FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS

The possibility of formation of an active interphase on iron particles in C/PVDF has been dictated by the thermochemical reactions of iron and iron oxides in the presence of carbon. The composition with polyvinylidene fluoride (PVDF) changed the redox activity of iron particles and decreased pure ir...

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Datum:2023
Hauptverfasser: Panteleimonov, Radyslav, Pershina, Katherine, Shcherbatiuk , Ivan
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Sprache:Englisch
Veröffentlicht: V.I.Vernadsky Institute of General and Inorganic Chemistry 2023
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Ukrainian Chemistry Journal
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author Panteleimonov, Radyslav
Pershina, Katherine
Shcherbatiuk , Ivan
author_facet Panteleimonov, Radyslav
Pershina, Katherine
Shcherbatiuk , Ivan
author_institution_txt_mv [ { "author": "Radyslav Panteleimonov", "institution": "Vernadskii Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kyiv, Palladin av., 32\/34, 03142 Ukraine" }, { "author": "Katherine Pershina", "institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, Palladin av., 32\/34,03142 Ukraine" }, { "author": "Ivan Shcherbatiuk ", "institution": "Joint Department of electrochemical Energy Systems, NAS of Ukraine" } ]
author_sort Panteleimonov, Radyslav
baseUrl_str https://ucj.org.ua/index.php/journal/oai
collection OJS
datestamp_date 2026-07-22T08:23:51Z
description The possibility of formation of an active interphase on iron particles in C/PVDF has been dictated by the thermochemical reactions of iron and iron oxides in the presence of carbon. The composition with polyvinylidene fluoride (PVDF) changed the redox activity of iron particles and decreased pure iron (Fe0) amount by 0,24 wt. %. The surface properties of various compositions have been characterized by scanning electron microscopy with the analytical mode for determining the relationship between the microstructure and local thermal reactions on the iron particle surface. A relationship between the surface composition, morpho­logy and electrochemical behavior of the Fe/C/PVDF electrodes has been found. Electric current affects the surface morphology and changes it from a mosaic structure to a monolith in atmosphere oxygen. The electrochemical properties of Fe/C/PVDF electrodes have been tested using cyclic voltammetry (CVA). The long air contact (for more than 3 hours) during electrochemical cycling changes the surface structure in the direction of decreasing crysta­llinity. The Fe/C/PVDF electrode can be charge in neutral solutions (pH ~7).
doi_str_mv 10.33609/2708-129X.89.02.2023.91-99
first_indexed 2025-09-24T17:43:49Z
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fulltext 91 UDC 621.351 doi: 10.33609/2708-129X.89.02.2023.91-99 FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS Panteleimonov R.A.1, Shcherbatiuk I.M.2, Pershina K.D.1,2 1V.I.Vernadskyi Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, Prospect Palladina, 32/34, 03142, Kyiv, Ukraine, 2Joint Department of Electrochemical Energy Systems, National Academy of Sciences of Ukraine, Prospect Vernadskoho, 38, 03142, Kyiv, Ukraine e-mail: radik20031@gmail.com The possibility of formation of an active interphase on iron particles in C/PVDF has been dictated by the thermochemical reactions of iron and iron oxides in the presence of carbon. The composition with polyvinylidene fluoride (PVDF) changed the redox activity of iron par- ticles and decreased pure iron (Fe0) amount by 0,24 wt. %. The surface properties of various compositions have been characterized by scanning electron microscopy with the analytical mode for determining the relationship between the microstructure and local thermal reac- tions on the iron particle surface. A relationship between the surface composition, morpho logy and electrochemical behavior of the Fe/C/PVDF electrodes has been found. Electric current affects the surface morphology and changes it from a mosaic structure to a monolith in atmosphere oxygen. The electrochemical properties of Fe/C/PVDF electrodes have been tested using cyclic voltammetry (CVA). The long air contact (for more than 3 hours) during electrochemical cycling changes the surface structure in the direction of decreasing crysta llinity. The Fe/C/PVDF