ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ
Thin electrolytic fine tin sediments were obtained from pyrophosphate electrolyte under different electrolysis conditions and duration. The electrochemical characteristics of tin coatings as anode materials of lithium-ion batteries are studied using potentiodynamic and galvanostatic cycling methods....
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| author | Shmatok, Yurii Globa, Natalia Nikitenko, Vasyl Babenkov, Eugen Kublanovsky, Valeriy |
| author_facet | Shmatok, Yurii Globa, Natalia Nikitenko, Vasyl Babenkov, Eugen Kublanovsky, Valeriy |
| author_institution_txt_mv | [
{
"author": "Yurii Shmatok",
"institution": "Joint Department оf Electrochemical Energy Systems оf NAS оf Ukraine, Vernadskogo blvd, 38а, Kyiv, 03680, Ukraine"
},
{
"author": "Natalia Globa",
"institution": "Joint Department оf Electrochemical Energy Systems оf NAS оf Ukraine, Vernadskogo blvd, 38а, Kyiv, 03680, Ukraine"
},
{
"author": "Vasyl Nikitenko",
"institution": "Vernadsky Institute of General & Inorganic Chemistry of National Academy of Sciences of Ukraine, Academic Palladin Avenue, 32\/34, Kyiv, 03142"
},
{
"author": "Eugen Babenkov",
"institution": "Vernadsky Institute of General & Inorganic Chemistry of National Academy of Sciences of Ukraine, Academic Palladin Avenue, 32\/34, Kyiv, 03142"
},
{
"author": "Valeriy Kublanovsky",
"institution": "Vernadsky Institute of General & Inorganic Chemistry of National Academy of Sciences of Ukraine, Academic Palladin Avenue, 32\/34, Kyiv, 03142"
}
] |
| author_sort | Shmatok, Yurii |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:41Z |
| description | Thin electrolytic fine tin sediments were obtained from pyrophosphate electrolyte under different electrolysis conditions and duration. The electrochemical characteristics of tin coatings as anode materials of lithium-ion batteries are studied using potentiodynamic and galvanostatic cycling methods. The effect of the properties of coatings, in particular their mass, on the value of specific capacitance and its stability, including during discharge with different current densities, has been established. It is shown that the studied tin sediments have high initial specific capacity that is close to theoretically possible. The maximum stability of the specific capacity during cycling is characteristic of electrodes with minimal masses of precipitation. The impedance spectra recorded for the studied electrodes in the initial state and after the first lithiation are analyzed. |
| doi_str_mv | 10.33609/0041-6045.85.10.2019.67-77 |
| first_indexed | 2025-09-24T17:43:33Z |
| format | Article |
| fulltext |
ФІЗИЧНА ХІМІЯ
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 67
UDC 541.136 doi: 10.33609/0041-6045.85.10.2019.67–77
Yu.V. Shmatok1, N.I. Globa1, V.M. Nikitenko2, E.A. Babenkov2, V.S. Kublanovsky2
ELECTROCHEMICAL CHARACTERISTICS OF TIN FILMS
IN CYCLING IN LITHIUM-ION BATTERIES **
1 Joint Department оf Electrochemical Energy Systems оf National Academy оf Sciences of Ukraine,
38а Vernadsky boulevard, Kyiv, 03680, Ukraine
2 V.I. Vernadsky Institute of General and Inorganic Chemistry of National Academy of Sciences
of Ukraine, 32/34 Academic Palladin Avenue, Kyiv, 03142, Ukraine
e-mail: gnl-n@ukr.net
Thin electrolytic fine tin sediments were obtained from pyrophosphate electrolyte under dif-
ferent electrolysis conditions and duration. The electrochemical characteristics of tin coatings
as anode materials of lithium-ion batteries are studied using potentiodynamic and galvanosta-
tic cycling methods. The effect of the properties of coatings, in particular their mass, on the
value of specific capacitance and its stability, including during discharge with different cur-
rent densities, has been established. It is shown that the studied tin sediments have high ini-
tial specific capacity that is close to theoretically possible. The maximum stability of the spe-
cific capacity during cycling is characteristic of electrodes with minimal masses of precipita-
tion. The impedance spectra recorded for the studied electrodes in the initial state and after the
first lithiation are analyzed.
