Head of Laboratory

Antipov, Evgeny V

DSc in Chemistry, Professor, Associate member of the Russian Academy of Sciences 
Publications
454
Citations
9 756
h-index
47
Authorization required.
Lab team

Development and study of inorganic materials that are used in electrochemical processes (in electrodes or electrolytes of various types of batteries). The work being carried out is based on a combination of the principles of materials science, inorganic chemistry and electrochemistry. Fundamental research is an integral part, and most of the studied objects are planned to be used in real devices in the foreseeable (3-10 years) future.

  1. Various types of inorganic syntheses: hydro (solvo) thermal, sol-gel, solid-phase
  2. X-ray phase analysis
  3. Scanning electron microscopy (SEM)
  4. Electrochemical research, including operando diffraction and spectroscopic experiments
Evgeny Antipov
Head of Laboratory
Semenikhin, Oleg
Oleg Semenikhin 🥼
Leading researcher
Oleg Drozhzhin
Senior Researcher
Alekseeva, Anastasia M
Anastasia Alekseeva
Senior Researcher
Maxim Zakharkin 🥼 🤝
Researcher
Vitalii Shevchenko 🥼
Researcher
Zoya Bobyleva 🥼 🤝
Researcher
Eduard Levin
Researcher
Emiliya Zharikova
Junior researcher
Ruslan Samigullin
Junior researcher
Grigorii Lakienko 🥼 🤝
PhD student
Sultanova, Yana Vladimirovna
Yana Sultanova 🤝
Student

Research directions

Scaling of synthesis methods and prototyping of metal-ion batteries

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Scaling of synthesis methods and prototyping of metal-ion batteries
Cathode materials with an olivine structure for the next generation of high-power batteries are now being produced within the framework of the Rustor startup, created jointly with the Skolkovo Institute of Science and Technology. Prototypes of sodium-ion batteries based on four types of materials developed in our laboratory at the Faculty of Chemistry of Moscow State University were presented at specialized exhibitions in 2019 and 2020 (example in the figure).

Development of experimental approaches for in situ and operando research methods

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Development of experimental approaches for in <em>situ</em> and <em>operando</em> research methods
A number of electrochemical cells have been developed and successfully tested for conducting operando studies using X-ray powder diffraction, synchrotron X-ray diffraction and X-ray absorption spectroscopy, neutron powder diffraction, and Mossbauer spectroscopy. The figure shows a diagram of one of these cells.

Synthesis and research of cathode and anode materials for metal-ion (lithium-ion, sodium-ion, potassium-ion) batteries

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Synthesis and research of cathode and anode materials for metal-ion (lithium-ion, sodium-ion, potassium-ion) batteries
The figure above shows the crystal structures of the main types of materials with which we work: 1 – layered oxides, 2 – phosphates with the structure of olivine, 3 - oxides with the structure of spinel, 4 – phosphates with the structure of NASICON, 5 – pyrophosphates with the structure of KAlP2O7, 6 – "solid carbon". The figure below shows the electrochemical characteristics in the "fast charge — slow discharge" mode of LiFePO4 phosphates (LFP) obtained by the method of solvothermal synthesis in our laboratory (1) and a commercially available analog (2). These materials are used as cathodes of safe and high-power lithium-ion batteries.

