ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ
In article was established the conditions for measuring thermal diffusion and thermoelectric effects in non-isothermal elements with composite electrodes of powdered iron and carbon in the alkaline electrolytes using electrochemical impedance spectroscopy. By the modeling of the impedance spectra of...
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|---|---|
| author | Boichuk, Oleksandr Pershina, Katherine Riabokin, Oleh Kravchenko, Alexandr Panteleimonov, Radyslav |
| author_facet | Boichuk, Oleksandr Pershina, Katherine Riabokin, Oleh Kravchenko, Alexandr Panteleimonov, Radyslav |
| author_institution_txt_mv | [
{
"author": "Oleksandr Boichuk",
"institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, 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": "Oleh Riabokin",
"institution": null
},
{
"author": "Alexandr Kravchenko",
"institution": null
},
{
"author": "Radyslav Panteleimonov",
"institution": null
}
] |
| author_sort | Boichuk, Oleksandr |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:42Z |
| description | In article was established the conditions for measuring thermal diffusion and thermoelectric effects in non-isothermal elements with composite electrodes of powdered iron and carbon in the alkaline electrolytes using electrochemical impedance spectroscopy. By the modeling of the impedance spectra of these systems has been established the most advantageous equivalent model scheme, which confirms that the external resistance has several components: the resistance of the electrolyte, the resistance of the capacity of the double electric layer and the resistance of thermal diffusion, which forms the dispersion of the capacity. By the calculations of the capacity and the dispersion of the capacity in the low- and high-frequency measurement range have been shown the effect of the concentration of composition components on the formation of the additional heat capacity, which creates the preconditions for realizing of the thermal electrical effects. Increasing of a concentration of the iron leads to the increase of the number of oxide (semiconductor) structures that increase the additional heat capacity. Such heat capacity induces electrical capacity and its dispersion. That is, it creates the preconditions for the occurrence of thermoelectric effects, especially Sore effects in the non-isothermal element. This work was realized due the projects of the Purpose Program for Basic Research of the Chemistry Department of NAS of Ukraine "Basic Research in Priority Areas of Chemistry" P - 1 - 17 DR 0117U000856 and "Strategy of creation of new heat-energy systems based on iron and its compounds, sulfur and oxygen" No. 0117U0008. |
| doi_str_mv | 10.33609/2708-129X.86.4.2020.108-117 |
| first_indexed | 2025-09-24T17:43:25Z |
| format | Article |
| fulltext |
Фізична хімія
108 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4
УДК 621.351 doi: 10.33609/2708-129X.86.4.2020.108-117
O.V. Boychuk1, O.A. Ryabokin2, O.V. Kravchenko2,
R.A. Panteleimonov1, K.D. Pershina1,2
THERMO-GALVANIC EFFECTS IN A NON-ISOTHERMAL ELEMENT BASED
ON THE OF IRON-CARBON COMPOSITIONAL ELECTRODE AND ALKALINE
ELECTROLYTE
1Institute of General and Inorganic Chemistry Vernadsky NAS of Ukraine
2Joint Department of Electrochemical Energy Systems NAS of Ukraine
*email:Pershina@ionc.kiev.ua
The conditions for measuring thermal diffusion and thermoelectric effects in a non-
isothermal element with composite electrodes based on powdered iron and carbon in al-
kaline electrolytes were determined using electrochemical impedance spectroscopy. The
impact of the concentration of the components with various nature of conductivity on the
appearance of additional heat capacitance and the Sore effect was shown by the calcula-
tions of the capacitance and the capacitance’s dispersion in the low and high- frequency
measurement ranges. An electrical equivalent circuit of a non- isothermal thermal gal-
vanic element based on an iron-carbon composite electrode and an alkaline electrolyte
was proposed.
K e y w o r d s: iron-carbon composite electrode, thermal galvanic element, Seebeck co-
efficient, impedance spectroscopy, electrical equivalent circuit, capacitance dispersion.
INTRODUCTION. Directed conversion
of thermal energy into electrical energy us-
ing thermogalvanic systems (TGS) is one of
the ways of modern chemical current
sources development. The first works on
study of thermogalvanic cells were focused
on the establishment of thermal diffusional
potentials, which are related to the Sore ef-
fect under non-isothermal conditions [4-6].