electrode can be charge in neutral solutions (pH ~7). Key words: iron particle, active interphase, polyvinylidene fluoride, carbon, electrode. INTRODUCTION. Using catalyst support materials is essential to nanostructured ca talytic systems in many energy-transforming devices. Ideal catalyst carriers should possess the following properties: high conductivity, high surface area, low cost, electrochemical inertness, and stability. Noble metals (Pt, Ru, etc.) are considered to be the most active and stable materials for green hydrogen (GH) pro- duction but extremely high cost and limited natural abundance impede their wide indus- trial applications. Thus, nonplatinum active metals such as Fe, Ni, or Co as well as their alloys and composites have received great at- tention as electrocatalysts for GH because of their relatively low prices and availability [1]. Iron nanoparticle/polymer nanocomposites have recently become some of the most active research areas in the materials science and en- gineering [1–3]. Among the nanosized fillers 92 ISSN 2708-129X. Укр. хім. журн., 2023 FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMSPHISICAL CHEMISTRY for these composites, iron and its oxides (FeO, Fe2O3, and Fe3O4) have attracted significant interest owing to their ability for redox reac- tions with huge heating effects and the ability to form surface interphases, leading to diverse applications in energy transforming devices [4–7]. For the polymeric matrix, polyvi- nylidene fluoride is a suitable semi-crystalline polymer owing to its remarkable thermal sta- bility, good chemical resistance, and extraordi- nary pyroelectric and piezoelectric properties [8]. These properties, combined with its high elasticity, relative transparency, and ease of processing, make this thermoplastic polymer suitable for various technological applications. PVDF shows a complex structure including five distinct crystalline phases related to different chain conformations designed, known as α,β, δγ and ε phases [9,10]. Adding nanoparticles to a matrix such as PVDF can enhance its con- ductive performance and provide an advanced response by changing the nature and proper- ties of the nanoscale filler [11]. This matrix forming an artificial interphase layer (a stable fluorine-doped amorphous carbon (CF) layer) for retaining uncontrollable metallic dendrites and side reactions is a highly desirable stra tegy for increasing coulombic efficiency and limiting long cycling stability of metal batteries [12]. Carbon-based materials have been used as catalyst supports for a long time due to their unique properties, such as physical stability, excellent conductivity, and high surface area. As the graphite anode in a lithium-ion battery, hard carbon is a widely accepted anode materi- al for different batteries and capacitors. Initial- ly, the PVDF binder was used in the electro- active hard-carbon anode. Nowadays, PVDF is the main component of composite electrodes. But this application of polyvinylidene fluoride exhibits poor reversibility of electrodes. Some authors attribute this impact to the formation of fluoropolymer - a product of the polyme rization of tetrafluoroethylene molecules [13]. CVA measurements and electrochemical im- pedance spectroscopy data showed that im- proved catalytic activity towards GH was the result of an increase in the effective surface area, a change in surface features upon heating and the electrocatalytic synergism of Fe with other components of composites [1]. That is why the study of the appearance of new inter- phases on the iron surface in composite Fe/C/ PVDF films and their impact on the electroca talytic properties of composites are topical for the development of a new generation of energy storage for GH production. EXPERIMENT AND DISCUSSION OF THE RESULTS. Preparation of Fe/C/PVDF electrode. A predetermined amount of iron powder (PGR 3.200.28-30) with a bulk density of 2.7 ± 0.2 g/cm3 (Ukraine) (Table 1), activa ted carbon BAU-A (Ukraine), and 1 % solution of PVDF in acetone (Sigma-Aldrich) stirred in an ultrasonic mixer up to homogeneity. Before mixing, powdered iron was treated with a solu- tion of 1 M HNO3 to obtain oxides on the sur- face of the iron particles. Then, the electrode mass was pressed on a steel grid with a size of 1 cm2. Table 1. Mass fraction of impurities in powdered iron, wt. % С Si Mn S P O 0.05± 0.01 0.08± 0.02 