulation. 2011;37(2):123-134. DOI:10.1080/08927022.2010.525513

47. Murad S, Oder K, Lin J. Molecular simulation of osmosis, reverse osmosis, and electro-osmosis in aqueous and methanolic electrolyte solutions. Molecular Physics. 1998;95(3):401-408. DOI:10.1080/00268979809483173

48. Berendsen HJC, van der Spoel D, van Drunen R. GROMACS - A message-passing parallel moleculardynamics implementation. Computer Physics Communication. 1995;91:43-56.

49. Lu G wu, Li Y feng, Sun W, Li C. Molecular dynamics simulation of hydration structure of KNO3 electrolyte solution. Chinese Journal of Chemical Physics. 2007;20(1):22-30. DOI:10.1360/cjcp2007.20(1).22.9

50. Kerisit S, Ilton ES, Parker SC. Molecular dynamics simulations of electrolyte solutions at the (100) goethite surface. The Journal of Physical Chemistry B. 2006;110(41):20491-20501. DOI:10.1021/jp0636569

51. Chaban VV, Andreeva NA. Aqueous electrolytes at the charged graphene Surface: Electrode-Electrolyte coupling. Journal of Molecular Liquids. 2023;387:122724.

52. Izarra AD, Coudert FX, Fuchs AH, Boutin A. Alchemical Osmo stat for Monte-Carlo simulation: sampling aqueous electrolyte solution in open systems. The Journal of Physical Chemistry B. 2023;127(3):766-776. DOI:10.1021/acs.jpcb.2c07902

53. Theiss M, Gross J. Nonprimitive model electrolyte solutions: comprehensive data from MonteCarlo simulations. Journal of Chemical & Engineering Data. 2020;65(2):634-639. DOI:10.1021/acs.jced.9b00855

54. Ozaki H, Kuratani K, Kiyobayashi T. MonteCarlo simulation of the ionic transport of electrolyte solutions at high concentrations based on the pseudo-lattice model. Journal of The Electrochemical Society. 2016;163(7):H576-H583. DOI:10.1149/2.0941607jes

55. Van Megen W, Snook I, Vincent B. Monte-Carlo simulation of small particle adsorption at the solid/electrolyte solution interface. Journal of Colloid and Interface Science. 1983;92(1):262-264. DOI:10.1016/0021-9797(83)90136-4

56. Lukšič M, Hribar-Lee B, Tochimani SB, Pizio O. Solvent primitive model for electrolyte solutions in disordered porous matrices of charged species. Replica Ornstein-Zernike theory and grand canonical monte Carlo simulations. Molecular Physics. 2012;110(1):17-30. DOI:10.1080/00268976.2011.631057

57. Jönsson M, Skepö M, Linse P. Monte-Carlo simulations of the hydrophobic effect in aqueous electrolyte solutions. The Journal of Physical Chemistry B. 2006;110(17):8782-8788. DOI:10.1021/jp0604241

58. Sørensen TS, Sloth P. Ion and potential distributions in charged and non-charged primitive spherical pores in equilibrium with primitive electrolyte solution calculated by grand canonical ensemble MonteCarlo simulation. Comparison with generalized Debye–Hückel and Donnan theory. Journal of the Chemical Society, Faraday Transactions. 1992;88(4):571-589. DOI:10.1039/FT9928800571

59. Svensson B, Jönsson B. The interaction between charged aggregates in electrolyte solution. A Monte-Carlo simulation study. Chemical Physics Letters. 1984; 108(6):580-584. DOI:10.1016/0009-2614(84)85058-7

60. Truzzolillo D, Bordi F, Sciortino F, Sennato S. Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte-Carlo simulation study in the Debye–Hückel approximation. The Journal of Chemical Physics. 2010;133(2):024901. DOI:10.1063/1.3459125

61. Li CX, Tian R, Lu GW, Wang ZH, Wang WC. Monte-Carlo simulation on model fluid of electrolyte solution. Acta Physico-Chimica Sinica. 2003;61(2):175-180.

62. Bedair MA, Abuelela AM, Melhi S, Yousif QA, et al. Highly effective inhibition of steel corrosion in 1.0 M HCl solution using a novel non-ionic surfactant with coumarin moiety: Practical and computational studies. Materials Chemistry and Physics. 2024;312:128644.

63. Duczinski R, Polesso BB, Duarte E, Bernard FL, et al. Separation of Co2/N2 mixtures by new il/acrylic polymer microcapsules designed by a one-step suspensionbased polymerization encapsulation process. Journal of Molecular Liquids. 2023;385:122394. DOI:10.1016/j.molliq.2023.122394

64. Chaban VV, Andreeva NA. Mutual miscibility of diethyl sulfoxide and acetonitrile: fundamental origin. Journal of Molecular Liquids. 2022;349:118110. DOI:10.1016/j.molliq.2021.118110

65. Chaban VV, Andreeva NA. Mixtures of diethyl sulfoxide and methanol: structure and thermodynamics. Journal of Solution Chemistry. 2022;51(7):788-801. DOI:10.1007/s10953-022-01167-x

66. Jones FGE, Dryfe RAW. Hydrodynamic voltammetry at the interface between immiscible electrolyte solutions: numerical simulation of the voltammetric response. Journal of Electroanalytical Chemistry. 2008;615(1):25-33. DOI:10.1016/j.jelechem.2007.11.021

