Dmytriv G. Interaction of lithium with d-metals and p-elements of III-V groups
Українська версіяThesis for the degree of Doctor of Science (DSc)
State registration number
0523U100191
Applicant for
Specialization
- 02.00.01 - Неорганічна хімія
04-10-2023
Specialized Academic Board
Д 35.051.10
Ivan Franko National University of Lviv
Essay
The purpose of the work is to solve a scientific problem, which consists in establishing regularities in the structure, nature of the chemical bond, and properties of compounds in lithium systems with d-metals and p-elements of groups III-V; determining phase equilibria in relevant systems and finding phases for materials of chemical current sources and with unique optical properties. The solution to the scientific problem is based on theoretical foundations and experimental approaches with the involvement of a complex of modern methods. Double, triple, and one quadruple system are investigated. In particular, changes to two state diagrams of binary Li-Ag and Li-Bi systems are proposed. The isothermal intersections of state diagrams of 10 ternary systems, in which 36 compounds are formed, were constructed, and refined. A regularity has been established that with the growth of the metallic properties of p-elements within the group, the concentration region in which intermetallic compounds are formed narrows. The classification of the structural types of compounds that are formed in the studied systems and all other structural types in the Li-T-M and Li-M-M' systems according to the classification of P. I. Krypyakevich was carried out. The regularity was established that with the increase in the period number for d-metals and p-elements, the number of structural types belonging to class 10 increases and decreases the number of structural types belonging to class 5. The electron density was calculated in a number of compounds, which made it possible to determine the types of bonds in these compounds: Li12Cu12,60Al14,37, Li8Cu12+xAl6-x (x = 1,16), Li18Cu15Al7, Li12Cu16+xAl26–x (x = 3,2), Li15Cu19Al16, Li1,36Zr4Si4, Li2-xAg1+xIn3 (х = 0,05), Li2B2C, LiBC3, Li4Ge2B and Li9Al4Sn5. Alloys from the homogeneity region of the continuous Li(ZnzAl1–z) solid solution series were investigated as anode materials for lithium-ion batteries and established that alloy with composition Li(Zn0,2Al0,8) has the best characteristics On the example of the Li-Ag-In model system, a new approach to the express determination of phases in ternary systems containing lithium is proposed, namely, the process of electrochemical delithiation of the lithium-rich phase in situ with simultaneous acquisition of powder diffractograms on synchrotron radiation high intensity. Based on the optical reflectance spectra, followed by the comparison of chrominance coordinates colored intermetallics that can be obtained without precious metals and that would be attractive for use are identified for the first time: LiCu2Al (red), LiCu2Ga (yellow), Li2ZnGa (purple), and Li2ZnIn (light blue). A crystal-chemical analysis of new structural types Li12Cu12,60Al14,37, Li8Cu12+xAl6–x, Li18Cu15Al7, Li2-xAg1+xIn3, Li278(In,Ag)154, Li2B2C, LiBC3, LiB2C2, Li4Ge2B and Li9Al4Sn5.
Research papers
1. Dmytriv G.S., Prystavskyj T.O., Pavlyuk V.V., Kevorkov D.G., Bodak O.I. Interaction of the components in the Li-Al-Sb ternary system at 470 K. Prace Naukowe WSP. Chemia. 1999. 3. 71-76.