K e y w o r d s: electrodeposition, pyrophosphate electrolyte, tin films, specific capacity,
reversibility, lithium-ion battery.
INTRODUCTION. In modern lithium-ion
batteries (LIB), graphite is most widely used as
anode. It is capable of providing more than a
thousand charge/discharge cycles with a relati-
vely low capacity loss. However, carbon anodes
do not meet a number of requirements for mo-
dern LIBs, since they have a low specific capa-
city (372 mA·h·g–1), a low discharge rate, and a
relatively narrow operating temperature range
[1]. The development of new anode materials, cha-
racterized by high specific capacitances and den-
sity of discharge currents, is an urgent task. Al-
loy-forming materials are considered as an alter-
native to replacing carbon anodes, among which
the most promising are silicon, tin, and tin-con-
taining composite coatings, in particular alloys of
tin with nickel, cobalt, copper, zinc, antimony [2, 3].
The authors of [4, 5] proposed methods for
increasing the specific characteristics of carbon
materials when used in LIB by producing thin
films of Sn/C nanocomposites on the carbon
surface or by dispersing tin into an electrically
** This work was carried out in the framework of the target research program of the National Academy
of Sciences of Ukraine ‘‘New Functional Substances and Materials of Chemical Engineering”, project
No. 7–19, 2019.
© Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky, 2019
mailto:gnl-n@ukr.net�
Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky
68 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10
conductive microporous carbon membrane.
One of the simplest and most easily con-
trolled methods for producing coatings with me-
tals and alloys, which makes possible to control
their structure and functional properties, is elec-
trochemical deposition of complex electrolytes
from aqueous solutions [6, 7].
The morphology, structure, and, consequ-
ently, the properties of the resulting coatings are
affected by the electrolysis parameters and the elec-
trolyte composition, in particular, the compositi-
on of electrochemically active complexes (EAC)
directly discharged on the electrode [8, 9]. The
authors of [10–12] substantiated the criteria for
the selection of ligands for complex, including
multiligand, electrolytes and the conditions for
their compatibility in one coordination sphere du-
ring the formation of mixed-ligand complex com-
pounds. This allows one to control the braking
of the electrode process and, therefore, the struc-
ture and functional properties of the resulting
coatings [12, 13].
Earlier [14], we published the results of stu-
dies of thin tin films obtained from complex tar-
trate (KNatart), citrate (Na3citr), and citrate-tri-
lonate (Na3citr/Na2H2edta) electrolytes as LIB ano-
des. It has been shown that the nature of the
ligand determines such electrochemical characte-
ristics as the specific capacitance value and cyc-
ling efficiency. The most stable charge/dischar-
ge characteristics were obtained for tin sedi-
ments deposited from citrate electrolyte [14].
Of scientific interest is the study of eleсt-
rochemical properties (specific capacity, corrosi-
on resistance, and cycling efficiency in LIB) of
thin tin deposits obtained from pyrophosphate
electrolyte under various electrolysis conditions, as
one of the most promising anode materials for LIB.
The process of electrodeposition of tin(II)
from a pyrophosphate electrolyte, unlike tartrate,
citrate, and citrate-trilonate electrolytes, is limited
by the previous chemical reaction of dissocia-
tion of the complexes [Sn(HP2O7)(P2O7)]5– or
Sn(P2O7)2]6–, composition of which is determi-
ned by pH [10]. This allows to control the
breaking of the electrode process and, therefore,
the morphology, structure and properties of the
obtained tin films, in particular their porosity. In
addition, pyrophosphate electrolytes are eco-
nomically more advantageous than, for example,
citrate or tartrate electrolytes.
