First virtual Bilateral Conference on Functional Materials (BiC-FM)

Acknowledgement.This work was supported by Universiti Sains Malaysia under Research University Grant (Project Grant No. 1001/PPSP/8012296).

Abstracts of Participants

Enhanced Electrochemical Performance of TiO2 Modified LiNi0.6Co0.2Mn0.2O2 Cathode Material via Atomic Layer Deposition

Zahra Ahaliabadeh1, Tanja Kallio1

1 – Department of Chemistry and Materials Science (CMAT), Aalto University, School of Chemical Engineering, 02150, Espoo, Finland

[e-mail]

Developing high-energy and high-power lithium-ion batteries (LIBs) is a key challenge to meet the demands for practical applications in electric vehicles. These demands have driven the recent studies on positive electrode materials. Ni-rich layered lithium transition metal oxides are promising positive electrode material for the next generation high energy density LIBs because of their good electrochemical stability, comparatively low cost, low toxicity, and high capacity. However, high Ni content leads to severe side reactions at positive electrode/electrolyte interface and secondary particle cracking during cycling which significantly degrade the electrochemical performance of this material [1]. Improving the performance of positive electrode by using surface coatings has proven to be an effective method for developing LIBs, while a high-quality film satisfying all requirements of electrochemical issues, chemical stability, and lithium ion conductivity is yet to be implemented [2]. Recently, surface modification via atomic layer deposition (ALD) has gain attention as an effective strategy to enhance the electrochemical performance of high-specific-capacity electrode materials [3]. In this study, we reported a strategy that employed metal oxides (TiO2) coating by ALD technique, in order to improve the bulk integrity, structure, and interfacial stability of the LiNi0.6Co0.2Mn0.2O2 (NMC622) and, hence, the long-term cycling capability. By varying the ALD parameters such as cycle number, mass of the substrate and precursor, an optimal ALD coating was achieved. The effects of TiO2 coating on the surface states, crystal structure and electrochemical performances of NCM622 material are studied in detail. All characterizations results confirm the coating layer on the surface of NMC622 particles. The electrochemical characterization results indicated that the coating of TiO2 ALD improved the cycling stability of NMC622 based electrodes by suppressing side reactions between the electrolyte and electrode. The improved electrochemical performance is ascribed to the high conformal and ultrathin TiO2 coating, which enhances the kinetics of Li+ diffusion and stabilizes the electrode/electrolyte interface.

References:

1. Croy, Jason R., Brandon R. Long, and Mahalingam Balasubramanian. "A path toward cobalt-free lithium-ion cathodes." Journal of Power Sources 440 (2019): 227113.

2. Liu, Siyang, et al. "Comparative studies of zirconium doping and coating on LiNi0. 6Co0. 2Mn0. 2O2 cathode material at elevated temperatures." Journal of Power Sources 396 (2018): 288-296

3. Zhu, Wenchang, et al. "Ultrathin Al2O3 coating on LiNi0. 8Co0. 1Mn0. 1O2 cathode material for enhanced cycleability at extended voltage ranges." Coatings 9.2 (2019): 92.

Development of ceramic composites based on hydroxyapatite and carbon nanomaterials

Ávila E.S.1, Antônio L.M. 1, Ladeira L.O. 1, Barabás R.2

1 – Universidade Federal de Minas Gerais, Escola de Engenharia Química, Belo Horizonte – MG – Brasil.

2 – Universitatea Babeș-Bolyai, Facultatea de Chimie și Inginerie Chimică, Cluj-Napoca – Romania.

[e-mail]

Graphene oxide has been studied 1–4 as an alternative instead graphene because the presence of carboxylic and hydroxyl functional groups, it has excellent mechanical properties and biocompatibility.

Carbon nanotubes (CNT) were first synthesized by Iijima in 19915. The great potential of applications of CNT are their physical and chemical properties and the possibility production of new biomaterials and composites 1,6,7.

Hydroxyapatite is one ceramic material produced using calcium phosphate and is good candidate already widely used as artificial bone in orthopedic or maxillofacial surgeries to repair bone defects, on the olther hand, present fragility and other imperfections 8,9. The ideal bone substitute must be biocompatible and gradually replaced the new bone tissue, need to have osteoinductive or osteoconductive properties 2.