In the work [7], a mathematical approxima-
tion was developed for a transitive open
thermal galvanic system that took into ac-
count the equilibrium of thermal diffusion
ions. Later the researches were focused on
using of various redox electrolytes and the
entropy analysis of their reactions with plat-
inum electrodes. They showed that aqueous
ferri/ferrocyanide potassium solutions have
one of the highest entropy (-180 J mol-K-1)
of the redox reactions. In addition to that, the
efficiency of these cells was low enough
<0.1% with a maximum electrical power up
to 3 W/m2 [8-11]. In 2001 it was demon-
strated the rapid kinetics of redox reactions
using ferric/potassium ferrocyanide on
electrodes from multilayer carbon nano-
© O.V. Boychuk, O.A. Ryabokin, O.V. Kravchenko, R.A. Panteleimonov,
K.D. Pershina, 2020
Thermo-galvanic effects in a non-isothermal element…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4 109
tubes (MWCNT) [11]. This confirmed the
significant influence of the electrode’s mate-
rials and its structure on the ways of redox
reactions and the formation of temperature
gradients Thus, it is possible to realize not
only the Sore effect, but also the Seebeck
effect, when the temperature difference ex-
ists between two different electrical conduc-
tors or semiconductors and creates a voltage
on two materials:
E = S(T2 – T1), V/К (1)
S – Seebeck coefficient.
So, it is possible the significant increas-
ing the efficiency of thermogalvanic (TG)
elements by using composite electrodes con-
sisted of the combination of materials with
different nature of the conductivity (presence
of the metal iron particles with electronic
conductivity covered by mixture of iron ox-
ides with ionic conductivity of n- and p-
types according to oxygen content [12-15])
and layered structure.
On the other hand, the thermogalvanic
element could be considered as a normal
current source in which the effective voltage
and electric current varies depending on the
external resistance (rext). The ion transport is
realized by combining of convection, migra-
tion and thermal diffusion in such source.
The current flow is presented during sup-
porting of the temperature difference [16].
When rext → 0, the current I → Io (Io is the
short-circuit current) and when rext → ∞,
I→0, the load voltage U→ U0 (U0 open cir-
cuit voltage). In the general case, the internal
resistance r can be calculated from the se-
cond Kirchhoff equation for a closed circuit
[16]:
𝑟 = 𝑈0 𝐼 − 𝑟𝑒𝑥𝑡⁄ (2)
Taking that into account it becomes
possible to use electrochemical impedance
spectroscopy (EIS) to establish the nature of
external and internal resistance in such sys-
tems.
Therefore, the aim of this work was to
determine the nature of the thermogalvanic
effects occurrence in non-isothermal ele-
ments with composite electrodes of pow-
dered iron and carbon in alkaline electrolytes
using electrochemical impedance spectros-
copy (EIS).
EXPERIMENT AND DISCUSSION OF
THE RESULTS. The thermogalvanic ele-
ments with composite electrodes based on
mixtures of powedered iron and carbon in
different ratios and 19 M NaOH electrolyte
were selected as non-isothermal TG systems.
The disk elements were assembled in the
standard size 20x16 mm. The iron brand
powder FGD 3.200.28-30 with a bulk densi-
ty of 2.7 ± 0.2 g/cm3 and a particle size of up
to 300 μm was chosen as the main compo-
nent of the electrode composition. (Table 1).
T a b l e 1.
Mass fraction of impurities in powdered iron,
wt. %
С Si Mn S P O
0,05 0,08 0,20 0,02 0,02 0,5
The elements were tested in the tem-
perature range 15-45 oC. OCV. The imped-
ance spectra have been obtained in the fre-
quency range 10-2-106 Hz in a two-electrode
cell (disk cell) on an Autolab 30
PGSTAT301N Metrohm Autolab
O.V. Boychuk, O.A. Ryabokin, O.V. Kravchenko, R.A. Panteleimonov, K.D. Pershina
110 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4
T a b l e 2.
Standard enthalpy of redox reactions with oxygen and carbon for iron and its oxides [13-16].
Reaction equation ΔH, kJ/M Reaction equation ΔH, 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
4FeO+O2 = 2Fe2O3 -400 2Fe2O3+C = 4FeO+CO2 + 200
electrochemical module equipped by a Fre-
quency Response Analyzer (FRA). For
providing the required temperature interval
during the cyclization it was used a thermo-
stat with temperature performance T ± 1 oC.
The EIS measurements were realized in the
frequency range 10-2-106 Hz. The results
were processed using Nova 2.1 and ZView2
software. The open circuit voltage (OCV) of
the elements was determined by two meth-
ods: using a DT-832 high-voltage voltmeter
and on the PGSTAT302N Metrohm Autolab
electrochemical module.
