ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ
By current study determined dependence between changing of the average capacitance of the destroyed electrodes of chemical current sources, surface geometry and chemical composition of electrodes surface. In case of the minimum destruction of the surface of the electrode, the maximum value of the av...
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| author | Riabokin, Oleg Boichuk, Oleksandr Pershina, Katherine |
| author_facet | Riabokin, Oleg Boichuk, Oleksandr Pershina, Katherine |
| author_institution_txt_mv | [
{
"author": "Oleg Riabokin",
"institution": null
},
{
"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_sort | Riabokin, Oleg |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:41Z |
| description | By current study determined dependence between changing of the average capacitance of the destroyed electrodes of chemical current sources, surface geometry and chemical composition of electrodes surface. In case of the minimum destruction of the surface of the electrode, the maximum value of the average capacity is achieved with the ratio Zn: Mn = 2: 1. The minimum capacity was been at a maximum concentration of manganese on the surface (Zn: Mn = 1: 3) and the maximum degree of destruction. That is, the destruction of the surface of the electrodes leads to a change in the ratio of Zinc and Manganese and with strong surface destruction, the number of Manganese increases significantly. The using of the second frequency-dependent parameter (capacitance dispersion) as a lumped parameter was allowed the application of the principles of electric current commutation for register the layered change in the electric characteristics of the destroyed electrodes. Due to that mathematical technique was obtained a visual picture of the quantitative and qualitative changes on the destroyed surfaces. The general view of the received diagrams repeated the contours of the SEM microphoto images of the same surfaces. There is a presence of sites with the local concentrated deviations from the total distribution of the capacitance in the specific frequency range in case of deep damage in the diagrams. Thus, these diagrams (EIS images) give a clear picture of the electrodes surface of and can be used to evaluate the type of surface damage and the degree of destruction of the electrodes of chemical current sources. |
| doi_str_mv | 10.33609/0041-6045.85.8.2019.59-65 |
| first_indexed | 2025-09-24T17:43:31Z |
| format | Article |
| fulltext |
ФІЗИЧНА ХІМІЯ
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8 59
UDC 542.87 doi: 10.33609/0041-6045.85.8.2019.59-65
O.L.Riabokin
1
, O.V.Boichuk
2
, K.D.Pershina
1,2
*
ASSESSMENT OF MECHANICAL DAMAGES IN THE PRIMARY Zn–MnO2
BATTERIES BY ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY
1
Inter-Agency Department of Electrochemical Energy Systems
of National Academy of Sciences of Ukraine.
2 V.I.Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences
of Ukraine, 32/34 Academic Palladin Avenue, Kiev, 03142, Ukraine
*e-mail: Pershina@ionc.kiev.ua
The mechanically destroyed elementary primary Zn–MnO2 batteries were studied using elect-
rochemical impedance spectroscopy, scanning electron microscopy and elemental analysis
of the surface. It has been experimentally proved that the change of the average capacity of
the destroyed elements in time is a function of not only the geometry of the surface, but also
its component composition. During study the correlation of the photomicrographic images
of the electrodes surface with three-dimensional contour diagrams in coordinates: changing
of capacitance means value, dispersion of capacitance and frequency was found.
K e y w o r d s: primary batteries, electrodes, mechanical destruction, impedance spectro-
scopy, capacitance dispersion.
INTRODUCTION. Today the modern me-
thods of electrochemical impedance spectrosco-
py (EIS) are widely used for measuring and in-
vestigation interphase and bulk electrochemical
properties of materials and devices based on
them [1]. The most well-known method is the
construction of equivalent electrochemical cir-
cuits with the corresponding set of elements that
simulate the behavior of components of the elec-
trochemical system (electrodes, interphase inter-
actions of the electrode and electrolyte, ion dif-
fusion, etc.). But disputes over the interpretation
of the elements of these chains, especially of the
constant phase element (CPE), are continued [2–
6]. It is well known, that a perfectly polarized
electrode is an electrode without any RedOx re-
actions on the surface. According to impedance
theory such electrodes are modeled by the ele-
ment of capacitance [3–6]. The formation of the
perfectly polarized electrode is possible only
on the geometrically and atomically homogene-
ous surfaces such as liquid mercury or single
crystals (monocrystal) electrodes. The surface of
polycrystalline solids is never completely homo-
geneous on an atomic level — as a result, ener-
gy heterogeneities along the surface are formed.