In this regard, this work is devoted to the
study of the electrochemical properties of thin
tin deposits obtained from pyrophosphate elect-
rolyte under different electrolysis conditions.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Tin precipitates were obtained
on a copper foil substrate with a surface of 2 cm2
from a pyrophosphate electrolyte of the compo-
sition, g·l–1: SnCl2
.·2H2O – 90, K4P2O7·3H2O –
425, NH4Cl – 50, at pH 7.2. Electrolysis was
carried out at current densities of 1–1.5 mA cm–2
and temperature of 25 °C for 15–45 min. Pla-
tinum was used as the anode. For the preparati-
on of electrolytes, reagents of the analytical grade
were used.
Before applying precipitation, the surface
of the copper substrate was degreased with soda
and Viennese lime, etched and activated accord-
ing to the procedure [15], washed with distilled
water and dried at a temperature of 60 °C. The
electrolysis parameters were set using a PI-50-1
potentiostat and a PR-8 programmer. The elect-
rolysis was carried out under conditions of na-
tural convection. The mass of tin precipitation
was determined on an analytical balance ”ADV-
200М” with an accuracy of ±0.01 mg.
Electrochemical studies of the obtained tin
precipitates were carried out in disk cells of size
2016. A 1M solution of lithium bis-(tri-fluoro-
methane) sulfonimide (LiTFSI) in a mixture of
fluoroethylene carbonate and dimethyl carbonate
solvents taken in a mass ratio of 1:3 was used as
an electrolyte. As an auxiliary electrode and a
reference electrode lithium metal was used. Cel-
gard 2400 polypropylene film with thickness of
Electrochemical characteristics of tin films in cycling in lithium-ion batteries
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 69
25 μm was used as a separator. Working elect-
rodes with tin precipitates ( S = 2 cm2) imme-
diately before assembling the cells were dried in
vacuum at a temperature of 100 °C. All operati-
ons related to the preparation of electrodes, elec-
trolytes and cell assembly were carried out in
dry glove boxes.
Current-voltage characteristics were recor-
ded on potentiostat P-30 ”Elins” at a sweep speed
of 0.5 mV·s–1, a temperature of 25 ± 2 °С, and
a voltage range of 0.01–1.20 V. For galvanosta-
tic tests Neware Battery Testing System was used
with the appropriate soft-ware. The cycling was
carried out in the voltage range of 0.01–1.1 V at
currents from 100 to 500 μA·cm–2.
The impedance curves of the two elect-
rodes cells with tin and lithium electrodes in
initial state and fully discharged (after the first
lithiation) state were obtained at the frequency
range from 0.08 Hz to 50 kHz and amplitude of
applied voltage of 10 mV. The experiment was
carried out after establishing a constant value of
the open circle voltage (OCV) in the cells.
The process of incorporation of lithium in-
to tin proceeds according to the mechanism of
alloy formation and is characterized by multista-
ge processes [16]. The maximum specific capa-
city of the tin electrode in the interaction with
lithium is 994 mA·h·g–1, which corresponds to
the formation of an alloy of the composition
Li4.4Sn. The mass of tin precipitation obtained
from pyrophosphate electrolyte, and the electro-
lysis parameters are presented in table 1.
A typical cyclic current–voltage curve of a
tin electrode obtained at a sweep speed of 0.5
mV·s–1 is shown in fig. 1. There are several ca-
thode and anode peaks on the curve. The ca-
thode peak in the potential region of 0.68 V is
associated with the formation of a solid electro-
lyte interface (SEI) on the tin surface [17], the
formation of which prevents further decompo-
sition of the electrolyte. A large peak at a poten-
tial of ~ 0.3 V corresponds to the formation of
T a b l e 1
Parameters of electrolysis and mass of tin preci-
pitation obtained from pyrophosphate electrolyte
Sam-
ple
Electrolysis
duration,
min
Current
density,
mА·cm–2
Mass of
precipitate,
mg·cm–2
Current
effici-
ency, %
1 15 1.0 0.25 44.7
2 15 1.5 0.27 33.0
3 30 1.0 0.51 45.7
4 30 1.5 0.53 31.8
5 45 1.0 0.78 46,7
6 45 1.5 0.87 34.8
Fig. 1. Typical current-voltage curve of a tin
electrode at the potential sweep rate of 0.5 mV∙s–1.
analloy of lithium with tin. Peaks on the anode
branch of the current–voltage curve at potenti-
als of 0.68, 0.75, and 0.84V are associated with
the reverse process, which is characterized by
the formation of intermetallic compounds of dif-
ferent phase composition [18].