The presence of the oxidized surface’s
forms of the iron is the preconditions for the
implementation of several thermochemical
reactions. According to thermodynamic
properties of the compounds, the nature of
the oxidation reactions with oxygen is exo-
thermic, the reduction reactions realized as
disproportionated reactions and the reactions
with carbon and carbon monoxide are endo-
thermic (Table 2).
The summary calculations of the basic
molar enthalpy of the iron reactions in these
systems: Σ ΔНекз.– Σ ΔНенд.= -1504 + 444,5
= 1059,5 (кJ/М) suggest that presence of
external impact of temperature, which
changes the thermodynamic equilibrium and
forms the local zones with appropriate
chemical potential. Thus, the presence of
carbon and powdered iron in the electrode
composition creates thermodynamic precon-
ditions for the appearance of temperature
gradients on the electrode surface in the ab-
sence of external electrical load [14-17].
Elemental analysis of the iron powder
surface determined the presence of the iron
oxides mixture on its surface [15]. Such
mixture of iron and iron oxides is a mixture
of conductors, n- and p-type semiconductors,
which under the exothermic reaction are able
to form temperature gradients and realize the
Seebeck effect. So, it is possible to use the
model of the heat exchanger in the system of
thermogalvanic element. In this case, the
typical values of the thermoelectric indices
considerable shift to the low frequency range
of the impedance spectra and be characteriz-
ing by the maximum of phase angle shift:
𝜑 = 𝑎𝑟𝑐 𝑡𝑎𝑛 �𝑍
"
𝑍′
� (3)
Thermo-galvanic effects in a non-isothermal element…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4 111
Correlating with a change |𝑍| :
|𝑍| = √𝑍"2 + 𝑍′2 = 𝑉𝑎𝑐
𝐼𝑎𝑐
(4)
By the values of |Z| it is possible to
calculate the RI parameter, the voltage drop
at the appearance of thermal power and the
changing of the current power in conditions
of constant external temperature:
𝑖0 = 𝑅𝐼
𝑍′ (0)−𝑍"(0)
𝐴
𝐿
(5)
𝑉 = 𝑅𝐼 + 𝑆(𝑇𝐿 − 𝑇0) (6)
𝑇𝐿 − 𝑇0 → −2𝜃(0) (7)
𝜃(0)- is the maximum shift of phase angle in
the low frequency range (the range of the
thermal power fixation), A – geometric sur-
face area of the electrode, L – length of the
electrode.
Then the impedance in the frequency
domain would be expressed as:
𝑍(𝑗𝜔) = 𝑅 − 𝑆2𝜃(0)
𝑖0
(8)
and the Seebeck coefficient as:
𝑆 = (𝑍0−𝑅0)
2𝜃
𝐴
𝐿
(9)
The measurements of the impedance
spectra of the samples with different iron
content have been established the existence
of such shifts (Fig. 1.b), which were fixed
only on the spectra in Bode coordinates (Fig.
1). It well conformed to Equations 4-8. Con-
sidering that the resistance of the thermoe-
lectric material was measured in the low fre-
quency range, the Seebeck coefficients were
calculated using equation 9 from the exper-
imental impedance spectra in the frequency
range 101-10-1 Hz. Calculated values of See-
beck coefficient are nearest to such values
Fig. 1. Impedance spectra of thermogalvanic
elements with different iron content: a- the EIS
spectrum of the samples in Nyquist coordinates,
b- the EIS spectrum of the samples in Bode co-
ordinates. The numbering of the samples accord-
ing to table 4.
T a b l e 3
The values of the calculated parameters of
the impedance spectra of TG samples with
different iron content
Mass
Fe, mg
𝑍0 −
𝑅0,
Ohm
2θ,
de-
gree
i0, А |S|, µV/К
0.1406 0.4 160 0.039 2500
0.1481 1.1 190 0.081 3800
0.1518 0.6 160 0.250 5900
a
b
O.V. Boychuk, O.A. Ryabokin, O.V. Kravchenko, R.A. Panteleimonov, K.D. Pershina
112 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4
T a b l e 4
Dependence of values of thermal EMF volt-
age on the ratio of iron and carbon compo-
nents under a thermal load of 30 оC
№
Sample
m(Fe),
g
m(С),
g
m(total)
, g
ОСV,
V
1 0.106 0.046 0.054 0.1
2 0.1492 0.0560 - 0.27
3 0.1586 0.0542 - 0.59
for composite metal-organic thin films at
room temperature and for polymer films [18,
19] (Table 3).