Such lack of homogeneity is reason of the for-
mation of kinks, dislocations, and on a much lar-
ger scale corrugation, scratches, pits, grooves, etc.
This makes the surface "disordered" from a geo-
metric point of view, so it has two types of geo-
metric irregularities: on the atomic level and le-
vel, that is much bigger than 10 nm [7]. Superfi-
cial disorders and roughness are interrelated be-
cause the mechanically rough surface has a large
number of dislocations. Therefore, on polycrys-
talline solid electrodes (even on smooth ones) the
impedance is not purely capacitive. This is con-
nected with such effect as the double electric
layer frequency dependent capacitance formation
© O.L.Riabokin, O.V.Boichuk, K.D.Pershina, 2019
mailto:Pershina@ionc.kiev.ua
O.L.Riabokin, O.V.Boichuk, K.D.Pershina
60 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8
named as "frequency capacitance dispersion", or
simply — a "capacitance dispersion", which de-
pends on the geometry of the surface and its
roughness. Thus, the total impedance of the elec-
trode is the sum of the real and complex functi-
ons of the resistive and capacitive elements for-
med in the volume of the solution and on the elec-
trode/electrolyte interphase, respectively, the inter-
facial capacity become a frequency dependent.
Assuming a certain geometry of the electrodes (po-
rous [3–5] or fractal [6]), the CPE element is
often use to calculate this capacity. However, ac-
cording to [7] these calculations were to give in-
flated results which саn not be used for inter-
preting the actually existing relationship bet-
ween roughness and the capacitance dispersion.
The second physicochemical explanation for the
occurrence of the capacitance dispersion is the
formation of a double electric layer (DEL) at the
electrode/electrolyte boundary with the atomic in-
homogeneities due the specific adsorption of ions.
The presence of such adsorption causes the dis-
tribution of the activation energy during kinetic
processes on the electrode surface [8–10]. The
relatively narrow distribution of the activation ener-
gy causes a wide distribution of reaction speed
constants (or time constants), because they con-
nected by the exponential relationship. This rela-
tionship gives a more pronounced frequency de-
pendence of capacitance [11]. This dependence
with combination of Kirgoff’s laws makes pos-
sible to use the principles of commutation [12–
14] for calculation of the impedance spectra of
batteries electrodes after changing surface geome-
try (mechanical destruction). So the purpose of the
current study is to obtain regularities between
the changing of the capacitance in time, the fre-
quency capacitance dispersion and the degree of
mechanical destruction of the electrodes of the
primary current sources.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. We chose the new commercial
alkaline zinc–manganese batteries 6LR61, with a
voltage of 9.0 V as the samples under investiga-
tion. Such elements consist of the six primary cur-
rent sources, which are connected in series by a
sequential circuit. Each primary current source
has the form of the square tablet and consists of
a cathode — the mixtures of MnO2 (pyrolusite)
with graphite (95 %) impregnated with an alka-
line electrolyte (mixtures of KOH and NH4Cl)
and an anode — the powder metal zinc (fig. 1).
Fig. 1. Scheme of the elementary element.
According to the design of the elemen-
tary battery, the cathode with a current collector
(graphite) is inside of the tablet, and the anode is
on its surface. Therefore, the level of mechanical
destruction should change not only the electro-
chemical characteristics of a single source, but
also the chemical composition of the surface.