Publications and patents

Marshenya S.N., Scherbakov A.G., Dembitskiy A.D., Golubnichiy A.A., Trussov I.A., Savina A.A., Kazakov S.M., Aksyonov D.A., Antipov E.V., Fedotov S.S.
2024-09-11 citations by CoLab: 0 Abstract
The synthesis of a cubic langbeinite NaZr2(PO4)3via an ion exchange reaction supported by mechanochemical activation is described. The crystal structure and Na transport properties are studied. HT XRD reveals negative thermal expansion.
Samigullin R.R., Bobyleva Z.V., Zakharkin M.V., Zharikova E.V., Rozova M.G., Drozhzhin O.A., Antipov E.V.
Energies Q1 Q3 Open Access
2024-08-10 citations by CoLab: 0 PDF Abstract
Sodium-ion batteries are a technology rapidly approaching widespread adoption, so studying the thermal stability and safety of their components is a pressing issue. In this work, we employed differential scanning calorimetry (DSC) and ex situ powder X-ray diffraction to study the thermal stability of several types of sodium-ion electrolytes (NaClO4 and NaPF6 solutions in PC, EC, DEC, and their mixtures) and various cathode and anode materials (Na3V2(PO4)3, Na3(VO)2(PO4)2F, β-NaVP2O7, and hard carbon) in combination with electrolytes. The obtained results indicate, first, the satisfactory thermal stability of liquid Na-ion electrolytes, which start to decompose only at 270~300 °C. Second, we observed that charged vanadium-based polyanionic cathodes, which appear to be very stable in the “dry” state, demonstrate an increase in decomposition enthalpy and a shift of the DSC peaks to lower temperatures when in contact with 1 M NaPF6 in the EC:DEC solution. However, the greatest thermal effect from the “electrode–electrolyte” interaction is demonstrated by the anode material: the heat of decomposition of the soaked electrode in the charged state is almost 40% higher than the sum of the decomposition enthalpies of the electrolyte and dry electrode separately.
Panin R.V., Cherkashchenko I.R., Zaitseva V.V., Samigullin R.R., Zakharkin M.V., Novichkov D.A., Babkin A.V., Mikheev I.V., Khasanova N.R., Antipov E.V.
2024-07-03 citations by CoLab: 1
Lakienko G.P., Bobyleva Z.V., Gorshkov V., Zybina A.I., Drozhzhin O.A., Abakumov A.M., Antipov E.V.
2024-06-03 citations by CoLab: 5 Abstract
With sodium-ion batteries (SIBs) finding widespread application, the demand grows for hard carbon, the most popular anode material for SIBs. Hydrothermal carbonization facilitates the production of hard carbon with desired characteristics from various sources. Despite the considerable volume of literature addressing this subject, there is a notable absence of investigations elucidating the relationship between synthesis conditions and the electrochemical characteristics of the product. Here we study systematically the influence of hydrothermal carbonization parameters on hard carbon characteristics and emphasize the potential of hard carbon as an anode material for SIBs. The initial Coulombic efficiency (ICE) is significantly affected by the particle size of the glucose-derived hard carbon, which, in turn, depends on glucose concentration in the initial solution, pH, and stirring regime. By optimizing the hydrothermal carbonization parameters, the ICE up to 91% and a good reversible capacity of ∼300 mAh g−1 in a half cell are achieved. Full cells with Na3(VO)2(PO4)2F cathode material demonstrate ICE of about 80% and reversible capacity of up to 100 mAh g−1 cath. Considering the effective performance of pouch-cell SIB prototypes based on Na3(VO)2(PO4)2F and hard carbon, hydrothermal carbonization of glucose yields hard carbon with the necessary characteristics required for its successful application in SIBs.
Ramezankhani V., Luchinin N.D., Marshenya S.N., Zakharkin M.V., Golubnichiy A.A., Morozov A.V., Emilianova O., Stevenson K.J., Antipov E.V., Abakumov A.M., Fedotov S.S.
2024-05-29 citations by CoLab: 5 Abstract
The novel Ti-containing anode for the K-ion battery.
Katorova N.S., Galushko A.S., Burykina J.V., Fakhrutdinov A.N., Klyuev V.V., Bulyukina V.A., Kramarev I.Y., Pazhetnov E.M., Abakumov A.M., Ananikov V.P., Antipov E.V.
2024-05-01 citations by CoLab: 0 Abstract