Thus, increasing of the concentration
of iron leads to increasing in thermoelectric
coefficients and creates certain preconditions
for the realization of the thermoelectric
transformations.
The high renewable activity of carbon
and its oxides can create additional precon-
ditions for the occurrence of thermal gradi-
ents in the volume of composites. Therefore,
our experiments were conducted the effect
of carbon concentration on the change in
Fig. 2. The model equivalent electrical circuit of
the TGE with composite electrode: R1- electro-
lyte resistance, C1- capacity of the DEL, R3 –
resistance of the surface’s structures of the elec-
trode, CPE2 – constant phase element connected
with dispersion of the capacity
thermal EMF.
Increasing the concentration of the car-
bon on the occurrence of thermal EMF does
not have the same effect as increasing the
concentration of iron (table 4).
By the modeling of the impedance
spectra of these systems has been established
the most profitable equivalent model scheme
(Fig. 2). Such circuit gives a possibility to
confirm the composition of an external re-
sistance: the resistance of the electrolyte, the
resistance of the capacity of the double elec-
tric layer (DEL) and the resistance of thermo
diffusion, which forms the dispersion of the
capacity.
This electrochemical model is in a
good agreement with experimental data of
the increasing of OCV. In samples with a
maximum OCV value, the CPE - T (closed
loop) the value is the highest and the C and
CPE – P the value is the lowest. However, a
clear correlation between the values of these
elements and the OCV is not observed
(table 5).
T a b l e 5
The values of the elements resistance of the
model equivalent electrical circuit of the TGE
with composite electrode
Elec-
trode∗
OCV,
V С, Om СРЕ-Т,
Om
СРЕ-
Р, Om
1 0.1 1•10-4 3•10-4 0,87
2 0.27 8•10-5 2•10-4 0,85
3 0.59 2•10-4 1.7•10-3 0,64
∗ Numbering according to table 4
Thermo-galvanic effects in a non-isothermal element…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4 113
Fig. 3. Diagrams of the capacity distribution
and its dispersion in the frequency range 101-
10-1 Hz for composite electrodes. Numbering
according to table 4.
Fig. 4. . Diagrams of the capacity distribution
and its dispersion in the 105 Hz frequency range
for composite electrodes. Numbering according
to table 4.
O.V. Boychuk, O.A. Ryabokin, O.V. Kravchenko, R.A. Panteleimonov, K.D. Pershina
114 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4
Therefore, it was considered the de-
pendence of the sample capacity distribution
and its dispersion in the frequency range
101-10-1 Hz. The capacity and the dispersion
of the capacity were calculated from the im-
pedance spectra according to the technique
[20- 23]. By the resulting calculations have
been established a correlation between the
increasing of OCV, the amount of iron and
the increasing of the dispersion of the capac-
ity with a decrease of the measurement’s
frequency (Fig. 3).
It is known [24] that at high electrolyte
concentrations (above 0.1 M), the diffusion
layer is so compact that most of the interfa-
cial potential only affects the reaction zone.
So, the fixed effects are summarized and
characterize the occurrence of primarily
thermal diffusion phenomena at the elec-
trode / electrolyte boundary [25]. Further
CEI measurements were performed using a
wide frequency domain of 106-10-1 Hz to
account of the possible impact of other
thermoelectric effects (Peltier, Thomson and
Sore) on the thermal diffusion parameters.
It was found, that the most informative
frequency range for these conditions is at
high frequency, namely 1 - 6 · 105 Hz (Fig.
3), which corresponds to the frequency of
measurement (0.1-1 MHz) of conductivity
on the surface of thin layers of semiconduc-
tors under the action of temperature [25-27].
Under the influence of the alternating
current the local heating of semiconductor
surface structures with a frequency of the
current is possible. It leads to the occurence
of additional heat capacity:
𝑑𝑝 = �𝐷𝑓 𝜋𝑓⁄ (10),
𝑓 - the frequency of periodic heating, 𝐷𝑓 -
the coefficient of thermal diffusion, which is
related to the electric capacity by the follow-
ing equation:
𝐷𝑓 = Λ𝑓 𝐶𝑓⁄ (11)
Λ𝑓- the thermal conductivity, 𝐶𝑓 - the elec-
tric capacity.