The production of ceramic nanocomposites based in hydroxyapatite and carbon nanomaterials can be the solution of join the better qualities of each separate materials.

This work is one study of the composites production based on graphene oxide, carbon nanotubes and hydroxyapatite with possibilities of application in engineering of bone tissues, mainly for the clinical treatments of bone defects caused by trauma, cancer, infection or congenital deformity also in dental restoration and implant processes field 10.

Acknowledgement.This work was supported by the Erasmus Mundus Program.

References:

[1] G. M. Neelgund. Et al, J. Colloid Interface Sci. 484, 2016, 135.

[2] P. Yu, Et al, Carbohydrate Polymers 155, 2017, 507.

[3] Y. Liu, J. Huang, H. Li, J. Mater. Chem. B 1, 2013,1826.

[4] Y. Bai, Et al., J Alloys Compd 688, 2016, 657.

[5] S. Iijima, Nature 354, 1991, 56.

[6] R. Barabás, Et al., Ceram. Int. 41, 2015, 12717.

[7] L. Costatini, Et al., J. Adv. Ceram. 5, 2016, 232.

[8] M.Czikó, Et al., Rev. Roum. de Chimie 59, 2014, 353.

[9] B. Cengiz, Et al., Colloids Surf A Physicochem Eng Asp 322, 2008, 293.

[10] R.Barabás, Et al., Arabian J. for Science and Eng. 45, 2020, 219.

About the intercalation of carbon dioxide molecule into the BC5 nanotube

Zaporotskova I.V.1, Boroznin S.V.1, Zaporotskov P.A.1, Boroznina N.P.1

1 – Volgograd State University, Volgograd, Russia

[e-mail]

The article is devoted to the study of methods of catching СО2 molecules using boroncarbon nanotubes of type ВС5. The paper considers the capillary method of filling nanotubes with a carbon dioxide molecule. The main method used in the work is the density functional theory (DFT) method within the B3LYP functional. As a result of the work, the most likely method of catching carbon dioxide molecules using boroncarbon nanotubes was established and the physicochemical characteristics of these phenomena were determined.

It was found that upon penetration into the cavity of the nanotube, the molecule is forced to overcome the potential energy barrier. This barrier was identified with the activation energy of this process. The calculated activation energy turned out to be less than 1 eV. This value indicates that the implementation of this mechanism has a high degree of probability. Accordingly, these nanostructures can be used as filters to trap harmful molecules from the atmosphere.

Acknowledgement.This work was supported by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a, by Russian President's grant № 798.2019.1, by Russian President's grant № MK-1758.2020.8.

On the possibility of creating a highly efficient sensor based on carbon nanotubes for determining air quality

Boroznina N.P.1, Zaporotskova I.V.1, Boroznin S.V.1, Zaporotskov P.A.1, Ivanov I.I.1, Petrov P.P.2

1 – Volgograd State University, Volgograd, Russia

[e-mail]

The presented article conducts a theoretical study of the possibility of interaction of substances that affect the quality of inhaled air – carbon dioxide and sulfur dioxide – with carbon nanotubes modified by the functional amine group. The article analyzed the results of addition and carried out a comparative analysis of sorption interaction of the nanosystem with molecules of carbon dioxide (CO2) and sulfur dioxide (SO2). Recommendations are given for further use of the results as a basis for creating a new generation of highly sensitive sensor device for detecting micro-quantities of substances. The calculations were carried out by the DFT method.

Our research will allow us to create instruments that can conduct a more efficient and more subtle study of air quality. They will allow detecting micro amounts of harmful substances to prevent pollution in a timely manner. A sensor based on modified carbon nanotubes will respond to the presence of ultra-small amounts of substances. This allows us to judge the prospects of its use in the field of chemistry, biology, medicine, etc.

Acknowledgement.The reported research was funded by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a, by Russian President's grant № 798.2019.1, by Russian President's grant № MK-1758.2020.8.