The galvanostatic charge/discharge curves
of Sn electrodes with a mass of 0.25–0.87 mg·
cm–2, obtained in the first cycle, are shown in
fig. 2. For efficient cycling, the range of charge/
discharge voltages, in accordance with the volt-
ammetry data, was set in the range from 0.01 to
Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky
70 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10
Fig. 2. Discharge/charge curves of the first cycle
at the cycling current density of 100 μA·cm-2 for
Sn-electrodes. The numbers on the curves cor-
respond to the numbers of the samples in table 1
(the same is presented in fig. 4,5).
1.1 V. This allows to reduce the ireversible loss
of capacity during the introduce-tion/extraction
of lithium, which occurs at a vol-tage above 1.5
V [19]. According to published data [20], fusion
of lithium with tin proceeds with the formation
of seven intermediate phases, the theoretically
calculated potentials of which, depending on
the phase composition, are in the range of 0.76–
0.38 V. However, the real potentials correspon-
ding to phase transitions are determined not only
by thermodynamics, but also by kinetic cons-
taints, depending on the conditions for obtaining
precipitation and the conditions of the cathodic
process. The voltage of the site on the presented
cathode curves corresponds to 0.4–0.45 V, and
its length is in the range from ~200 to ~500 mA∙
h∙g–1 and depends on the weight of the preci-
pitate and electrolysis conditions. The further pro-
cess of alloy formation is characterized by a gent-
le curve. The anode curves are more complex
and have several kinks at voltages of 0.58, 0.71
and 0.78 V, which are close in magnitude to the
potentials of the anode process (fig. 1).
The corresponding values of the specific
T a b l e 2
Specific capacities and coulombic efficiency of Sn-
electrodes at the first cycle
Sample
Qdischarge * Qcharge * Coulombic
efficiency, % mА·h·g–1
1 860 602 70
2 1029 733 71
3 928 588 63
4 1151 802 70
5 1087 737 68
6 1158 830 72
* Q, mА·h·g–1 — specific capacity of tin films on
the first cycle.
capacities of the discharge and charge, as well as
the coulombic efficiency in the first cycle for the
studied electrodes are presented in table 2. The
obtained values of the discharge specific capa-
city are in the range of 860–1158 mA∙h∙g–1, and
their analysis indicates an increase in specific
capacity with increasing mass of sediment. Cor-
responding charging capacities range from 602
to 830 mA∙h∙g–1. The relatively low value of
coulombic efficiency (63–72 %) in the first cyc-
le of lithium incorporation and extraction is as-
sociated with side processes caused by the for-
mation of SEI and the decomposition of elect-
rolyte [5]. However, already from the second cy-
cle, the coulombic efficiency increases to 90 %.
Fig. 3 shows the dependence of the spe-
cific capacity of tin precipitates obtained at elec-
trolysis currents of 1.0 and 1.5 mA·cm–2 during
the first lithiation on their mass. The obtained de-
pendences in both cases are not linear, which im-
plies a decrease in the utilization coefficient of the
tin precipitate when a certain mass (thickness) is
reached at different cyclic current densities.
The results of galvanostatic cycling of tin
electrodes (samples 1–4) at differen t discharge
current densities are presented in fig. 4. The mi-
nimum loss of specific capacity both within one
Electrochemical characteristics of tin films in cycling in lithium-ion batteries
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 71
Fig. 3. Dependences of the specific discharge
capacity at the first lithiation on the mass of tin
precipitation.