2. Zatorska G.M., Dmytriv G.S., Pavlyuk V.V., Bartoszak-Adamska E., Jaskólski M. Crystal Structure of the New Intermetallic Compound Zr2-xSi1-xLix+y (x = 0.17, y = 0.12) and its Relation with the Disilicide ZrSi2. J. Alloys and Compounds. 2002. 346. 154-157. https://doi.org/10.1016/S0925-8388(02)00493-0
3. Zatorska G.M., Dmytriv G.S., Pavlyuk V.V., Davydov V.M., Bartoszak-Adamska E., Jaskólski M. Crystallographic investigation of the ternary compounds in the Zr-Li-Si system. J. of Light Metals. 2002. 2. 77-80. https://doi.org/10.1016/S1471-5317(02)00025-1
4. Dmytriv G., Pauly H., Ehrenberg H., Pavlyuk V., Vollmar E. Homogeneity range of the NaTl-type Zintl phase in the ternary system Li-In-Ag. J. Solid State Chem. 2005. 178(9). 2825-2831. https://doi.org/10.1016/j.jssc.2005.06.033
5. Pavlyuk V., Dmytriv G., Chumak I., Ehrenberg H., Pauly H. The crystal structure of the LiAg2In compound J. Solid State Chem. 2005. 178. 3303-3307. https://doi.org/10.1016/j.jssc.2005.08.005
6. Pavlyuk V.V., Dmytriv G.S., Tarasiuk I.I., Pauly H., Ehrenberg H. The ternary indide Li278(In,Ag)154: a new n = 6 variant of cubic n×n×n W-type superstructures. Intermetallics. 2007. 15. 1409-1415. https://doi.org/10.1016/j.intermet.2007.04.014
7. Dmytriv G., Pavlyuk V., Tarasiuk I., Pauly H., Ehrenberg H., Marciniak B., Prochwicz W., Schroeder G. Li-Zn-{Al,Sn} Zintl Phase alloys for the anode materials of lithium batteries. Вісник Львівського університету. Серія хімічна. 2007. 48. 172-178.
8. Pavlyuk V.V., Dmytriv G.S., Tarasiuk I.I., Pauly H., Ehrenberg H. Li12Cu16+xAl26-x (x = 3.2): a new intermetallic structure type. Acta Cryst. 2008. С64. i15-i17. https://doi.org/10.1107/S0108270108022476
9. Pavlyuk V.V., Dmytriv G.S., Tarasiuk I.I., Pauly H., Ehrenberg H. Li8Cu12+xAl6-x (x = 1.16): a new structure type related to Laves phases. Acta Cryst. 2008. C64. i73-i75. https://doi.org/10.1107/S0108270107065985
10. Тарасюк І., Дмитрів Г., Павлюк В., Паулі Г., Еренберг Г. Взаємодія компонентів у потрійній системі Li-Ag-Sb. Вісник Львівського університету. Серія хімічна. 2008. 49. 58-63.
11. Chumak I., Dmytriv G., Pavlyuk V., Oswald S., Eckert J., Trill H., Eckert H., Pauly H., Ehrenberg H. Li(Al1–zZnz) alloys as anode materials for rechargeable Li-ion batteries // J. Mater. Res. 2010. 25(8). 1492-1499. https://doi.org/10.1557/JMR.2010.0191
12. Pavlyuk V.V., Dmytriv G.S., Tarasiuk I.I., Chumak I.V., Pauly H., Ehrenberg H. Polymorphism of LiAg. Solid State Sci. 2010. 12. 274-280. https://doi.org/10.1016/j.solidstatesciences.2009.11.006
13. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Chumak I., Pauly H. Crystal structure of the Li18Cu15Al7 intermetallic compound. Acta Cryst. 2010. A66. s150-s151. https://doi.org/10.1107/S0108767310096649
14. Тарасюк І., Дмитрів Г., Павлюк В., Паулі Г., Еренберг Г. Взаємодія компонентів у потрійній системі Li-Ag-Sn. Вісник Львівського університету. Серія хімічна. 2010. 51. 10-17.
15. Dmytriv G.S., Pavlyuk V.V., Pauly H., Eckert J., Ehrenberg H. New real ternary and pseudoternary phases in the Li-Au-In-system. J. Solid State Chem. 2011. 184. 1328–1332. https://doi.org/10.1016/j.jssc.2011.03.020
16. Pavlyuk V., Dmytriv G., Tarasiuk I., Chumak I., Ehrenberg H. Li12Cu12.60Al14.37: a new ternary derivative of the binary Laves phases. Acta Cryst. 2011. C67. i59-i62. https://doi.org/10.1107/S0108270111048566
17. Галапац Н., Тарасюк I., Дмитрів Г., Павлюк В. Поліморфізм бінарної сполуки Li3Sb. Вісник Львівського університету. Серія хімічна. 2012. 53. 133-139.
18. Chumak I., Pavlyuk V., Dmytriv G., Pauly H., Ehrenberg H. The crystal and electronic structure of the Li2-xAg1+xIn3 (x = 0.05) indide. J. Solid State Chem. 2013. 197. 248-253. https://doi.org/10.1016/j.jssc.2012.08.049
19. Дмитрів Г., Тарасюк І., Павлюк В. Система Li–Ag–Ga. Вісник Львівського університету. Серія хімічна. 2014. 55. 29-36.