Thus, the nine-volt batteries are a good system
for investigating the effect of mechanical dam-
age on the electrochemical and chemical proper-
ties of these energy sources. Mechanical impact
on elements with varying degrees of depth and
area was made by force using a scalpel. Electro-
chemical impedance spectra were measured in
two electrode cells on an electrochemical modu-
le Autolab-30 PGSTAT302N Metrohm Autolab,
with FRA (Frequency Response Analyzer) in-
stalled in the range of 10
--3
–10
6
Hz. Wrecking
Assessment of mechanical damages in the primary Zn–MnO2 batteries …
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8 61
electrodes were further impregnated with 1M aqu-
eous solution KCl to ensure good contact during
measurements. Control of the FRA module was
carried out using the program Autolab 4.9 at an
amplitude perturbation signal of 5 mV with
further processing of the obtained results in the
package Zview 2.0. Calculations of the capacity
dispersion were performed using impedance spec-
tra in Bode coordinates based on the Zview 2.0
software package, using the formulas:
( ) ([( ) ( )] ), (1)
where C() – dispersion of capacitance; Z() –
impedance data on preset frequency; Z() –
impedance data on high frequency.
С =
, (2)
C – capacitance data on fixed frequency; Z’– data
of real part of impedance; f – frequency.
Photomicrographic images and chemical
composition of the surface were obtained by a
scanning electron microscope (TESCAN VEGA
3) with Bruker Company software, which is
used for determination the local chemical com-
position and building a ―map‖ of distribution of
chemical elements on the electrodes surface.
The degree of the surface destruction of the ele-
ment was calculated by the ratio of the visual
area of the destroyed surface (Sd) to the total sur-
face area (ST):
αd =
x 100 %. (3)
During comparison of the impedance spec-
tra of elements with different degrees of destruc-
tion with their chemical composition and surface
photomicrographs were determined that the radii
of the semicircles of the spectra correlate with
the degree of surface destruction (fig. 2, 3). It was
found that the values of the capacitances calcu-
lated according to equation 2 are a function of
the radius of the semicircle of the impedance
spectra (table 1).
Fig. 2. SЕМ images of the elements surface.
Fig. 3. ЕІS of the elements in the Nyquist plots,
numeration of samples according fig. 2.
Increasing of the capacitance and the de-
gree of the element destruction has an antibate
character.
The capacitance of samples is increased in
following way: № 2 > № 1 > № 4 > № 3, and the
degree of destruction is decreased in similar way:
№ 3 > №. 4 > № 1 > № 2. Thus, a decreasing of
the value of t he capacitance is correlated with
an increasing of the degree of destruction of the
O.L.Riabokin, O.V.Boichuk, K.D.Pershina
62 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8
T a b l e 1
The degree destruction and the calcula-
ted capacitance of the elementary elements
Sample d, % С, F
1 5 1.34·10
–5
2 7 1.28·10
–5
3 25 7.46·10
–6
4 85 9.94·10
–6
electrode surface. The subsequent studies of the
chemical composition of the surface found that
the mechanical destruction of the electrodes le-
ads to a change in the Zn : Mn ratio, which had
changed the value of the capacitance (table 2).
The maximum value of the capacitance is rea-
ched at the ratio Zn: Mn = 2:1 and accorded
with the minimum destruction of the electrode
surface. The minimum capacity is observed in
sample № 3, which has the maximum concent-
ration of Manganese on the surface (Zn: Mn =
1:3) and the maximum degree of destruction
(fig. 2). That is, the destruction of the electrode
surface leads to a change in the ratio of Zinc and
Manganese. With strong volume destruction of
the sample, the number of Manganese increases
significantly. But the anode surface destruction
T a b l e 2
Chemical composition of the samples surface,
mas. %
Sample [Zn] [ Mn] [C] Zn:Mn
1 45.29
±0.01
21.32
±0.03
33.39
±0.01
2:1
2 26.66
±0.01
42.96
±0.03
30.37
±0.01
1:2
3
17.46
±0.01
46.92
±0.03
35.62
±0.01
1:3
4
60.76
±0.01
16.40
±0.03
22.84
±0.03
4:1
Fig. 4. SЕМ images and components ―map‖ of
the samples: minimum (a) and maximum (b) of
the surface and volume destruction.