0.20± 0.01 0.02± 0.02 0.02± 0.02 0.5± 0.01 93https://ucj.org.ua Panteleimonov R.A., Shcherbatiuk I.M., Pershina K.D. UCJ № 02/ Vol. 89 An electrochemical module Autolab 30 PGSTAT301N Metrohm Autolab with 3-elec- trode cells was used for electrochemical stu dies. Powdered iron was the working electrode, the counter electrodes were platinum (Pt), car- bon (C), and Ag/AgCl was reference electrode. Cyclic voltammograms (CVA) and open cir- cuit potential (OCP) data were recorded at a potential scan rate of 0,1 and 50 mV/s in 0.1, 5 M solutions of NaOH and 1 M NaCl. Elec- trochemical impedance spectra were recorded in the potentiostatic mode both at open circuit potentials and at overpotentials of 100, 200, and 300 mV under H2 evolution in a frequency range of 0.01 Hz ÷ 105 kHz with a constant ac voltage amplitude of 10 mV. The data of elec- trochemical impedance spectroscopy were pro- cessed by FRA and Zview software packages. The micromorphological studies of com- posite samples and the quantitative microana lysis of the surface were performed on a scan- ning electron microscope Tescan Mira 3 LMU on the cathode with Schottky field emission and automatic measurement on images and on an energy dispersive spectrometer Oxford In- struments X-Max 80 mm2 SDD (table). The an- alytical mode of the scanning microscope was used to determine the relationship between the microstructure and local thermal reactions on iron particles. The CVA of the Fe/C/PVDF electrode in neutral and basic media has considerable diffe rences in cathodic and anodic wave shapes and they have different potential ranges of stability (fig. 1 a, b). In the neutral media (NaCl), this range is 0.5 – 0.75 V with surface passivation in a wide potential range – 0.76 ÷ + 1.9 V vs NHE (fig 1 a) with increasing internal area of CVA. Fig 1. CVA curves of iron powder electrode: a – in 1 M NaCl (neutral media), b – in 0,1 M NaOH (alkali media). а b Fig 1. CVA curves of iron powder electrode: a – in 1 M NaCl (neutral media), b – in 0,1 M NaOH (alkali media). The increase in these areas during the cycling of the electrode indicates its capability to charge. In the alkaline media, the potential range of stability increased up to 1.2–1.4 V without any passivation (fig. 1 b, 2) explained by the formation of the hydroxides on the surface [6]. Logarithmic dependences of current changes have specified differences in the electrochemical behavior of electrodes (Fig. 2). a а b Fig 1. CVA curves of iron powder electrode: a – in 1 M NaCl (neutral media), b – in 0,1 M NaOH (alkali media). The increase in these areas during the cycling of the electrode indicates its capability to charge. In the alkaline media, the potential range of stability increased up to 1.2–1.4 V without any passivation (fig. 1 b, 2) explained by the formation of the hydroxides on the surface [6]. Logarithmic dependences of current changes have specified differences in the electrochemical behavior of electrodes (Fig. 2). a The increase in these areas during the cy- cling of the electrode indicates its capability to charge. In alkaline media, the potential range of stability increased to 1.2 – 1.4 V without any passivation (fig 1 b, 2), which is explained by the formation of hydroxides on the surface [6]. Logarithmic dependences of current changes have specific differences in the electrochemical behavior of electrodes (Fig.2). 94 ISSN 2708-129X. Укр. хім. журн., 2023 FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMSPHISICAL CHEMISTRY Fig. 2. Polarization curves of iron powder electrode in: a- 1 M NaCl; b - 0,1 M NaOH. а b Fig 1. CVA curves of iron powder electrode: a – in 1 M NaCl (neutral media), b – in 0,1 M NaOH (alkali media). The increase in these areas during the cycling of the electrode indicates its capability to charge. In the alkaline media, the potential range of stability increased up to 1.2–1.4 V without any passivation (fig. 1 b, 2) explained by the formation of the hydroxides on the surface [6]. Logarithmic dependences of current changes have specified differences in the electrochemical behavior of electrodes (Fig. 2). a b Fig. 2. Polarization curves of iron powder electrode in: a- 1 M NaCl; b - 0,1 M NaOH. According to the Tafel equations, the Fe/C/PVDF electrodes have only one zero net current potential at the – 0.173 V, with further dissolution in a wide potential range from – 0.5 V to – 2.29 V in neutral