20. Pavlyuk V., Milashys V., Dmytriv G., Ehrenberg H. A new tetragonal structure type for Li2B2C. Acta Cryst. 2015. C71. 39-43. https://doi.org/10.1107/S2053229614025510
21. Дмитрів Г., Созанський М., Павлюк В., Тарасюк I., Еренберг Г. Система Li–Cu–Bi. Вісник Львівського університету. Серія хімічна. 2015. 56. 40-45.
22. Pavlyuk V., Sozanskyi M., Dmytriv G., Indris S., Ehrenberg H. Amendment of the Li-Bi Phase Diagram Crystal and Electronic Structure of Li2Bi. J. Phase Equilib. Diffus. 2015. 36. 544-553. https://doi.org/10.1007/s11669-015-0409-z
23. Pavlyuk V., Ciesielski W., Rozdzynska-Kielbik B., Dmytriv G., Ehrenberg H. Li4Ge2B as a new derivative of the Mo2B5 and Li5Sn2 structure types. Acta Cryst. 2016. C72. 561-565. https://doi.org/10.1107/S2053229616009384
24. Pavlyuk V., Dmytriv G., Tarasiuk I., Ehrenberg H. Li9Al4Sn5 as a new ordered superstructure of the Li13Sn5 type. Acta Cryst. 2017. C73. 337-342. https://doi.org/10.1107/S205322961700420X
25. Milashius V., Pavlyuk V., Kluziak K., Dmytriv G., Ehrenberg H. LiBC3: a new borocarbide based on the graphene and heterographene networks. Acta Cryst. 2017. C73. 984-989. https://doi.org/10.1107/S2053229617015182
26. Milashius V., Pavlyuk V., Dmytriv G., Ehrenberg H. Phase equilibria and crystal structure relationships in the ternary Li–B–C system. Inorg. Chem. Front. 2018. 5. 853-864. https://doi.org/10.1039/C7QI00787F
27. Dmytriv G., Pavlyuk V., Ehrenberg H. Peculiarities of solid solutions with NaTl-type structure in Li-Zn-X (X = Al,Ga,In) systems. Acta Cryst. 2019. А75. е422. https://doi.org/10.1107/S2053273319091344
28. Mishra V., Iyer A. K., Mumbaraddi D., Oliynyk A.O., Zuber G., Boucheron A., Dmytriv G., Bernard G.M., Michaelis V.K., Mar A. Coloured intermetallic compounds LiCu2Al and LiCu2Ga. J. Solid State Chem. 2020. 292. 121703. https://doi.org/10.1016/j.jssc.2020.121703
29. Jomaa M., Mishra V., Mumbaraddi D., Chaudchray M., Dmytriv G., Michaelis V.K., Mar A. Coloured intermetallic compounds Li2ZnGa and Li2ZnIn. J. Solid State Chem. 2022. 306. 122792. https://doi.org/10.1016/j.jssc.2020.121703
30. Зайцева К., Дмитрів Г. Кристалічна структура сполук Li2CuGa та LiCu2Ga // Вісник Львівського університету. Серія хімічна. 2022. 63. 82-87. http://dx.doi.org/10.30970/vch.6301.082
31. Dmytriv G.S., Prystavskyj T.O., Pavlyuk V.V., Kevorkov D.G., Bodak O.I. Interaction of the components in the Li-Al-Sb ternary system at 470 K. Vth International Seminar on Physics and Chemistry of Solids. Zloty Potok k/Czestochowy (Poland), 1999, 26.
32. Dmytriv G., Zatorska G., Pavlyuk V., Bartoszak-Adamska E., Jaskólski M. Crystal Structure of the New Intermetallic Compound Zr2-xSi1-xLix+y (x = 0.17, y = 0.12) and its Relation with Disilicide ZrSi2. 20th European Crystallographic Meeting, Kraków (Poland), 2001, 346.
33. Dmytriv G., Pauly H., Ehrenberg H., Pavlyuk V., Fuess H. Preliminary results for the quasibinary Zintle phase cut Lix(Ag0.5In0.5)1-x. 14th International Conference on Solid Compounds of Transition Elements, Linz (Austria), 2003, POII-05.