The change in the composition of the electrolyte after life cycle testing (cycling) of lithium-ion batteries (LIBs) was studied. The cell with a nominal capacity of 22 A h was composed of a cathode based on nickel-rich layered lithium oxide LiNi0.6Mn0.2Co0.2O2 (NMC622) and an anode based on graphite. NMR and high-resolution mass spectrometry demonstrated the continuous decomposition of dimethyl carbonate and ethyl methyl carbonate, related to the disruption of the formation of protective surface layers on the graphite electrode. The degradation of the LIB is related to the formation of polyethylene oxide oligomers of various compositions as a result of the decomposition of the electrolyte components and the precipitation of the salt MeOCO2Li, which is poorly soluble in carbonate solvents, on the separator. A water content of more than 20 ppm in the electrolyte leads to the hydrolysis of the salt LiPF6 with the formation of HPO2F2 and HF. The presence of HF facilitates the dissolution of the components of the surface film at the graphite/electrolyte interface with the regeneration of H2O and the formation of a “fresh” surface on the graphite, which participates in the electrochemical decomposition of the carbonate solvents. Organophosphate C2H5O4P is formed upon the interaction of the electrolyte components with HF.
Semerukhin D.Y., Kubarkov A.V., Sergeyev V.G., Semenikhin O.A., Antipov E.V.
2024-05-01 citations by CoLab: 12 Abstract
The distribution of relaxation times (DRT) approach was used to analyze the electrochemical impedance spectra obtained for lithium-ion cells as a function of their state of charge as well as the cell preparation conditions. The cells were made using LiFePO4 cathodes with PEDOT:PSS binder and Li anodes. The following parameters were varied: the load of the active mass with LiFePO4, the presence or absence of carbon nanotubes, the presence or absence of the carbon coating of the current collector, die-pressing of the active mass, as well as artificial degradation of the binder using thermal treatment. The results support the view adopted in the literature that the DRT response of Li-ion cells involves 4 main regions attributed to (i) contact resistance between the particles of the active mass or the particles and the current collector; (ii) ionic resistance of the active layer including that of SEI on the surface of the electrodes; (iii) faradaic resistance of the electrochemical charge transfer at the surface of the active material, and (iv) solid-state diffusion/transport of Li+ ions in the particles of active material. Moreover, we identified yet another contribution to the DRT spectra related to the ionic conductivity of the binder and electrolyte in the active mass of the cathode.
Shraer S., Dembitskiy A., Trussov I., Komayko A., Aksyonov D., Luchinin N., Morozov A., Pollastri S., Aquilanti G., Ryazantsev S., Nikitina V., Abakumov A., Antipov E., Fedotov S.
2024-04-01 citations by CoLab: 3 Abstract
Advances in sodium-ion batteries hugely rely on perfecting the performance of active electrode materials. In this paper, we offer a new NaVOPO4 polymorph adopting a KTiOPO4-type framework as a promising high-rate, low-strain and long-life positive electrode material for sodium-ion batteries. NaVOPO4 is prepared via a facile hydrothermally-assisted solid-state ion exchange. The crystal structure is refined based on synchrotron X-ray powder diffraction (XRD) and validated by X-ray absorption spectroscopy (XAS), transmission electron microscopy analysis and density functional theory (DFT) calculations. The electrochemical performance of NaVOPO4 is evaluated through galvanostatic charge/discharge tests, cyclic voltammetry, potentiostatic intermittent titration and electrochemical impedance spectroscopy. A carbon-coated NaVOPO4 demonstrates a specific capacity of ∼110 mAh g–1 at a C/10 rate at an average potential of ∼3.93 V vs. Na+/Na. The material exhibits decent capacity retention and rate capability, maintaining over 74 % of the initial capacity after 1000 cycles at a C/2 rate and around 87% at a 2C charge/discharge rate. Diffusion coefficients of 10–11 cm2 s–1 and DFT-calculated energy barriers of ∼0.15–0.35 eV indicate fast Na+ ion diffusion within the NaVOPO4 framework. The vanadium oxidation state and charge compensation mechanism in NaVOPO4 are studied by XAS and DFT. Moreover, the operando XRD analysis coupled with DFT elucidates several phase transitions occurring in NaVOPO4 with an exceptionally low volume variation of 2.4% in total, highlighting the reversibility and structural stability during Na+ de/insertion. Overall, NaVOPO4 exhibits attractive electrochemical performance and stability, making it a potential candidate for sodium-ion battery cathode materials.