media (fig.2, a). In the alkaline electrolytes, the system has two zero net potentials at the – 0.68 V and +0.35 V with a passivation range between -0.23 ÷ – 0.88 V (fig. 2,b) connecting with the impact of reversible redox reactions in the Fe/FexOy (x = 0 ÷ 3) systems. Such behavior is connected with the active interphase generation on the electrode surface based on the thermodynamics of the redox reactions (Table 2). Table 2. Standard enthalpies of redox reactions with oxygen and carbon for iron and its oxides [15]. Equation of reaction ΔН, kJ/M Equation of reaction ΔН, kJ/M 2Fe + 3/2O2→ FeO -824 FeO + C→ Fe + CO +100 2FeO+ 1/2 O2→ Fe3O4 -280 FeO + CО→ Fe + CO2 +17 Fe2O3+Fe= 3FeO +14,7 3Fe2O3 + CO =2Fe3O4+ CO2 +58 Fe2O3+Fe= 4FeO +16,8 Fe3O4 + CO = 3FeO + CO2 +38 Analysis of the Fe/C/PVDF electrode samples after 1 cycle found decreasing in the amount of pure iron (Fe0) on 0.24 mas.% which would, probably, be connected with oxidizing of the iron in reactions Fe2O3+Fe= 3FeO and Fe2O3+Fe= 4FeO under the current upload. The impact of oxygen has a good correlation with surface morphology. Cycling under the limited presence of oxygen brings the surface into a state of increasing of particle size with retention of the mosaic surface structure (fig. 3 a). If the electrode surface has long contact with air, such a mosaic structure became to monolayer structure (fig. 3 b). According to the Tafel equations, the Fe/C/ PVDF electrodes have only one zero net cur- rent potential at – 0.173 V with further disso- lution in a wide potential range from – 0.5 V to – 2.29 V in neutral media (fig.2, a). In al- kaline electrolytes, the system has two zero net potentials at – 0.68 V and +0.35 V with a passivation range between – 0.23 and – 0.88 V (fig.2,b) which is associated with the impact of reversible redox reactions in Fe/FexOy (x = 0 ÷ 3)systems. This behavior is connected with active interphase generation on the electrode surface based on the thermodynamics of redox reactions (Table 2). 95https://ucj.org.ua Panteleimonov R.A., Shcherbatiuk I.M., Pershina K.D. UCJ № 02/ Vol. 89 Table 2. Standard enthalpies of redox reactions with oxygen and carbon for iron and its oxides [15]. Equation of reaction ΔН, kJ/M Equation of reaction ΔН, kJ/M 2Fe + 3/2O2→ FeO -824 FeO + C→ Fe + CO +100 2FeO+ 1/2 O2→ Fe3O4 -280 FeO + CО→ Fe + CO2 +17 Fe2O3+Fe= 3FeO +14,7 3Fe2O3 + CO =2Fe3O4+ CO2 +58 Fe2O3+Fe= 4FeO +16,8 Fe3O4 + CO = 3FeO + CO2 +38 An analysis of Fe/C/PVDF electrode sam- ples after 1 cycle showed a decrease in the amount of pure iron (Fe0) by 0.24 mas.% which would, probably, be connected with the oxida- tion of iron in the reactions Fe2O3+Fe= 3FeO and Fe2O3+Fe= 4FeO under current load. The impact of oxygen has a good correlation with surface morphology. Cycling in the limited presence of oxygen brings the surface into a state of increasing particle size with retention of the mosaic surface structure (fig.3 a). If the electrode surface has long contact with air, this a mosaic structure becomes a monolayer structure (fig.3 b). Fig. 3. SEM images of the surface of the electrode in the potential range – 0.23 ÷ -1.0 V: a – after cycling in the limited presence of oxygen; b – after cycling in the prolonged contact with air. a b Fig. 3. SEM images of the surface of the electrode in the potential range – 0.23 ÷ -1.0 V: a – after cycling under the limited presence of oxygen; b – after cycling in the prolonged contact with air. In this case, the transformation of surface morphology takes place. According to the thermodynamic laws, the presence of an oxidized iron surface creates prerequisites for the implementation of several thermochemical reactions. Oxidative reactions with oxygen are exothermic, and reduction reactions of disproportionation and reactions with carbon and carbon monoxide are endothermic (Table 3). Final calculations of the main molar enthalpies of iron reactions in these systems: Σ ΔHex – Σ ΔHend = -1504 + 444.5 = 1059.5 (kJ/M) allows us to assume that the presence of external temperature influence should lead to a shift in thermodynamic equilibrium, i.e. can form local zones with the appropriate chemical potential. Thus, the presence of carbon and powdered iron in the electrode composition creates thermodynamic prerequisites for the appearance of temperature gradients on the electrode surface in the absence of an electrical load. Enhancement