Doping of inner and outer surface of single-walled carbon nanotubes

Anastasia E. Goldt1, Orysia Zaremba1, Mikhail O. Bulavskiy1, Fedor S. Fedorov1,

Konstantin V. Larionov2,3, Alexey P. Tsapenko1, Zakhar I. Popov2,4, Pavel Sorokin2,

Anton S. Anisimov5, Albert G. Nasibulin1,6

1 – Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russian Federation

2 – National University of Science and Technology “MISiS”, Leninsky prospect 4, Moscow 119049, Russian Federation

3 – Moscow Institute of Physics and Technology, Institutskiy lane 9, Dolgoprudny, Moscow region 141700, Russian Federation

4 – Emanuel Institute of Biochemical Physics RAS, Moscow 119334, Russian Federation

5 – Canatu Ltd., Konalankuja 5, 00390 Helsinki, Finland

6 – Aalto University, 00076 Espoo, Finland

[e-mail]

An increasing growth of flexible electronics market facilitates the development of new generation of materials that to be employed as flexible transparent conducting films (TCF) [1]. Even though, single-walled carbon nanotube (SWCNT) films are considered the most promising candidates for flexible TCFs, they still cannot meet the demanded characteristics [2]. Thus, the existing approaches to doping need a revision or improvement to allow SWCNTs achieve optoelectrical properties required for application as new generation TCFs.

In this work, we have utilized and investigated the new approach, which comprises the thermal treatment of SWCNTS in ambient air atmosphere with subsequent doping in ethanol solution of HAuCl4. We have shown that thermal treatment at temperatures higher than 300 oC leads to the SWCNT cap’s removal. Consequently, such opening of nanotubes is responsible for the more efficient doping of the treated films due to providing an additional inner surface doping when compared to the untreated samples. Stronger level of p-doping effect of opened via thermal treatment SWCNT films in comparison to pristine ones were confirmed by DFT-calculations and open circuit potential (OCP) measurements during the doping procedure. The utilized approach has allowed us to achieve the record equivalent sheet resistance value of 31 ± 4 Ω/sq for the SWCNT films treated at 400 oC.

Acknowledgement.This work was supported by the Russian Science Foundation, grant No. 17-19-01787.

References:

[1] S. Zhang, N. Nguyen, B. Leonhardt, C. Jolowsky, A. Hao, J.G. Park, R. Liang, Adv. Electron. Mater., 5 (6), 1800811 (2019)

[2] Y. Zhou, R. Azumi, Sci. Technol. Adv. Mater., 17 (1), 493–516 (2016)

Influence of boron atoms in surface-carboxylated boron-carbon BC3 and BC5 nanotubes in the creation of sensory devices

Zaporotskova I.V.1, Dryuchkov E.S.1, Vilkeeva D.E. 1, Elbakyan L.S. 1

1 – Volgograd State University, Volgograd, Russia

[e-mail]

In this article, discusses the possibility of the fabrication of a highly sensitive sensor based on single-walled boron-carbon BC5 nanotubes surface modified with functional carboxyl groups (-COOH) and a comparative analysis of the sensory properties of BC3 [1] and BC5 single-walled boron-carbon nanotubes surface-modified with a functional carboxyl group (-COOH) was carried out. The potential of the sensor for detecting alkali (lithium, potassium and sodium) metals was investigated. Results of computer simulation of process of sensor interaction with arbitrary surface of modified tube containing atoms of analysed metals are presented. The effect of boron atoms on the sensory properties of the obtained systems is concluded. Calculations were carried out as part of the Density Functional Theory (DFT) method using a molecular cluster model. Surface-modified boron-carbon nanotubes according to the carboxyl group have been shown to exhibit high sensitivity to the metal atoms under study and can be used as a sensor device. However, modification of the surface of the nanotube BC3 leads to a better result relative to BC5: this system has the maximum energy of sensory interaction, which suggests that an increase in the number of boron atoms in the nanotubular system improves its sensory properties.

Acknowledgement.The research was carried out with the financial support of the RFBR and The administration of the Volgograd region in the framework of the scientific project no.19-43-340005 r_a.

References:

[1] N.P. Boroznina, I.V. Zaporotskova, S.V. Boroznin, L.V.Kozhitov, A.V. Popkova, On the Practicability of Sensors Based on Surface Carboxylated Boron-Carbon Nanotubes, Russian Journal of Inorganic Chemistry, 64 (2019) 74–78.

Ultrashort optical Mathieu pulses in a carbon nanotube medium

Dvuzhilova Yu.V.1, Belonenko A.M.1, Dvuzhilov I.S.1, Belonenko M.B.1

1 – Volgograd State University, Volgograd, Russia

[e-mail]

A theoretical study of three-dimensional ultrashort optical pulses, Mathieu cross-section, which propagate in the medium of semiconductor carbon nanotubes. Using numerical simulations, it is shown that such pulses propagate stably, while conserving their energy in a limited spatial region. The pulse undergoes reflection from the walls of the optical cavity and further interference. The calculations were carried out at times up to 140 ps, which is important for possible practical applications [1–4].