Fig. 4. Cycling performance of Sn-electrodes at
different discharge currents (charge current – 100
μA·cm-2).
discharge current and with its increase from 100
to 500 μA·cm–2 was obtained for sample 1,
which is characterized by a minimum sediment
mass of 0.25 mg·cm–2. Sample 2 with almost the
same mass of the tin film (0.27 mg/cm2), as
follows from fig. 4, is characterized by a signifi-
cantly larger loss of specific capacity during pro-
longed cycling. This is apparently due to the dif-
ferent morphology, structure and properties of
tin films, primarily their porosity, obtained at
two different polarizing current densities. With
increasing deposition current density (sample 2),
the porosity of the tin film and its stability du-
ring long-term cycling decrease. For the remai-
ning samples, an increase in the rate of decrease
in specific capacity with an increase in the mass
of precipitation is observed. At the same time, in
all cases, at later stages of cycling, relative sta-
bilization of the specific capacity is observed,
which after the 60 cycles is in the range from
470 to 710 mA∙h∙g–1. The corresponding dischar-
ge/charge curves of the final cycles are pre-
sented in fig. 5.
The profile of charge/discharge curves chan-
ges significantly in comparison with the curves
of the first cycle (fig.2). The kinks observed on
Fig. 5. Discharge/charge curves of the 60th cycle
at the cycling current density of 100 μA·cm–2 for
Sn-electrodes.
Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky
72 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10
the corresponding curves of the first cycle at the
end of the cycle are smoothed. These differences
are associated with a change in the structure of
tin deposits and the release of the electrode to a
more stable cycling mode. This is confirmed by
a decrease in capacity loss during cycling in la-
ter charge/discharge cycles.
Comparison of the obtained results with the
data of [14] indicates that the specific capacity
of tin films obtained from pyrophosphate elec-
trolyte is significantly higher compared to the ca-
pacity of tin films obtained from citrate-trilonate
(750 mA∙h∙g–1), citrate ( 500 mA∙h∙g–1) and tar-
trate (400 mA∙h∙g–1) electrolytes. Higher specific
characteristics of tin precipitation during lithium
incorporation and extraction may be due to the
difference in the mechanism of their electrolytic
production. The process of electrodeposition of tin
(II) from a pyrophosphate electrolyte is limited by
the previous chemical reaction of dissociation of
the unprotonated complex [Sn(P2O7)2]6– [10]:
[Sn(P2O7)2]6– ↔ [SnP2O7]2– + P2O7
4–,
that allows you to control the morphology, struc-
ture and quality of the obtained tin sediments,
especially their thickness and porosity.
The influence of electrolysis conditions on
the effective resistance of tin electrodes is deter-
mined. For studies, we used cells with the initial
(unlithiated) Sn electrodes and cells after the
first cycle of lithium intercalation (lithiation) to
a voltage of 0.01 V.
The impedance spectra of the original cells
in the Nyquist coordinates Z´ – Z´´, where Z΄
and Z´´ are the real and imaginary components
of the impedance, respectively, are shown in fig.
6, a. The presented curves are characterized by
two sections: the first is in the high-frequency
region (from 50 kHz to 1 Hz), and the second in
the frequency range from 1 to 0.08 Hz. The
initial resistance value obtained by extrapolating
the hodograph to the real Z´ axis at a frequency
of 50 kHz is responsible for the resistance of the
Fig. 6. Impedance spectra of the Li–Sn system in
Nyquist coordinates before cycling (a) and after the
first discharge (b).
electrolyte layer (Rel) in the interelectrode spa-
ce and the separator. The value of this resistance
for all the studied electrodes is quite close and is
about 2 Ohm. Using the well-known equation
k = l/S·R, where k is the conductivity, l is the
thickness of the electrolyte layer (corresponds to
the thickness of the separator –2.5∙10–3 cm), S is
the electrode surface (2 cm2), and R = Rel, the
conductivity of the electrolyte layer was calcu-
lated, which is ~0,6∙10–3 mS∙cm–1, which is clo-
se to the conductivity of the electrolyte in the
layer of the Celgard 2400 separator [21].
The dependences obtained in the high-
Electrochemical characteristics of tin films in cycling in lithium-ion batteries
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 73
frequency region can be considered as a curve in
the form of an incomplete arc. At low frequ-
encies, this curve turns into a straight line with
tilt angles of 48° and 41°, respectively, for pre-
cipitation with a tin mass of 0.25 and 0.27 mg∙
cm–2 (curves 1 and 2). This tilt angle may be due
to the presence of slight diffusion limitations.