34. Заторська Г., Дмитрів Г., Давидов В., Павлюк В. Нові тернарні галіди ZrLi2Ga, ZrLiGa та Zr2Li0,5Ga0,5. IX наукова конференція "Львівські хімічні читання", Львів, 2003, Н16.
35. Dmytriv G., Pavlyuk V., Dolotko O., Kozlov A., Marciniak B., Schroeder G. Nowe Materjaly Anodowe dla Litowych Chemicznych Żródeł Prądu. CLA Sympozjum “Ogniwa i Akumulatory Chemiczne Zródła Prądu w Nauce i Technice”, Poznań (Poland), 2004, 65-66.
36. Dmytriv G., Pauly H., Ehrenberg H. Solid solutions with NaTl structure in the Li-Ag-In and Li-Zn-Al systems. Xth International Seminar on Physics and Chemistry of Solids, Lviv, 2004, 76.
37. Pavlyuk V., Dmytriv G., Chumak I., Ehrenberg H., Pauly H. The Crystal structure of LiAu2In and LiAg2In. IX International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2005, 53.
38. Чумак І., Павлюк В., Дмитрів Г., Паулі Г., Егренберг Г. Дослідження області гомогенності тернарної фази LiAg2In. X наукова конференція "Львівські хімічні читання-2005", Львів, 2005, Н43.
39. Pavlyuk V., Dmytriv G., Tarasiuk I., Ehrenberg H., Pauly H. The crystal structure of the Li139Ag20-xIn57+x and Li139Au20-xIn57+x (x = 0÷9) ternary indides. 15th International Conference on Solid Compounds of Transition Elements, Krakow (Poland), 2006, 8.
40. Dmytriv G.S., Pavlyuk V.V., Tarasiuk I.I., Ehrenberg H., Pauly H. Zintl Phases and compounds with related structures in the Li-{Ag,Au}-In systems. XIIth International Seminar on Physics and Chemistry of Solids, Lviv, 2006, 30.
41. Tarasiuk I.I., Pavlyuk V.V., Dmytriv G.S., Ehrenberg H., Pauly H. A new Li8Cu12+xAl6-x and Li12Cu16+xAl26-x phases in the Li–Cu–Al system. X International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2007, 133.
42. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Pauly H., Marciniak B. New compounds in the Li-Cu-Al system. XIIIth International Seminar on Physics and Chemistry of Solids, Ustronie Slaskie (Poland), 2007, 29.
43. Павлюк В., Дмитрів Г., Тарасюк І., Паулі Г., Еренберг Г. Про кристалічну структуру сполук LiCu2Al, LiCu2Sn та Li2CuSn // XI наукова конференція “Львівські хімічні читання – 2007”, Львів, 2007, Н49.
44. Тарасюк І., Павлюк В., Дмитрів Г., Еренберг Г. Паулі Г. Кристалічна структура фаз Li1+xT2-xSn (T = Cu, Ag). XVII Українська конференція з неорганічної хімії, Львів, 2008, 121.
45. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Pauly H. Interaction of components in the Li-Cu-Al system. 16th International Conference on Solid Compounds of Transition Elements, Dresden (Germany), 2008, 128.
46. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Pauly H., Marciniak B. Crystal structures of the Li12Cu16+хAl26-х (x = 3.2), Li8Cu12+xAl6-x (x = 1.16), Li12Cu13Al14 and LiCu2Al ternary compounds. 50 Konwersatorium Krystalograficzne, Wrocław (Poland), 2008, 139-140.
47. Копоть С., Дмитрів Г., Павлюк В., Тарасюк І., Еренберг Г., Паулі Г. Взаємодія компонентів у системі Li–Ag–Al. XII наукова конференція “Львівські хімічні читання – 2009”, Львів, 2009, Н81.
48. Chumak I., Ehrenberg H., Trots D., Pavlyuk V., Dmytriv G., Pauly H., Eckert J. Structural changes in Li278Ag40In114 during electrochemical lithium extraction. Lithium Battеry Discussion. Electrode materials, Arcachon (France), 2009, P44.