has influence, which comparable with volume de-
struction (sample № 4) (table 1, 2, fig. 4). So, the
capacitance is a function not only of the geome-
try of the surface, but also of its components com-
position. This gives grounds for its further use as
a test parameter for the assessment of the state
of art and the degree of destruction of the batte-
ries. It is possible to use a capacitance’s disper-
sion as a second test parameter to account for a
certain electrode surface geometry for increasing
the self-descriptiveness of the analysis [3–5]. Mo-
reover, the using of only this testing function le-
ads to high errors gaining, which allows it to use
only for qualitative evaluation of the electrode
surface [7]. Based on the exponential relation-
ship between the impedance value and frequen-
cy — dependent capacitance:
Zw =
( )
, (4)
Y0 – frequency-dependent factor; n – level of
frequency dependence. With n, the frequ-
ency dependence is increased. So, such depend-
ence gives reason to use imaginary part of im-
pedance as a concentrated parameter. It is me-
ans, that it is possible to consider the changes in
Assessment of mechanical damages in the primary Zn–MnO2 batteries …
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8 63
the AC wavelength from the moment of its oc-
currence to a certain point in time as function
of the impedance of the system in the assign
frequency range. Then, based on Kirchhoff's
circuit laws, the dependence between changing
of the capacitance, current and voltage will be
looking as:
=
( ) =
(
)
(5)
To solve this equation at different time in-
tervals we suggesting to use Duhamel`s integrals:
for the interval :
( ) ∫
( ) ( )
(6)
for the interval :
( ) ∫ ( ) ( )
(
( )) ∫ ( ) ( )
(7)
for the interval :
( ) ∫ ( ) ( )
(
( )) ∫ ( ) ( )
( ( ))
. (8)
So, if impedance spectra of samples sepa-
rate into three frequency zones, which satisfied
for such mathematical conditions, it has been ob-
tained an integral picture of the sample. Moreo-
ver it can be possible to register the surface
changes of the destroyed electrodes using this
method. For obtaining EIS images the capaci-
tance value and capacitance dispersions calcu-
lated in the three frequency ranges: 10
–3
–10
1
Hz,
10
2
–10
4
Hz and 10
4
–10
6
Hz, after that, the ob-
tained value was used for building contour dia-
grams in coordinates: capacitance means value,
dispersion of capacitance and frequency. So, the
obtained picture gives the ability to trace the la-
yer-by-layer change of the electrical parameters
of the research objects and to establish the inter-
nal structure of the electrode/electrolyte bounda-
ry. That is, according to existing ideas [15], such
dependence falls under the signs of a tomogram.
Also, the comparison of the obtained diagrams
with photomicrographs showed the correlation
between them. The general appearance of the ob-
tained diagrams repeated the contours of surface
damage (fig. 5). It is fixed a presence of sections
with local concentrated deviations from the total
distribution of capacity in the specific frequency
range in the case of deep damage of the samples
on the obtained diagrams.
Moreover, the ratio of the capacitance
values (C0) and the dispersion of the capacitan-
Fig. 5. Photomicrographs of samples surfaces (SEM
images) and integral diagrams of capacitance chang-
es on their surface (EIS images).
O.L.Riabokin, O.V.Boichuk, K.D.Pershina
64 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8
ce (Cd) are correlated with the component com-
position of the surface of the destroyed samples
(table 2, fig. 4, 5). Thus, these diagrams can be
used to estimate the type of damage to the elec-
trodes of chemical current sources.
CONCLUSIONS. The results of the cur-
rent study show that the changes in the capaci-
tance and dispersion of capacitance of destroyed
primary Zn–MnO2 batteries in wide frequency
range is a function not only of the geometry of
the surface, but also of its chemical composition
of the surface. The using of the second frequen-
cy-dependent value (dispersion of the capacitan-
ce) as a concentrated parameter allowed the ap-
plication of the principles of the electric current
commutation to register the layer-by-layer chan-
ges of the destroyed electrodes and obtained a
visual picture of the quantitative and qualitative
changes of the destroyed samples. The images gai-
ned through calculation of the impedance spec-
tra have a strong correlation with SEM images.
ACKNOWLEDGEMENTS. The authors
would like to thank National Academy of Scien-
ces of Ukraine for grant and technical assistance.