67. Chaban V. Competitive solvation of the imidazolium cation by water and methanol. Chemical Physics Letters. 2015;623:76-81. DOI:10.1016/j.cplett.2015.01.051

68. Ohba T, Hata K, Chaban VV. Nanocrystallization of imidazolium ionic liquid in carbon nanotubes. The Journal of Physical Chemistry C. 2015;119(51): 28424-28429. DOI:10.1021/acs.jpcc.5b09423

69. Chizhik VI, Egorov AV, Komolkin AV, Vorontsova AA. Microstructure and dynamics of electrolyte solutions containing polyatomic ions by NMR relaxation and molecular dynamics simulation. Journal of Molecular Liquids. 2002;98-99:173-182. DOI:10.1016/S0167-7322(01)00306-3

70. Chaban VV, Voroshylova IV, Kalugin ON, Prezhdo OV. Acetonitrile boosts conductivity of imidazolium ionic liquids. The Journal of Physical Chemistry B. 2012;116(26):7719-7727. DOI:10.1021/jp3034825

71. Thakur RC, Sharma A, Sharma R, Kaur H. A comparative analysis of volumetric, viscometric and conductometric properties of triethylmethylammonium tetrafluoroborate (TEMABF4) and tetraethylammonium tetrafluoroborate (TEABF4) in pure propylene carbonate (PC) and binary aqueous propylene carbonate solvents. Journal of Molecular Liquids. 2023;374:121244. DOI:10.1016/j.molliq.2023.121244

72. Piatti E, Guglielmero L, Tofani G, Mezzetta A, et al. Ionic liquids for electrochemical applications: correlation between molecular structure and electrochemical stability window. Journal of Molecular Liquids. 2022;364:120001. DOI:10.1016/j.molliq.2022.120001

73. Dočkal J, Mimrová P, Lísal M, Moučka F. Structure of aqueous alkali metal halide electrolyte solutions from molecular simulations of phase-transferable polarizable models. Journal of Molecular Liquids. 2024;394:123797. DOI:10.1016/j.molliq.2023.123797

74. Panagiotopoulos AZ. Simulations of activities, solubilities, transport properties, and nucleation rates for aqueous electrolyte solutions. The Journal of Chemical Physics. 2020;153(1):010903. DOI:10.1063/5.0012102

75. Maftoon-Azad L. Electrochemical stability windows of Ali-cyclic ionic liquids as lithium metal battery electrolytes: a computational approach. Journal of Molecular Liquids. 2021;343:117589. DOI:10.1016/j.molliq.2021.117589

76. Chaban VV, Prezhdo OV. Ionic and molecular liquids: working together for robust engineering. The Journal of Physical Chemistry Letters. 2013;4(9): 1423-1431. DOI:10.1021/jz400113y

77. Bdey S, Boussadoune N, Allard F, Huot J, et al. Synthesis, structural study, and Na+ migration pathways simulation of the new phase Na3Al3(AsO4)4. Journal of Solid State Chemistry. 2024;330:124459. DOI:10.1016/j.jssc.2023.124459

78. Colherinhas G, Fileti EE, Chaban VV. Can inorganic salts tune electronic properties of graphene quantum dots? Physical Chemistry Chemical Physics. 2015;17(26):17413-17420. DOI:10.1039/C5CP02083B

79. Yun Y, Wu S, Wang D, Luo X, et al. Molecular dynamics simulations in semiconductor material processing: a comprehensive review. Measurement. 2025; 241:115708. DOI:10.1016/j.measurement.2024.115708

80. De Araujo Chagas H, Fileti EE, Colherinhas G. Comparing supercapacitors with graphene/graphyne electrodes and [Bmim][PF6], [Emim][BF4], [Ch][Gly] and [Pyr][Tfsi] ionic liquids using molecular dynamics. Journal of Molecular Liquids. 2023;379:121703. DOI:10.1016/j.molliq.2023.121703

81. Messias A, Fileti EE. Assessing the impact of valence asymmetry in ionic solutions and its consequences on the performance of supercapacitors. Physical Chemistry Chemical Physics. 2022;24(34):20445-20453. DOI:10.1039/D2CP00348A

82. Brieske DM, Warnecke A, Sauer DU. Modeling the volumetric expansion of the lithium-sulfur battery considering charge and discharge profiles. Energy Storage Materials. 2023;55:289-300. DOI:10.1016/j.ensm.2022.11.053

83. Zhang J, Pagotto J, Duignan TT. Towards predictive design of electrolyte solutions by accelerating ab initio simulation with neural networks. Journal of Materials Chemistry A. 2022;10(37):19560-19571. DOI:10.1039/D2TA02610D

84. Chaban VV, Andreeva NA. Sodium-ion electrolytes based on ionic liquids: a role of cation-anion hydrogen bonding. Journal of Molecular Modeling. 2016;22(8):172. DOI:10.1007/s00894-016-3042-9

85. Chaban VV. The tricyanomethanide anion favors low viscosity of the pure ionic liquid and its aqueous mixtures. Physical Chemistry Chemical Physics. 2015;17(47):31839-31849. DOI:10.1039/C5CP05666G