of this effect is possible due to the a b Fig. 3. SEM images of the surface of the electrode in the potential range – 0.23 ÷ -1.0 V: a – after cycling under the limited presence of oxygen; b – after cycling in the prolonged contact with air. In this case, the transformation of surface morphology takes place. According to the thermodynamic laws, the presence of an oxidized iron surface creates prerequisites for the implementation of several thermochemical reactions. Oxidative reactions with oxygen are exothermic, and reduction reactions of disproportionation and reactions with carbon and carbon monoxide are endothermic (Table 3). Final calculations of the main molar enthalpies of iron reactions in these systems: Σ ΔHex – Σ ΔHend = -1504 + 444.5 = 1059.5 (kJ/M) allows us to assume that the presence of external temperature influence should lead to a shift in thermodynamic equilibrium, i.e. can form local zones with the appropriate chemical potential. Thus, the presence of carbon and powdered iron in the electrode composition creates thermodynamic prerequisites for the appearance of temperature gradients on the electrode surface in the absence of an electrical load. Enhancement of this effect is possible due to the In this case, a transformation of surface morphology takes place. According to ther- modynamic laws, the presence of an oxidized iron surface creates prerequisites for the im- plementation of several thermochemical re- actions. Oxidation reactions with oxygen are exothermic, and reduction disproportionation reactions and reactions with carbon and car- bon monoxide are endothermic (Table 3). Fi- nal calculations of the main molar enthalpies of iron reactions in these systems: Σ ΔHex– Σ ΔHend= -1504 + 444.5 = 1059.5 (kJ/M) 96 ISSN 2708-129X. Укр. хім. журн., 2023 FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMSPHISICAL CHEMISTRY allows us to assume that external temperature influence should lead to a shift in thermody- namic equilibrium, i.e. can form local zones with the appropriate chemical potential. Thus, the presence of carbon and powdered iron in the electrode composition creates thermo- dynamic prerequisites for the appearance of temperature gradients on the electrode sur- face in the absence of electrical load. The en- hancement of this effect is possible due to the introduction of impurities with low thermal conductivity good thermal stability and tough- ness. Polyvinylidene fluoride has all of these properties. On the other hand, PVDF is a well- known semicrystalline polymer in which the percentage of the crystalline phase remarkably affects almost all physical properties of poly- mers. So, the change in surface morphology can be the result of changes in PVDF crystal- linity under temperature impact in the local zones near iron particles. [14]. Further analysis of oxygen content detected a difference in the oxygen content on the surface of iron particles and in the bulk of graphite (Fig.4, Table 3). This difference is related to the ability of Fe coated by Fe3O4 in the presence of graphite to induce the reduction of Fe3+ to Fe2+ with the generation of free high reactive oxygen. [16]. High by reactive oxygen is able to form -O–O- and C=O groups on PVDF main- ly due to the exchange of F in C-F groups [17]. According to these properties, PVDF could have an initiator function to produce an active oxygen species. Fig.4. SEM image and analyzed zones on the surface of a Fe/C/PVDF film introduction of impurities with low thermal conductivity with good thermal stability and toughness. The polyvinylidene fluoride has all of these properties. On other hand, PVDF is a well-known semicrystalline polymer in which the percentage of the crystalline phase remarkably affects almost all physical properties of polymers. So, the changing of surface morphology can be the result of changes in PVDF level crystallinity under temperature impact in the local zones near iron particles. [14]. Further analysis of oxygen content detected the difference in the oxygen content on the surface of iron particles and in the volume of graphite (Fig.4, Table 3). Such difference is related to the ability of Fe coated by Fe3O4 in the presence of graphite to induce the reduction of Fe3+ to Fe2+ with the generation of free high reactive oxygen. [16]. High reactive oxygen is able to form -O–O- and C=O groups on PVDF mainly due to exchanging F in C–F groups [17]. According to these properties, PVDF could have an initiator function to produce an active oxygen species. Fig.4. SEM image and analyzed zones on the surface of Fe/C/PVDF film Table 3. The elementary composition of the composite film’s surface, wt.