Abramova Elena N., Bobyleva Zoya V., Drozhzhin Oleg A., Abakumov Artem M., Antipov Evgeny V.
2024-03-07 citations by CoLab: 5 PDF Abstract
The development of large-scale energy storage systems based on the mature technology of lithium-ion batteries is hampered by the high cost of lithium. Therefore, analogous technologies based on other alkali metals (sodium and potassium) are being developed. Among various types of negative electrode (anode) materials for such batteries, carbon materials are most promising; in particular, hard carbon is of most interest. The present review addresses the current state of research on the structure, composition and properties of this type of material and gives analysis of methods of its preparation and investigation. Description of the microstructure of hard carbon is a highly ambiguous and challenging problem; therefore, the review pays special attention to various microstructural models. In addition, the methods of synthesis are systematized and the results of studies of the physicochemical properties of hard carbon are analyzed. The correlations between the preparation method, characteristics and electrochemical properties in metal-ion batteries are identified. A large array of results of electrochemical studies is considered, the views on the mechanisms of electrochemical interactions of Na+ and K+ cations with hard carbon are systematized, and the currently existing contradictions in various models of the interaction mechanisms are shown.Bibliography — 247 references.
Samarin A.S., Ivanova T.V., Nazarov E.E., Marshenya S.N., Luchinin N.D., Antipov E.V., Fedotov S.S.
2024-03-01 citations by CoLab: 0 Abstract
Phase-pure NaMPO4 (M = Mn, Mn/Fe; isotypic to triphylite) and Li(Mn/Fe)PO4 were isolated as a result of the low- temperature reaction between NH4MPO4·H2O (M = Mn, Mn/Fe) and AcONa·3H2O or AcOLi, respectively. Electrochemical tests in half-cells revealed that Na-based compounds exhibit poor electrochemical activity vs. metallic Na, while the similarly synthesized Li counterpart demonstrates decent cycling in Na cells. The synthetic features, crystal structures and properties of related members of the olivine family are discussed.
Shevchenko V.A., Komayko A.I., Sivenkova E.V., Samigullin R.R., Skvortsova I.A., Abakumov A.M., Nikitina V.A., Drozhzhin O.A., Antipov E.V.
2024-03-01 citations by CoLab: 7 Abstract
Layered O3-type NaMO2 oxides (M = transition metals) are the main candidates for cathode materials in the actively developing technology of sodium-ion batteries. Nevertheless, despite many years of research, the optimal composition of such materials is still a matter of debate. In this work, we studied the effect of the Fe, Mn and Ni content on the phase composition, structure, thermal stability and electrochemical properties of the cathode materials NaNi1/3Fe1/3Mn1/3O2 (NFM111), NaNi0.5Fe0.25Mn0.25O2 (NFM211), NaNi0.25Fe0.5Mn0.25O2 (NFM121) and NaNi0.25Fe0.25Mn0.5O2 (NFM112). All materials demonstrate similar discharge capacity (125–131 mAh·g−1) when cycling in the 1.9–4.0 V vs Na/Na+ potential range. However, only the NFM111 and NFM112 samples show a low increase in charge transfer resistance during cycling and acceptable thermal stability. Low-temperature experiments revealed good capacity retention for the NFM111 electrode material with loss of only ∼20 % of capacity when the temperature drops from +25 to −30°С. Thus, the NFM111 oxide exhibits a balanced combination of the electrochemical properties and, along with manganese-enriched composition, can be considered as a good choice for further development of cathode materials for sodium-ion batteries.
Babkin A.V., Kubarkov A.V., Styuf E.A., Sergeyev V.G., Drozhzhin O.A., Antipov E.V.
2024-01-01 citations by CoLab: 2 Abstract