Increasing of a concentration of the
iron leads to the increase of the number of
oxide (semiconductor) structures that in-
crease the additional heat capacity. Such
heat capacity induces electrical capacity and
its dispersion. That is, it creates the precon-
ditions for the occurrence of thermoelectric
effects, especially Sore effects in the non-
isothermal element.
CONCLUSIONS. It was established the
conditions for measuring thermal diffusion
and thermoelectric effects in non-isothermal
elements with composite electrodes of pow-
dered iron and carbon in the alkaline electro-
lytes using electrochemical impedance spec-
troscopy. By the modeling of the impedance
spectra of these systems has been established
the most advantageous equivalent model
scheme, which confirms that the external
resistance has several components: the re-
sistance of the electrolyte, the resistance of
the capacity of the double electric layer and
the resistance of thermal diffusion, which
forms the dispersion of the capacity. By the
calculations of the capacity and the disper-
sion of the capacity in the low- and high-
frequency measurement range have been
shown the effect of the concentration of
composition components on the formation of
the additional heat capacity, which creates
the preconditions for realizing of the thermal
electrical effects.
Thermo-galvanic effects in a non-isothermal element…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4 115
This work was realized due the projects
of the Purpose Program for Basic Research
of the Chemistry Department of NAS of
Ukraine "Basic Research in Priority Areas of
Chemistry" P - 1 - 17 DR 0117U000856 and
"Strategy of creation of new heat-energy
systems based on iron and its compounds,
sulfur and oxygen" No. 0117U0008.
ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗО-
ТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ
ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙ-
НОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕК-
ТРОЛІТУ
О.В. Бойчук, О.А. Рябокінь, О.В. Кравченко,
Р.А. Пантелеймонов, К.Д. Першина
Інститут загальної та неорганічної хімії ім.
В.І. Вернадського НАН України, пр.. Палладі-
на, 32/34, Київ, 03142, Україна
Міжвідомче відділення електрохімічної енер-
гетики НАН України, вул. Академіка вер-
надського, 38а, Київ, 03680, Україна
*e-mail: Pershina@ionc.kiev.ua
За допомогою спектроскопії електрохі-
мічного імпедансу було встановлено умови
вимірювання термодифузійних та термоелек-
тричних ефектів у неізотермічних елементах
із композиційними електродами на основі
порошкового заліза та вуглецю в лужних
електролітах. Моделювання спектрів імпеда-
нсу цих систем встановило найбільш ймовір-
ну еквівалентну схему, яка підтверджує, що
зовнішній опір має декілька компонентів:
опір електроліту, опір ємності подвійного
електричного шару і опір термодифузії, що
формує дисперсію ємності. Розрахунками
ємності та дисперсії ємності у низько- та ви-
сокочастотному діапазоні вимірювань пока-
зано вплив концентрації суміші часточок
заліза з електронною провідністю та складо-
вих, що утворюються оксидами заліза з йо-
ною провідністю на виникнення додаткової
теплоємності та створення передумов для
реалізації термогальванічних ефектів (Зеєбе-
ку та Соре).
К л ю ч о в і с л о в а: термогальванічний
елемент, коефіцієнт Зеєбеку, імпедансна спе-
ктроскопія, дисперсія ємності, еквівалентна
електрична схема, залізо-вуглецевий компо-
зитний електрод.
ТЕРМОГАЛЬВАНИЧЕСКИЕ ЭФФЕКТЫ В
НЕИЗОТЕРМИЧЕСКОМ ЭЛЕМЕНТЕ НА
ОСНОВЕ ЖЕЛЕЗО-КАРБОНОВОГО КОМ-
ПОЗИЦИОННОГО ЭЛЕКТРОДА И ЩЕ-
ЛОЧНОГО ЭЛЕКТРОЛИТА
А.В. Бойчук, О.А. Рябокинь, А.В. Кравченко,
Р.А. Пантелеймонов, К.Д. Першина
Институт общей и неорганической химии
им. В.І. Вернадского НАН Украины, пр. Пал-
ладина, 32/34, Киев, 03142, Украина
Межведомственное отделение электрохи-
мической энергетики НАН Украины, ул. Ака-
демика Вернадского, 38а, Киев, 03680, Ук-
раина
*e-mail: Pershina@ionc.kiev.ua
С использованием спектроскопии элек-
трохимического импеданса установлены
условия измерения термодиффузионных и
термоелектрических эффектов в неизотерми-
ческих элементах с композиционными элект-
родами на основе ипорошкового железа и
графита в щелочных электролитах. Расчета-
ми емкости и дисперсии емкости в низко- и
высокочастотном диапазоне измерений пока-
зано влияние концентрации полупроводни-
ковых компонентов композиции на появле-
ние дополнительной теплоемкости и эффекта
Соре. Предложена модельная эквивалентная
электрическая схема неизотермического тер-
могальванического элемента на основе желе-
O.V. Boychuk, O.A. Ryabokin, O.V. Kravchenko, R.A. Panteleimonov, K.D. Pershina
116 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4
зо- графитового композиционного электрода
и щелочного электролита.