% Zones of the sample C O Fe F Ratio (formula) Zone 1 23.21±2.1 48.83±0.3 26.23±0.5 0.77±0.5 FeC4O6 Zone 2 96.44±2.1 2.79±0.3 26.23±0.5 0.77±0.5 Fe3O C48 So, on the surface of iron particles forms a new interface (with size 30 ÷ 80 nm) (fig.4) saturated by active oxygen compounds with high mobility. Confirmation of high mobility of oxygen species is the analysis of graphite in the volume, where at a distance of more than 30 μm the presence of oxygen is found, but in smaller quantities. Also, this region has detected Fe0. If the presence of Fe2O3 takes place, the probability of the formation of Fe3C increases in the graphite space. Thus, the simultaneous presence of proactive compounds of oxygen and iron carbide should significantly affect the formation of gradient phenomena and change the thermoelectric and electrochemical properties of the whole system. CONCLUSIONS. The presence of an oxidized iron surface creates prerequisites for the realization of several thermochemical reactions and induces the appearance of the local zones with high temperatures. Under these temperatures, the probability of the iron ions reduction in the presence of carbon and exchanging fluorine in C–F groups on oxygen with the formation of - O–O- and C=O groups on PVDF is increasing. In this case, iron particles are becoming the centers of formation of new active interphase with a high ability to redox transformation. Temperature and changing chemical structure are the factors of changing level of crystallinity of 97https://ucj.org.ua Panteleimonov R.A., Shcherbatiuk I.M., Pershina K.D. UCJ № 02/ Vol. 89 Table 3. The elementary composition of the composite film surface, wt.% Zones of the sample C O Fe F Ratio (formula) Zone 1 23.21±2.1 48.83±0.3 26.23±0.5 0.77±0.5 FeC4O6 Zone 2 96.44±2.1 2.79±0.3 26.23±0.5 0.77±0.5 Fe3O C48 So, on the surface of iron particles forms a new interface (with a size of 30 ÷ 80 nm) (fig.4) saturated by active oxygen compounds with high mobility. A confirmation of the high mo- bility of oxygen species is the analysis of gra phite in the bulk, where at a distance of more than 30 μm the presence of oxygen is found, but in smaller quantities. Also, in this region we detected Fe0. If the presence of Fe2O3 takes place, the probability of the formation of Fe3C increases in the graphite space. Thus, the si- multaneous presence of proactive compounds of oxygen and iron carbide should significant- ly affect the formation of gradient phenomena and change the thermoelectric and electro- chemical properties of the whole system. CONCLUSIONS. The presence of an oxi- dized iron surface creates prerequisites for the realization of several thermochemical reactions and induces the appearance of the local zones with high temperatures. At these temperatures, the probability of the iron ions reduction in the presence of carbon and exchanging fluorine in C-F groups on oxygen with the formation of -O–O- and C=O groups on PVDF increases. In this case, iron particles become the centers of formation of a new active interphase with a high ability for redox transformation. Tem- perature and changing chemical structure are the factors of changing level of crystallinity of PVDF, which affect the surface morphology of Fe/C/PVDF electrodes. Under electric cur- rent impact such composition is able to change their electrochemical properties depending on the pH of the electrolyte. In neutral solu- tions (pH  ~7), Fe/C/PVDF electrode has the property of a capacitor and has battery redox properties in alkaline solutions (pH~ 10). AKNOLEDGEMENT. This work was supported by the National Academy of Sciences of Ukraine in the framework of project 0122U200794. УТВОРЕННЯ АКТИВНОЇ ІНТЕРФАЗИ НА ЧАСТИНКАХ ЗАЛІЗА В ЕЛЕКТРОХІМІЧНИХ СИСТЕМАХ C/PVDF Р. А. Пантелеймонов1., І. М. Щербатюк2, К. Д. Першина1,2 1Інститут загальної та неорганічної хімії імені В. І. Вернадського НАН України, проспект Академіка Палладіна, 32/34, Київ 03142, Україна 2Міжвідомче відділення електрохімічної енергетики НАН України, проспект Академіка Вернадського, 38 А, Київ 03142, Україна e-mail: radik20031@gmail.com 98 ISSN 2708-129X. Укр. хім. журн., 2023 FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMSPHISICAL CHEMISTRY Можливість утворення активної між- фази на частинках заліза в середовищі C/PVDF була продиктована термохіміч- ними реакціями заліза та оксидів залі- за за присутності вуглецю. Композиція з полівініліденфторидом (PVDF) змінила окисно-відновну активність частинок за- ліза та зменшила кількість чистого заліза (Fe0) на 0,24 мас. %. Властивості поверхні різних композицій було охарактеризовано за допомогою скануючої електронної мі- кроскопії з аналітичним режимом для ви- значення зв'язку між мікроструктурою та локальними тепловими реакціями на по- верхні частинки заліза. Було знайдено зв’я- зок між складом поверхні, морфологією та електрохімічною поведінкою електродів Fe/C/PVDF. Електричний струм впливає на морфологію поверхні та змінює її з моза- їчної структури на моноліт за присутності кисню повітря. Тривалий контакт повітря (понад 3 години) під час електрохімічно- го циклування змінює структуру поверхні в бік зниження кристалічності. Електрод Fe/C/PVDF може заряджатися в нейтраль- них розчинах (pH ~7). Ключові слова: частинка заліза, актив- на міжфаза, полівініліденфторид, вуглець, електрод. REFERENCES 1. Moeez I., Susanto D., Chang W., Lim H. D., & Chung K. Y. Artificial cathode electrolyte in- terphase by functional additives toward long- life sodium-ion batteries.  Chemical Engineer- ing Journal. 2021. 425: 130547. https://doi.org/10.1016/j.cej.2021.130547 2. Bock D. C., Waller G. H., Mansour A. N., Marschilok A. C., Takeuchi K. J., & Takeuchi E. S.. Investigation of solid electrolyte inter- phase layer formation and electrochemical reversibility of magnetite, Fe3O4, electrodes: a combined X-ray absorption spectroscopy and X-ray photoelectron spectroscopy study. The Journal of Physical Chemistry C. 2018. 122(26): 14257–14271. https://doi.org/10.1021/acs.jpcc.8b01970 3. Bruck A. M., Gannett C. N., Bock D. C., Smith P. F., Marschilok A. C., Takeuchi K. J., & Takeuchi E. S. The electrochemistry of Fe3O4/polypyrrole composite electrodes in lithium-ion cells: the role of polypyrrole in ca- pacity retention. Journal of The Electrochemical Society. 2016. 164(1): A6260. doi: 10.1149/2.0361701jes 4. Naber W. J. M., Faez S., & van der Wiel W. G.  Wilfred Gerard. Organic spintronics.  Journal of Physics D: Applied Physics. 2007. 40(12): R205. doi: 10.1088/0022-3727/40/12/R01 5. Tsonos C., Zois H., Kanapitsas A., Soin N., Siores E., Peppas G. D., ... & Psarras G. C. Pol- yvinylidene fluoride/magnetite nanocompos- ites: Dielectric and thermal response.  Journal of Physics and Chemistry of Solids. 2019. 129: 378–386. https://doi.org/10.1016/j.jpcs.2019.01.025 6. Kravchenko O. V., Pershina K. D., Panteley- monov R. A., & Potapenko O. V. Electrochem- ical Properties of Powder Iron/Carbon System in Basic Solution.  Materials Today: Proceed- ings]. 2019. 6: 65–72. https://doi.org/10.1016/j.matpr.2018.10.076 7. Boichuk O., Pershina K., Riabokin O., Krav chenko A., & Panteleimonov R. Thermo-gal- vanic effects in a non-isothermal element based on the of iron-carbon compositional electrode and alkaline electrolyte.  Ukrainian Chemistry Journal. 2020. 86(4): 108–117 https://doi.org/10.33609/2708-129X.86.4. 2020.108–117 8. Sencadas V., Moreira M. V., Lanceros-Méndez S., Pouzada A. S., & Gregório Filho R. α-to β 99https://ucj.org.ua Panteleimonov R.A., Shcherbatiuk I.M., Pershina K.D. UCJ № 02/ Vol. 89 Transformation on PVDF Films Obtained by Uniaxial Stretch. In:  Materials science forum. Trans Tech Publications Ltd, 006. 514: 872–876. https://doi.org/10.4028/www.scientific.net/ MSF.514-516.872 9. Broadhurst M.G., Davis G.T., McKinney J.E., & Collins R.E. Piezoelectricity and pyroelec- tricity in polyvinylidene fluoride—A mod- el.  Journal of applied physics. 1978. 49(10): 4992–4997. https://doi.org/10.1063/1.324445 10. Lovinger Andrew J. Annealing of poly (vi- nylidene fluoride) and formation of a fifth phase.  Macromolecules. 1982. 15(1): 40–44. https://doi.org/10.1021/ma00229a008 11. Ramazanov M. A., Alizade R. A., Maharra mov A. M., Hajiyeva F. V., Sultanova J. R., & Shirinova H. A. Theoretical and experimental study of the magnetic properties and size of distribution of PVDF+ Fe based nanocompos- ites.  Journal of Inorganic and Organometallic Polymers and Materials. 2018. 