ВИЯВЛЕННЯ МЕХАНІЧНИХ ПОШКОД-
ЖЕНЬ ПЕРВИННИХ Zn–MnO2 ХІМІЧНИХ
ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕ-
КТРОХІМІЧНОГО ІМПЕДАНСУ
О.Л. Рябокінь
1
, О.В. Бойчук
2
, К.Д. Першина
1,2
*
1
Міжвідомче відділення електрохімічної енер-
гетики НАН України, бульвар Академіка Вер-
надського, 38-А, Київ, 03142, Україна
2
Інститут загальної та неорганічної хімії
ім. В.І.Вернадського НАН України, просп.
Академіка Палладіна, 32/34, Київ, 03142,
Україна.
*e-mail: Pershina@ionc.kiev.ua
Результати проведених досліджень показа-
ли, що зміна середньої ємності зруйнованих еле-
ктродів хімічних джерел струму в часі є функці-
єю не тільки геометрії поверхні, а й її компонен-
тного складу. Максимальне значення середньої
ємності досягається при співвідношенні Zn:Mn =
2:1 та мінімальній зруйнованості поверхні елект-
рода. Мінімальна ємність має максимальну кон-
центрацію марганцю на поверхні (Zn:Mn = 1:3)
та максимальний ступінь зруйнованості. Тобто
руйнування поверхні електродів приводить до
зміни співвідношення цинку та марганцю. При
сильному руйнуванні поверхні кількість марган-
цю значно зростає. Використання другої частот-
но-залежної величини (дисперсії ємності) в яко-
сті зосередженого параметру дозволило застосу-
вання принципів комутації електричного стру-
му для реєстрації пошарової зміни ємносних ха-
рактеристик зруйнованих електродів та отри-
мання наочної картини кількісних та якісних
змін, що відбуваються в результаті руйнування.
Загальний вигляд отриманих діаграм відтворював
контури пошкоджень поверхні. У разі глибоких
пошкоджень на діаграмах спостерігається наяв-
ність ділянок з концентрованими відхиленнями
від загального розподілу в часі показників єм-
ності. Отже, отримана картина дає можливість
відстежувати пошарові зміни електричних пара-
метрів об'єктів дослідження та встановлювати
внутрішню структуру межі електрода/електро-
літу. Тобто, згідно з існуючими ідеями, і така за-
лежність підпадає під ознаки томограми. Та-
кож порівняння оброблених діаграм з мікрофото-
графіями показало кореляцію між ними. Загаль-
на характеристика отриманих діаграм повтори-
ла контури поверхневого пошкодження. На оде-
ржаних діаграмах також фіксується наявність
секцій з локальними концентрованими відхи-
леннями від загального розподілу ємності у кон-
кретному діапазоні частот у разі глибокого по-
шкодження зразків.
К л ю ч о в і с л о в а: первинні хімічні джерела
струму, електроди, механічне руйнування, спект-
роскопія імпедансу, дисперсія ємності.
ОБНАРУЖЕНИЕ МЕХАНИЧЕСКИХ ПОВРЕ-
ЖДЕНИЙ ПЕРВИЧНЫХ Zn–MnO2 ХИМИЧЕ-
СКИХ ИСТОЧНИКОВ ТОКА CПЕКТРОСКО-
ПИЕЙ ЭЛЕКТРОХИМИЧЕСКОГО ИМПЕДАНСА
О.Л.Рябоконь
1
, А.В.Бойчук
2
, Е.Д.Першина
2
mailto:Pershina@ionc.kiev.ua
Assessment of mechanical damages in the primary Zn–MnO2 batteries …
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 8 65
1
Межведомственное отделение электрохими-
ческой энергетики НАН Украины, бульвар Ака-
демика Вернадского, 38-А, Киев, 03142, Украина
2
Институт общей и неорганической химии
им. В.И.Вернадского НАН Украины, просп. Ака-
демика Палладина, 32/34, Киев, 03142, Украина
*e-mail: Pershina@ionc.kiev.ua
Проведено исследование механически по-
врежденных электродов первичных химических
источников тока с использованием спектроско-
пии электрохимического импеданса, сканирую-
щей электронной микроскопии и элементного
анализа поверхности. Экспериментально доказа-
но, что изменение средней емкости разрушенных
электродов во времени является функцией не
только геометрии поверхности, но и ее компо-
нентного состава. Найдена корреляция между
микрофотографиями поверхности и тройными
контурными диаграммами скорости изменения
емкости, дисперсии емкости и частоты.