К л ю ч е в ы е с л о в а: термогальваниче-
ский элемент, коэффициент Зеебека, импе-
дансная спектроскопия, дисперсия емкости,
эквивалентная электрическая схема, железо-
углеродный композитный электрод.
REFERENCES
1. Straughan, B., Hutter, K. A priori bounds
and structural stability for double-diffusive
convection incorporating the Soret ef-
fect. Proceedings of the Royal Society of
London. Series A: Mathematical, Physical
and Engineering Sciences. 1999.
455(1983): 767-777.
2. Rowe, D. M.. Thermoelectrics, an envi-
ronmentally-friendly source of electrica l
power. Renewable energy. 1999. 16(1-4) :
1251-1256.
3. Petit, C. J., Hwang, M. H., Lin, J. L. Ther-
mal diffusion of dilute aqueous NH 4 Cl,
Me 4 NCl, Et 4 NCl, n-Pr 4 NCl, andn-Bu 4
NCl solutions at 25° C. Journal of solution
chemistry. 1988. 17(1): 1-13.
4. Malashetty, M. S., Gaikwad, S. N., Swamy,
M. An analytical study of linear and non-
linear double diffusive convection with
Soret effect in couple stress liq-
uids. International journal of thermal sci-
ences. 2006. 45(9): 897-907.
5. Jokinen, M., Manzanares, J. A., Kontturi,
K., & Murtomäki, L. Thermal potential o f
ion-exchange membranes and its application
to thermoelectric power generation. Journal
of Membrane Science. 2016. 499: 234-244.
6. Yella, A., Lee, H. W., Tsao, H. N., Yi, C.,
Chandiran, A. K., Nazeeruddin, M. K., ... &
Grätzel, M. Porphyrin-sensitized solar cells
with cobalt (II/III)–based redox electrolyte
exceed 12 percent efficiency. Science.
2011. 334(6056): 629-634.
7. Burrows, B. Discharge behavior of redox
thermogalvanic cells. Journal of The Elec-
trochemical Society. 1976. 123(2): 154.
8. Ikeshoji, T. Thermoelectric conversion by
thin- layer thermogalvanic cells with soluble
redox couples. Bulletin of the Chemical So-
ciety of Japan. 1987. 60(4): 1505-1514.
9. Mua, Y., Quickenden, T. I. Power conver-
sion efficiency, electrode separation, and
overpotential in the ferricyanide/fer-
rocyanide thermogalvanic cell. Journal of
The Electrochemical Society. (1996).
143(8): 2558-2564.
10. Nuwayhid, R. Y., Moukalled, F., &
Noueihed, N. On entropy generation in
thermoelectric devices. Energy conversion
and management. 2000. 41(9): 891-914.
11. Hu, R., Cola, B. A., Haram, N., Barisci,
J. N., Lee, S., Stoughton, S., ... Gestos, A.
ME d. Cruz, JP Ferraris, AA Zakhidov and
RH Baughman. Nano Lett. 2010. 10: 838-
846.
12. Tannhauser D.S. Conductivity in iron ox-
ides. Journal of Physics and Chemistry of
Solids. 1962. 23(1-2): 25-34.
13. Xu X., Li H., Zhang Q., Hu H., Zhao Z.,
Li J., Li J., Qiao Yu, Gogotsi Yu Self-
Sensing, Ultralight, and Conductive 3D
Graphene/Iron Oxide Aerogel Elastomer
Deformable in a Magnetic Field. ACS Nano.
2015. 9(4): 3969-3977.