28: 2179–2186. https://doi.org/10.1007/s10904-018-0863-2 12. Wang H., Chen Y., Yu H., Liu W., Kuang G., Mei L., ... & Chen L. A Multifunctional Arti- ficial Interphase with Fluorine-Doped Amor- phous Carbon layer for Ultra-Stable Zn An- ode.  Advanced Functional Materials. 2022. 32(43): 2205600   https://doi.org/10.1002/adfm.202205600 13. Ramaprabhu S., & Ajay P. V. Handbook of Sodi- um-Ion Batteries. 2023. 323–344. 14. Xu H.P., Dang Z.M. Electrical property and microstructure analysis of poly (vinylidene fluoride)-based composites with different con- ducting fillers.  Chemical physics letters. 2007. 438(4–6): 196–202 https://doi.org/10.1016/j.cplett.2007.02.076 15. Galvez M. E., Loutzenhiser P. G., Hischier I., & Steinfeld A. CO2 splitting via two-step so- lar thermochemical cycles with Zn/ZnO and FeO/Fe3O4 redox reactions: thermodynamic analysis.  Energy & Fuels. 2008. 22(5): 3544– 3550. https://doi.org/10.1021/ef800230b 16. Correia D. M., Ribeiro C., Sencadas V., Bo- telho G., Carabineiro S.A.C., Ribelles J. G., & Lanceros-Méndez S. Influence of oxygen plas- ma treatment parameters on poly (vinylidene fluoride) electrospun fiber mats wettability. Pro- gress in Organic Coatings. 2015. 85: 151–158 https://doi.org/10.1016/j.porgcoat.2015.03.019 17. Ross G. J., Watts J. F., Hill M. P., & Morrissey P. Surface modification of poly (vinylidene fluoride) by alkaline treatment1. The deg- radation mechanism.  Polymer. 2000. 41(5): 1685–1696. https://doi.org/10.1016/S0032- 3861(99)00343-2 Стаття надійшла 05. 02. 2023.
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5322026-07-22T08:23:51Z FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS Panteleimonov, Radyslav Pershina, Katherine Shcherbatiuk , Ivan iron particle, active interphase, polyvinylidene fluoride, carbon, electrode. The possibility of formation of an active interphase on iron particles in C/PVDF has been dictated by the thermochemical reactions of iron and iron oxides in the presence of carbon. The composition with polyvinylidene fluoride (PVDF) changed the redox activity of iron particles and decreased pure iron (Fe0) amount by 0,24 wt. %. The surface properties of various compositions have been characterized by scanning electron microscopy with the analytical mode for determining the relationship between the microstructure and local thermal reactions on the iron particle surface. A relationship between the surface composition, morpho­logy and electrochemical behavior of the Fe/C/PVDF electrodes has been found. Electric current affects the surface morphology and changes it from a mosaic structure to a monolith in atmosphere oxygen. The electrochemical properties of Fe/C/PVDF electrodes have been tested using cyclic voltammetry (CVA). The long air contact (for more than 3 hours) during electrochemical cycling changes the surface structure in the direction of decreasing crysta­llinity. The Fe/C/PVDF electrode can be charge in neutral solutions (pH ~7). V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-03-24 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/532 10.33609/2708-129X.89.02.2023.91-99 Ukrainian Chemistry Journal; Vol. 89 No. 2 (2023): Ukrainian Chemistry Journal; 91-99 Украинский химический журнал; ##issue.vol## 89 ##issue.no## 2 (2023): Ukrainian Chemistry Journal; 91-99 Український хімічний журнал; Том 89 № 2 (2023): Український хімічний журнал; 91-99 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/532/268 Copyright (c) 2023 Radyslav Panteleimonov, Katherine Pershina, Ivan Shcherbatiuk https://creativecommons.org/licenses/by-nc/4.0
spellingShingle Panteleimonov, Radyslav
Pershina, Katherine
Shcherbatiuk , Ivan
FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title_full FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title_fullStr FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title_full_unstemmed FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title_short FORMATION OF ACTIVE INTERPHASE ON THE IRON PARTICLES IN C/PVDF ELECTROCHEMICAL SYSTEMS
title_sort formation of active interphase on the iron particles in c/pvdf electrochemical systems
topic_facet iron particle
active interphase
polyvinylidene fluoride
carbon
electrode.
url https://ucj.org.ua/index.php/journal/article/view/532
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AT pershinakatherine formationofactiveinterphaseontheironparticlesincpvdfelectrochemicalsystems
AT shcherbatiukivan formationofactiveinterphaseontheironparticlesincpvdfelectrochemicalsystems