К л ю ч е в ы е с л о в а: первичный химиче-
ский источник тока, электроды, механическое
повреждение, спектроскопия импеданса, дис-
персия емкости.
REFERENCES
1. Borisova T. I., Ershler B.V. Determination of the
zero voltage points of solid metals from meas-
urements of the capacity of the double layer. Zh.
Fiz. Khim. 1950. 24: 337.
2. Sapoval B., Sapoval R., Gutfraind P., Meakin M.,
Keddam H. Takenouti Equivalent-circuit, scaling,
random-walk simulation, and an experimental
study of self-similar fractal electrodes and inter-
faces. Physical Review E. 1993. 48 (5): 3333.
3. Pershina E.D., Kokhanenko V.V., Maslyuk L.N.,
Kazdobin K.A. Conductivity of aqueous suspen-
sions of alumosilicates. Surface Engineering and
Applied Electrochemistry. 2011. 47 (5): 441.
4. De Levie R. On porous electrodes in electrolyte
solutions: I. Capacitance effects. Electrochimica
Acta. 1963. 8 (10) : 751.
5. Riabokin O.L., Boichuk A.V., Pershina K.D.
Control of the State of Primary Alkaline Zn––
MnO2 Cells Using the Electrochemical Impe-
dance Spectroscopy Method. Surface Engineering
and Applied Electrochemistry. 018. 54 (6): 614.
6. Pajkossy T. Heterogeneous. Chem. Rev. 1995. 2: 143.
7. Pajkossy T. Impedance of rough capacitive elec-
trodes. Journal of Electroanalytical Chemistry.
1994. 364 (1–2): 111.
8. Pajkossy T. Wandlowski T., Kolb D.M. Imped-
ance aspects of anion adsorption on gold single
crystal electrodes. Journal of Electroanalytical
Chemistry. 1996. 414 (2): 209.
9. Pajkossy T. Capacitance dispersion on solid elec-
trodes: anion adsorption studies on gold single
crystal electrodes. Solid state ionics. 1997. 94
(1–4): 123.
10. Kerner Z., Pajkossy T. Impedance of rough ca-
pacitive electrodes: the role of surface disorder.
Journal of Electroanalytical Chemistry. 1998.
448 (1): 139.
11. Diamant V.A., Malovanyy S.M., Pershina K.D.,
Kazdobin K.A. Electrochemical properties of So-
dium bis [salicylato (2-)]-borate-γ-butyrolactone
Electrolytes in Sodium Battery. Materials Today:
Proceedings. 2019. 6: 86.
12. Jamnik J., Maier J. Generalised equivalent cir-
cuits for mass and charge transport: chemical
capacitance and its implications. Phys. Chem.
Chem. Phys. 2001. 3: 1668.
13. Emadi A., Khaligh A., Rivetta C.H, Williamson
G.A. Constant Power Loads and Negative Impe-
dance Instability in Automotive Systems: Defi-
nition, Modeling, Stability, and Control of Power
Electronic Converters and Motor Dri-ves. IEEE
Transactions on vehicular technology. 2006. 55
( 4): 1112.
14. Chassaing E., Sapoval B. Electrochemical Impe-
dance of Blocking Quasi‐Fractal 3‐d Electrodes.
Journal of the Electrochemical Society. 1994.
141 (10): 2711.
15. Chung E.T., Chan T.F., Tai X.-C. Electrical im-
pedance tomography using level set represen-
tation and total variational regularization. Jour-
nal of Computational Physics.2005. 205 (1): 357.