14. Trofimenko, N.E., Ullmann, H. Oxygen
stoichiometry and mixed ionic-electronic
conductivity of Sr1−aCeaFe1−bCobO3−x
perovskite-type oxides. Journal of the Eu-
ropean Ceramic Society. 2000. 20(9): 1241-
1250.
https://www.sciencedirect.com/science/article/abs/pii/0022369762900537#!
https://www.sciencedirect.com/science/journal/00223697
https://www.sciencedirect.com/science/journal/00223697
https://www.sciencedirect.com/science/article/abs/pii/S0955221999002927?via%3Dihub#!
https://www.sciencedirect.com/science/article/abs/pii/S0955221999002927?via%3Dihub#!
https://www.sciencedirect.com/science/journal/09552219
https://www.sciencedirect.com/science/journal/09552219
Thermo-galvanic effects in a non-isothermal element…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 4 117
15. Kravchenko, A. V., Pershina, K. D.
Thermochemical and microstructural prop-
erties of the powdered iron– graphite–
alumosilicate mixture. Ukrainian Chemistry
Journal. 2017. 83(6): 117-124.
16. Sokirko, A. V. Theoretical study of
thermogalvanic cells in steady state.
Electrochimica acta. 1994. 39(4): 597-609.
17. De Bokx, P. K., Kock, A. J. H. M.,
Boellaard, E., Klop, W., Geus, J. W. The
formation of filamentous carbon on iron and
nickel catalysts: I. Thermodynamics. Jour-
nal of catalysis. 1985. 96(2): 454-467.
18. Erickson, K. J., Léonard, F., Stavila, V.,
Foster,M. E, Spataru, C. D., Jones, R. E.,
Foley, B. M., Hopkins, P. E., Allendorf, M.
D, Talin, A. A. Thin Film Thermoelectric
Metal–Organic Framework with High See-
beck Coefficient and Low Thermal Conduc-
tivity. Adv. Mater. (2015). 27: 3453–3459.
19. Mateeva, N., Niculescu, H., Schlenoff, J. B.,
Testardi, L. Correlation of Seebeck Coeffi-
cient and Electric Conductivity in
Polyaniline and Polypyrrole. Journal of Ap-
plied Physics. 1998. 83: 3111 – 3119.
20. Kravchenko, A. V., & Pershina, K. D.
Thermochemical and electrochemical de-
scription of the Fe-C catalytic sys-
tem. Promising materials and processesin
applied electrochemistry. 2017. 224-230.
21. Kravchenko, O. V., Pershina, K. D.,
Panteleymonov, R. A., & Potapenko, O. V.
Electrochemical Properties of Powder
Iron/Carbon System in Basic Solu-
tion. Materials Today: Proceedings.
2019. 6: 65-72.
22. Riabokin, O. L., Boichuk, A. V., &
Pershina, K. D. Control of the State of Pri-
mary Alkaline Zn–MnO2 Cells Using the
Electrochemical Impedance Spectroscopy
Method. Surface Engineering and Applied
Electrochemistry. 2018. 54(6): 614-622.
23. Riabokin, O., Boichuk, O., Pershina, K.
Assessment of mechanical damages in the
primary Zn-MnO2 batteries by electrochem-
ical impedance spectroscopy. Ukrainian
Chemistry Journal. 2019. 85(8): 59-65.
24. Mulenko, S. A., Gorbachuk, N. T., &
Stefan, N. Laser synthesis of nanometric
iron oxide films with high Seebeck coeffi-
cient and high thermoelectric figure of mer-
it. Lasers in Manufacturing and Materials
Processing. 2014. 1(1-4): 21-35.
25. Regner, K. T., Majumdar, S., & Malen,
J. A. Instrumentation of broadband frequen-
cy domain thermoreflectance for measuring
thermal conductivity accumulation func-
tions. Review of Scientific Instruments.
2013. 84(6): 064901.
26. Regner, K. T., Sellan, D. P., Su, Z.,
Amon, C. H., McGaughey, A. J., & Malen,
J. A. Broadband phonon mean free path
contributions to thermal conductivity meas-
ured using frequency domain thermo-
reflectance. Nature communications. 2013.
4(1): 1-7.
27. Koh, Y. K., Cahill, D. G. Frequency de-
pendence of the thermal conductivity of
semiconductor alloys. Physical Review B.
2007. 76(7): 075207.