The precipitation method is an efficient, economically feasible, and reproducible synthetic route to cathode materials for lithium-ion batteries with attractive performance characteristics, in particular, lithium iron phosphate (LiFePO4). This paper reviews the mechanisms of the key steps of the synthesis, namely, precipitation of iron phosphate FePO4 followed by its sintering with a lithium-containing raw material to give the LiFePO4 phase. The most probable interactions determining the kinetics of the precipitation process are considered using the data on the dissociation degree of the reacting components. The influence of the nature and concentrations of the commonly used sources of iron (FeSO4, FeCl3, Fe(NO3)3) and phosphorus (H3PO4, NH4H2PO4, (NH4)2HPO4), as well as the precipitation conditions (pH, temperature) on the precipitation efficiency of FePO4 is analyzed. The effect of the nature of the lithium-containing raw material (LiOH, Li2CO3, LiNO3) and the sintering (calcination) temperature on the morphology, phase composition, and electrochemical properties of the resulting LiFePO4 is discussed. The possibility is considered of obtaining spherical particles with high bulk density, which provides high specific and volumetric energy density of electrochemical cells. Based on the relationships established, optimal parameters for the synthesis of LiFePO4 with preliminary FePO4 precipitation step are proposed.
Drozhzhin O.A., Zharikova E.V., Lakienko G.P., Rozova M.G., Antipov E.V.
2023-12-01 citations by CoLab: 0 Abstract
Lithium and transition-metal phosphates are promising cathode materials for lithium-ion batteries. Lithium manganese phosphate LiMnPO4 has a higher specific energy density than LiFePO4 used in practice: theoretical values of 700 and 580 W h/kg, respectively. However, its use is hampered by a number of disadvantages: reduced electronic and ionic conductivity, inferior stability of the structure in the charged form, and large changes in the volume during (de)lithiation. LiMnPO4 and LiMn0.95Ni0.05PO4 samples are synthesized by the solvothermal method and studied using X-ray powder diffraction, low-temperature nitrogen adsorption, scanning electron microscopy, and electrochemical methods. It is shown that a small degree of substitution of Mn for Ni (5 at %) leads to an increase in the capacity and Coulombic efficiency of LiMnPO4, a decrease in charge-transfer resistance, and an increase in Li+ diffusion coefficients.
Levin E.E., Morozov D.A., Frolov V.V., Arkharova N.A., Khmelenin D.N., Antipov E.V., Nikitina V.A.
Nanomaterials Q1 Q2 Open Access
2023-11-23 citations by CoLab: 4 PDF Abstract
Copper-based electrocatalytic materials play a critical role in various electrocatalytic processes, including the electroreduction of carbon dioxide and nitrate. Three-dimensional nanostructured electrodes are particularly advantageous for electrocatalytic applications due to their large surface area, which facilitates charge transfer and mass transport. However, the real surface area (RSA) of electrocatalysts is a crucial parameter that is often overlooked in experimental studies of high-surface-area copper electrodes. In this study, we investigate the roughness factors of electrodeposited copper foams with varying thicknesses and morphologies, obtained using the hydrogen bubble dynamic template technique. Underpotential deposition (UPD) of metal adatoms is one of the most reliable methods for estimating the RSA of highly dispersed catalysts. We aim to illustrate the applicability of UPD of lead for the determination of the RSA of copper deposits with hierarchical porosity. To find the appropriate experimental conditions that allow for efficient minimization of the limitations related to the slow diffusion of lead ions in the pores of the material and background currents of the reduction of traces of oxygen, we explore the effect of lead ion concentration, stirring rate, scan rate, monolayer deposition time and solution pH on the accuracy of RSA estimates. Under the optimized measurement conditions, Pb UPD allowed to estimate roughness factors as high as 400 for 100 µm thick foams, which translates into a specific surface area of ~6 m2·g−1. The proposed measurement protocol may be further applied to estimate the RSA of copper deposits with similar or higher roughness.
Marshenya S.N., Dembitskiy A.D., Fedorov D.S., Scherbakov A.G., Trussov I.A., Emelianova O., Aksyonov D.A., Buzlukov A.L., Zhuravlev N.A., Denisova T.A., Medvedeva N.I., Abakumov A.M., Antipov E.V., Fedotov S.S.
2023-11-10 citations by CoLab: 2 Abstract
The first demonstration of a KTP-type material as a solid sodium-ion conductor.

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Химфак МГУ к. Ц10, этаж цокольный
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