49. Dmytriv G.S., Pavlyuk V.V., Tarasiuk I.I., Chumak I.V., Pauly H., Ehrenberg H. Phase transition in the LiAg binary compound. XVth International Seminar on Physics and Chemistry of Solids, Szklarska Poręba (Poland), 2009, 23.
50. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Chumak I., Pauly H. Crystal structure of the Li18Cu15Al7 intermetallic compound. 26th European Crystallographic Meeting, Darmstadt (Germany), 2010, s150-s151.
51. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Chumak I., Pauly H. Crystal structure of the Li15Cu19Al16 compound. 17th International Conference on Solid Compounds of Transition Elements, Annecy (France), 2010, 90.
52. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H., Chumak I., Pauly H. Lithium intermetallic compounds as perspective materials for anode materials. XVIth International Seminar on Physics and Chemistry of Solids, Lviv, 2010, 43.
53. Tarasiuk I., Pavlyuk V., Dmytriv G., Ehrenberg H., Pauly H. Li12Cu12.6Al14.4 – a new ternary derivative of the W6Fe7 structure type. XI International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2010, 132.
54. Ehrenberg H., Chumak I., Dmytriv G., Pavlyuk V., Pauly H., Oswald S. New concept for intermetallic composite anodes in Li-ion batteries. XI International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2010, 18.
55. Мілашюс В., Дмитрів Г., Тарасюк І., Павлюк В. Структурні дослідження фаз системи Li-B-C. XIV наукова конференція “Львівські хімічні читання – 2013”, Львів, 2013, Н85.
56. Созанський М., Дмитрів Г., Павлюк В. Система Li-Cu-Bi при 200°C. XIV наукова конференція “Львівські хімічні читання – 2013”, Львів, 2013, Н57.
57. Dmytriv G., Pavlyuk V. Interaction of lithium with d- and some p-elements. XIXth International Seminar on Physics and Chemistry of Solids and Advanced Materials, Czestochowa (Poland), 2013, 67.
58. Dmytriv G., Halapats N., Pavlyuk V., Ehrenberg H. Crystal structure of a continuous solid solution in the Li-Cu-Ag-Sn system. XII International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2013, 118.
59. Tarasiuk I., Dmytriv G., Korenovska N., Pavlyuk V., Knapp M., Ehrenberg H. The Li17Si4-хSnх (х = 0-4) solid solution. XXth International Seminar on Physics and Chemistry of Solids, Lviv, 2015, 101.
60. Ehrenberg H., Chumak I., Pavlyuk V., Dmytriv G. Structural compatibilities in solid state batteries. Second Sino German Symposium on All Solid State Battery, Karlsruhe (Germany), 2015, 62
61. Dmytriv G., Pavlyuk V., Tarasiuk I., Ehrenberg H. Crystal and electronic structure of Li9Al4Sn5. XIII International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2016, 85.
62. Milashius V., Pavlyuk V., Dmytriv G., Ehrenberg H. New hexagonal structure type of LiBC3. XVІ наукова конференція “Львівські хімічні читання – 2017”, Львів, 2017, H20.
63. Dmytriv G., Pavlyuk V., Ehrenberg H. Perespective method for receiving of nanostructured Zn-Al alloys. EUROMAT 2017, Thessaloniki (Greece), 2017, A7-I-P-TUE-P1-3.
64. Dmytriv G., Pavlyuk V., Ehrenberg H. Peculiarities of quasisection Li(Zn1-zInz) with Zintl phases. XX Українська конференція з неорганічної хімії за участю закордонних учених, Дніпро, 2018, 93.
65. Dmytriv G., Pavlyuk V. Peculiarities of the interaction of d-metals with lithium and p-metals and semimetals. XIV International Conference on Crystal Chemistry of Intermetallic Compounds, Lviv, 2019, 39.
66. Dmytriv G., Pavlyuk V., Ehrenberg H. Peculiarities of solid solutions with NaTl-type structure in Li-Zn-X (X = Al,Ga,In) systems. 32nd European Crystallographic Meeting, Vienna (Austria), 2019, 410.
67. Зайцева К.В., Дмитрів Г.С. Кристалічна структура сполук Li2CuGa та LiCu2Ga. XVIII наукова конференція “Львівські хімічні читання – 2021”, Львів, 2021, Н33.
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