Надійшла 08.05.2020
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-147 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:02:05Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/32/1bd3ab501a81e23230597f00059abb32.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1472026-07-22T08:23:42Z THERMO-GALVANIC EFFECTS IN A NON-ISOTHERMAL ELEMENT BASED ON THE OF IRON-CARBON COMPOSITIONAL ELECTRODE AND ALKALINE ELECTROLYTE ТЕРМОГАЛЬВАНИЧЕСКИЕ ЭФФЕКТЫ В НЕИЗОТЕРМИЧЕСКОМ ЭЛЕМЕНТЕ НА ОСНОВЕ ЖЕЛЕЗО-КАРБОНОВОГО КОМ-ПОЗИЦИОННОГО ЭЛЕКТРОДА И ЩЕЛОЧНОГО ЭЛЕКТРОЛИТА ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ Boichuk, Oleksandr Pershina, Katherine Riabokin, Oleh Kravchenko, Alexandr Panteleimonov, Radyslav iron-carbon composite electrode, thermal galvanic element, Seebeck coefficient, impedance spectroscopy, electrical equivalent circuit, capacitance dispersion. In article was established the conditions for measuring thermal diffusion and thermoelectric effects in non-isothermal elements with composite electrodes of powdered iron and carbon in the alkaline electrolytes using electrochemical impedance spectroscopy. By the modeling of the impedance spectra of these systems has been established the most advantageous equivalent model scheme, which confirms that the external resistance has several components: the resistance of the electrolyte, the resistance of the capacity of the double electric layer and the resistance of thermal diffusion, which forms the dispersion of the capacity. By the calculations of the capacity and the dispersion of the capacity in the low- and high-frequency measurement range have been shown the effect of the concentration of composition components on the formation of the additional heat capacity, which creates the preconditions for realizing of the thermal electrical effects. Increasing of a concentration of the iron leads to the increase of the number of oxide (semiconductor) structures that increase the additional heat capacity. Such heat capacity induces electrical capacity and its dispersion. That is, it creates the preconditions for the occurrence of thermoelectric effects, especially Sore effects in the non-isothermal element. This work was realized due the projects of the Purpose Program for Basic Research of the Chemistry Department of NAS of Ukraine "Basic Research in Priority Areas of Chemistry" P - 1 - 17 DR 0117U000856 and "Strategy of creation of new heat-energy systems based on iron and its compounds, sulfur and oxygen" No. 0117U0008. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-04-07 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/147 10.33609/2708-129X.86.4.2020.108-117 Ukrainian Chemistry Journal; Vol. 86 No. 4 (2020): Ukrainian Chemistry Journal; 108-117 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 4 (2020): Украинский химический журнал; 108-117 Український хімічний журнал; Том 86 № 4 (2020): Український хімічний журнал; 108-117 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/147/92 Copyright (c) 2020 Oleksandr Boichuk, Katherine Pershina, Oleh Riabokin, Alexandr Kravchenko, Radyslav Panteleimonov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Boichuk, Oleksandr Pershina, Katherine Riabokin, Oleh Kravchenko, Alexandr Panteleimonov, Radyslav ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title | ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title_alt | THERMO-GALVANIC EFFECTS IN A NON-ISOTHERMAL ELEMENT BASED ON THE OF IRON-CARBON COMPOSITIONAL ELECTRODE AND ALKALINE ELECTROLYTE ТЕРМОГАЛЬВАНИЧЕСКИЕ ЭФФЕКТЫ В НЕИЗОТЕРМИЧЕСКОМ ЭЛЕМЕНТЕ НА ОСНОВЕ ЖЕЛЕЗО-КАРБОНОВОГО КОМ-ПОЗИЦИОННОГО ЭЛЕКТРОДА И ЩЕЛОЧНОГО ЭЛЕКТРОЛИТА |
| title_full | ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title_fullStr | ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title_full_unstemmed | ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title_short | ТЕРМОГАЛЬВАНИЧНІ ЕФЕКТИ У НЕІЗОТЕРМІЧНОМУ ЕЛЕМЕНТІ НА ОСНОВІ ЗАЛІЗО-КАРБОНОВОГО КОМПОЗИЦІЙНОГО ЕЛЕКТРОДУ ТА ЛУЖНОГО ЕЛЕКТРОЛІТУ |
| title_sort | термогальваничні ефекти у неізотермічному елементі на основі залізо-карбонового композиційного електроду та лужного електроліту |
| topic_facet | iron-carbon composite electrode thermal galvanic element Seebeck coefficient impedance spectroscopy electrical equivalent circuit capacitance dispersion. |
| url | https://ucj.org.ua/index.php/journal/article/view/147 |
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