Received 14.05.2019
mailto:Pershina@ionc.kiev.ua
https://link.springer.com/article/10.3103/S1068375511050176
https://link.springer.com/article/10.3103/S1068375511050176
https://link.springer.com/article/10.3103/S1068375518060108
https://www.sciencedirect.com/science/article/pii/S2214785318323733
https://www.sciencedirect.com/science/article/pii/S2214785318323733
https://www.sciencedirect.com/science/article/pii/S2214785318323733
https://pubs.rsc.org/en/results?searchtext=Author%3AJ.%20Jamnik
https://pubs.rsc.org/en/results?searchtext=Author%3AJ.%20Maier
https://www.sciencedirect.com/science/article/pii/S0021999104004711?via%3Dihub#%21
https://www.sciencedirect.com/science/article/pii/S0021999104004711?via%3Dihub#%21
https://www.sciencedirect.com/science/journal/00219991
https://www.sciencedirect.com/science/journal/00219991
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-69 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:04:05Z |
| publishDate | 2019 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/eb/8f5a96e4ca9ef7e73b52d8e2f43a30eb.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-692026-07-22T08:23:41Z ASSESSMENT OF MECHANICAL DAMAGES IN THE PRIMARY Zn-MnO2 BATTERIES BY ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY ОЦЕНКА МЕХАНИЧЕСКИХ ПОВРЕЖДЕНИЙ ПЕРВИЧНЫХ Zn-MnO2 ХИМИЧЕСКИХ ИСТОЧНИКОВ ТОКА CПЕКТРОСКОПИЕЙ ЭЛЕКТРОХИМИЧЕСКОГО ИМПЕДАНСА ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ Riabokin, Oleg Boichuk, Oleksandr Pershina, Katherine primary batteries, electrodes, mechanical destruction, impedance spectroscopy, capacitance dispersion. первичный химический источник тока, электроды, механическое повреждение, спектроскопия импеданса, дисперсия емкости. первинні хімічні джерела струму, електроди, механічне руйнування, спектроскопія імпедансу, дисперсія ємності. By current study determined dependence between changing of the average capacitance of the destroyed electrodes of chemical current sources, surface geometry and chemical composition of electrodes surface. In case of the minimum destruction of the surface of the electrode, the maximum value of the average capacity is achieved with the ratio Zn: Mn = 2: 1. The minimum capacity was been at a maximum concentration of manganese on the surface (Zn: Mn = 1: 3) and the maximum degree of destruction. That is, the destruction of the surface of the electrodes leads to a change in the ratio of Zinc and Manganese and with strong surface destruction, the number of Manganese increases significantly. The using of the second frequency-dependent parameter (capacitance dispersion) as a lumped parameter was allowed the application of the principles of electric current commutation for register the layered change in the electric characteristics of the destroyed electrodes. Due to that mathematical technique was obtained a visual picture of the quantitative and qualitative changes on the destroyed surfaces. The general view of the received diagrams repeated the contours of the SEM microphoto images of the same surfaces. There is a presence of sites with the local concentrated deviations from the total distribution of the capacitance in the specific frequency range in case of deep damage in the diagrams. Thus, these diagrams (EIS images) give a clear picture of the electrodes surface of and can be used to evaluate the type of surface damage and the degree of destruction of the electrodes of chemical current sources. By current study determined dependence between changing of the average capacitance of the destroyed electrodes of chemical current sources, surface geometry and chemical composition of electrodes surface. In case of the minimum destruction of the surface of the electrode, the maximum value of the average capacity is achieved with the ratio Zn: Mn = 2: 1. The minimum capacity was been at a maximum concentration of manganese on the surface (Zn: Mn = 1: 3) and the maximum degree of destruction. That is, the destruction of the surface of the electrodes leads to a change in the ratio of Zinc and Manganese and with strong surface destruction, the number of Manganese increases significantly. The using of the second frequency-dependent parameter (capacitance dispersion) as a lumped parameter was allowed the application of the principles of electric current commutation for register the layered change in the electric characteristics of the destroyed electrodes. Due to that mathematical technique