Thus, diffraction-free three-dimensional extremely short Mathieu pulses propagate stably in the medium of carbon nanotubes. The pulse energy remains localized in a limited spatial region. Evolving in time, the pulse moves from the axis of the resonator to its walls, reflecting from them, and then interference of counter propagating waves occurs, due to which the pulse retains its energy concentrated, with a slight change in shape.

As a result, it becomes possible to control pulse broadening along the cavity axis. It should be noted that the numerical simulation of the pulse dynamics was carried out at long times, which determines the importance of the results obtained for practical applications.

Acknowledgement.The reported research was funded by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a.

References:

[1] M.A. Bandres, J.C. Gutiérrez-Vega, S. Chávez-Cerda, Optics Letters, 29, P. 44 (2004)

[2] J.W. Jiang, J.S. Wang, Journal of Applied Physics, 110, P. 124319 (2011)

[3] H. Leblond, D. Mihalache, Physical Review A, 86, P. 043832 (2012)

[4] Zhukov A.V., Bouffanais R., Belonenko M.B., Dvuzhilov I.S., Nevzorova, Y.V., Applied Physics B, 123 (2017)

The technology for producing new composite polymer materials based on polymethylmethacrylate doped with carbon nanotubes

Elbakyan L.S.1, Zaporotskova I.V.1, Vilkeeva D.E.1

1 – Institute of Priority technologies, Volgograd State University, University Av 100, Volgograd 400062, Russia

[e-mail]

Butylmethacrylate is used for the production of polybutylmethacrylates and related copolymers. BMA is used in the production of coatings and inks, plastics, paper, adhesives and sealants. In addition, BMA is a part of adhesives, photo-cured and other composites for dental use, various additives to lubricants, etc.[1]

To realize the possibility of obtaining composite polymer materials with improved strength properties, it is necessary to ensure the most uniform dispersion of carbon nanotubes into the polymer matrix. To create and test the technology of introducing CNT into polymer matrices, the method of ultrasonic action with simultaneous mechanical mixing under temperature influence was developed [2–4]. This method makes it possible to obtain stable polymer complexes, to increase the strength characteristics of the polymer. To study the strength properties of the obtained polymer materials, the breaking point of these samples with different percentages of CNT and the sample without them was determined.

Table 2. The breaking point composite polymer materials doped with CNT

CNT, % – Breaking point σср, [MPa]

0 – 0,041

0,01 – 0,043

0,03 – 0,046

0,05 – 0,049

Experimental studies on the creation of stable polymer complexes make it possible to obtain new composite systems reinforced with carbon nanotubes. This makes it possible to predict a larger-scale use of polymer materials.

Acknowledgement.The research was carried out with the financial support of the RFBR and the administration of the Volgograd region in the framework of the scientific project no.19-43-340005 r_a.

References:

[1] George Wypych Handbook of Polymers, Second Edition. ChemTec Publishing (2016) 712.

[2] L.S. Elbakyan, I.V. Zaporotskova Obtaining New Dental Materials Reinforced with Carbon Nanotubes, J. of nano- and electronic physics. Vol. 6, № 3 (2014) 03008-1 – 03008-3.

[3] M.S. Dresselhaus, G. Dresselhaus, P. Avouris, Carbon Nanotubes: Synthesis, Structure, Properties, and Application, Berlin/Heidelberg, Germany, 2001.

[4] L. S. Elbakyan, I. V. Zaporotskova. On the possibility of creating polymer nanocomposites based on methacrylic acid by reinforcing them with carbon nanotubes, J. Eurasian Union of scientists. Kh. (2014) 39–42.

Synthesis of Pt nano-microspheres at TiO2 – decorated Ti wire

Fedorov F.S.1, Vasilkov M.Yu.2,3, A. Goldt1, Shurygina L.I.4, Nasibulin A.G.1,5

1 – Skolkovo Institute of Science and Technology, Moscow, Russia

2 – Saratov Branch of Kotelnikov Institute of Radioengineering and Electronics of RAS, Saratov, Russia

3 – Yuri Gagarin State Technical University of Saratov, Saratov, Russia

4 – Kemerovo State University, Kemerovo, Russia.