was obtained a visual picture of the quantitative and qualitative changes on the destroyed surfaces. The general view of the received diagrams repeated the contours of the SEM microphoto images of the same surfaces. There is a presence of sites with the local concentrated deviations from the total distribution of the capacitance in the specific frequency range in case of deep damage in the diagrams. Thus, these diagrams (EIS images) give a clear picture of the electrodes surface of and can be used to evaluate the type of surface damage and the degree of destruction of the electrodes of chemical current sources. By current study determined dependence between changing of the average capacitance of the destroyed electrodes of chemical current sources, surface geometry and chemical composition of electrodes surface. In case of the minimum destruction of the surface of the electrode, the maximum value of the average capacity is achieved with the ratio Zn: Mn = 2: 1. The minimum capacity was been at a maximum concentration of manganese on the surface (Zn: Mn = 1: 3) and the maximum degree of destruction. That is, the destruction of the surface of the electrodes leads to a change in the ratio of Zinc and Manganese and with strong surface destruction, the number of Manganese increases significantly. The using of the second frequency-dependent parameter (capacitance dispersion) as a lumped parameter was allowed the application of the principles of electric current commutation for register the layered change in the electric characteristics of the destroyed electrodes. Due to that mathematical technique was obtained a visual picture of the quantitative and qualitative changes on the destroyed surfaces. The general view of the received diagrams repeated the contours of the SEM microphoto images of the same surfaces. There is a presence of sites with the local concentrated deviations from the total distribution of the capacitance in the specific frequency range in case of deep damage in the diagrams. Thus, these diagrams (EIS images) give a clear picture of the electrodes surface of and can be used to evaluate the type of surface damage and the degree of destruction of the electrodes of chemical current sources. V.I.Vernadsky Institute of General and Inorganic Chemistry 2019-08-15 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/69 10.33609/0041-6045.85.8.2019.59-65 Ukrainian Chemistry Journal; Vol. 85 No. 8 (2019): Ukrainian Chemistry Journal; 59-65 Украинский химический журнал; ##issue.vol## 85 ##issue.no## 8 (2019): Украинский химический журнал; 59-65 Український хімічний журнал; Том 85 № 8 (2019): Український хімічний журнал; 59-65 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/69/44 Copyright (c) 2019 Oleg Riabokin, Oleksandr Boichuk, Katherine Pershina https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | первинні хімічні джерела струму електроди механічне руйнування спектроскопія імпедансу дисперсія ємності. Riabokin, Oleg Boichuk, Oleksandr Pershina, Katherine ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title | ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title_alt | ASSESSMENT OF MECHANICAL DAMAGES IN THE PRIMARY Zn-MnO2 BATTERIES BY ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY ОЦЕНКА МЕХАНИЧЕСКИХ ПОВРЕЖДЕНИЙ ПЕРВИЧНЫХ Zn-MnO2 ХИМИЧЕСКИХ ИСТОЧНИКОВ ТОКА CПЕКТРОСКОПИЕЙ ЭЛЕКТРОХИМИЧЕСКОГО ИМПЕДАНСА |
| title_full | ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title_fullStr | ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title_full_unstemmed | ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title_short | ОЦІНЮВАННЯ МЕХАНІЧНИХ ПОШКОДЖЕНЬ ПЕРВИННИХ Zn-MnO2 ХІМІЧНИХ ДЖЕРЕЛ СТРУМУ СПЕКТРОСКОПІЄЮ ЕЛЕКТРОХІМІЧНОГО ІМПЕДАНСУ |
| title_sort | оцінювання механічних пошкоджень первинних zn-mno2 хімічних джерел струму спектроскопією електрохімічного імпедансу |
| topic | первинні хімічні джерела струму електроди механічне руйнування спектроскопія імпедансу дисперсія ємності. |
| topic_facet | primary batteries electrodes mechanical destruction impedance spectroscopy capacitance dispersion. первичный химический источник тока электроды механическое повреждение спектроскопия импеданса дисперсия емкости. первинні хімічні джерела струму електроди механічне руйнування спектроскопія імпедансу дисперсія ємності. |
| url | https://ucj.org.ua/index.php/journal/article/view/69 |
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