5 – Aalto University, Aalto, Finland

[e-mail]

Nowadays the development of new functional materials with improved characteristics for application in electrocatalysis [1], gas sensors, etc. [2] is directly related to their design at the nanoscale. However, one needs to consider appearing technological issues, i.e. the applicability of such nanostructured materials in the industry. For example, the use of arrays of titanium dioxide nanotubes at the Ti substrate may include potential applications when it is in the form of wires or meshes that enable flow-through design. But, anodization of the metal of such geometries is not trivial because the surface profile is characterized by a given curvature. Besides, modifying the surface of such structures with precious metals such as platinum, which helps to improve the catalytic activity, can be quite challenging. Here, we investigated the growth processes of titanium dioxide nanotube arrays obtained by anodizing titanium wire in aqueous organic solutions and the decoration of such arrays with platinum.

Electrochemical anodization of a titanium wire (d=250 µm, ω(Ti)=99.7 %-wt.) was studied in an electrolyte containing glycerol, water, and ammonium fluoride with a mass ratio of 74.6: 24.6: 0.75 at a constant voltage of 30 V for 70 hours. Further, the obtained samples were modified with platinum in a solution of 400 µl 0.02 M H2PtCl6, 400 µl H2O, and 400 µl 85 %-wt. HCOH for 120 hours. The obtained samples were studied by scanning electron microscopy with a help of a focused ion beam and transmission electron microscopy.

The synthesized structures represent arrays of ordered nanotubes decorated with platinum. The platinum appears as polycrystalline spheres whose diameter ranges from 100 nm to 2–3 µm. The structure of the spheres is represented as a complex network of nanowires with voids made by titanium dioxide nanotubes. This material has a large surface area and is promising for application as a gas sensor and as a catalyst.

Acknowledgment.This work was supported by a grant of Russian Science Foundation (no. 19-72-00136).

References:

[1] F.S. Fedorov et al. International Journal of Hydrogen Energy, 44, 10593 (2019)

[2] A.V Lashkov et al. Sensors & Actuators B: Chemical, 306, 127615 (2020)

New phosphates and fluoride-phosphates as promising electrode materials for rechargeable batteries

Luchinin N. D.1, Samarin A. Sh.1, Shraer S. D.1, Fedotov S. S.1

1 – Skolkovo Institute of Science and Technology, Moscow, Russia

[e-mail]

The progress in grid applications of metal-ion batteries pushes forward the development of electrode materials for Na-ion and K-ion batteries (NIBs and KIBs) as cost-efficient alternatives to the conventional Li-ion technology. Analogous to the Li-ion systems, the Na and K-based mixed oxides and polyanion materials are being developed as potential cathodes with attractive specific energy, stability and rate performance. Contrary to layered oxides, the polyanion materials usually display better cycling and thermal stability, as well as higher C-rate capabilities due to covalently bonded structural frameworks. At the same time, the polyanion compounds reveal a much more diverse crystal chemistry, which significantly extends the playground for designing new materials with unique electrochemical properties. Further advancements come from the synergy of coupling different anion species (such as XO4m- and F-) in the anion sublattice enabling higher redox potentials and richer structural diversity.

Recently we proposed a novel series of AMPO4F (A = Li, Na, K; M = Ti, V) cathode materials crystallizing in a unique KTiOPO4 (KTP)-type structure [1–4]. The target materials were synthesized via different soft-chemistry routes including hydrothermal method and freeze-drying. The materials featured outstanding specific energy, rate capability, and capacity retention outperforming most of benchmarked NIBs and KIBs electrode materials.

A short overview of the recent research and activities of our group on novel transition metal phosphates and fluoride-phosphates adopting the unique KTP-type crystal structure as potential electrode materials for NIBs and KIBs will be presented with a special focus on the interrelation between chemical composition, synthesis conditions, crystal structure peculiarities, and electrochemical properties of the materials aimed at practical applications.

Acknowledgement.This work was supported by the Russian Science Foundation, grant 20-73-10248.

References:

[1] S.S. Fedotov et al Chemistry of Materials, 28, 411 (2016)

[2] S.S. Fedotov et al Nature Communications, 11, 1 (2020)