An increase in the mass of tin sediment leads to
an increase in tilt angles that are 69–73°, which
indicates the presence of polarization phenome-
na associated with the accumulation or adsorp-
tion of charged particles on the surface of the ele-
ctrode. This type of impedance curve is charac-
teristic for ionistors in which the main electro-
chemical processes occur due to adsorption-de-
sorption of charged particles and the absence of
Faraday processes [21]. It should be noted that
the source electrodes have sufficiently large re-
sistances, which reaches several thousand Ohm.
This can be caused by the presence of an oxide
film formed on the surface of tin sediments after
their obtaining, dry ing and storage.
The impedance spectra of electrochemical
cells after the first cycle of lithiation of Sn-elec-
trodes are significantly different from the initial
ones, both in nature and in the resistance of the
active and reactive parts of the impedance curve
(fig.6, b). They consist of semicircles capturing
a high frequency region, turning into samples 4
and 6, the impedance curves in the low frequ-
T a b l e 3
Resistance of the active and reactive parts of the impedance of the studied electrolytic
precipitations of tin
Sample
Initial sample (OCV-2.2 V) Sample after 1st discharge to 0.01 V*
f, Hz Z΄, Ω –Z΄΄, Ω f, Hz Z΄, Ω –Z΄΄, Ω
1 50 000 2.23 3.14 50 000 8.48 2.65
1 1053 793 10 47.17 1.891
0.08 2965 3000 0.1 58.6 32.42
2 50 000 4.87 4.39 50 000 9.47 9.48
1 2068 1485 10 94 4
0.08 5305 4419 0.1 110 34.9
3 50 000 2.3 1.55 50 000 5.21 3.1
1 1645 2920 10 42.4 1.71
0.08 6963 21640 0.1 50.64 24.38
4 50 000 2.32 1.91 50 000 7.5 7.72
1 2314 3433 10 61.36 3.15
0.08 9691 22500 0.1 73.4 15.86
5 50 000 2.29 7.7 50 000 4.94 3.56
1 1763 2960 10 42.6 1.28
0.08 7344 21080 0.1 48.96 10.7
6 50 000 2.31 1.88 50 000 6.65 8.24
1 1798 2472 10 82.8 6.09
0.08 6702 17000 0.1 100 12.04
* The values of OCV of discharged cells: 1 – 0.315 V, 2 – 0.347 , 3 – 0.487 , 4 – 0.441 , 5 –
0.396, 6 – 0.391 V.
Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky
74 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10
ency region have an additional section in the
form of a small semicircle. The semicircle in the
high-frequency region is characteristic for many
lithium systems in which a passive film is for-
med on the lithium electrode, the nature and cha-
racter of which depend on the composition of the
electrolyte and the state of the electrodes [22, 23].
Such character of the impedance spectra,
according to the authors of [24], allows to sepa-
rate the stages of electrochemical processes, the
first of which corresponds to the transfer of lithi-
um cations across the electrode/electrolyte inter-
face taking into account the formed SEI, and the
second stage of the process is the diffusion of lithi-
um incorporated into the LixSn alloy. The pre-
sence of a second semicircle in the impedance cur-
ves for electrodes with maximum tin deposit
mass indicates the formation of an additional so-
lid electrolyte layer on their surface. As a result,
the resistance of such electrodes increases in
both the high and low frequencies. The angle of
inclination of the straight line at low frequencies
is greater than 45°. The authors of [25], who stu-
died the impedance spectroscopy of thin tin de-
posits during the incorporation and extraction of
lithium, showed that an inclination angle of 45°,
corresponding to the limiting stage of diffusion,
is characteristic only at a voltage of 0.65 V. At mo-
re positive potentials, other processes including
the accumulation of charge, which causes the de-
viation of the slope of the curve in the low-fre-
quency region from 45°, limit lithium diffusion
in the tin structure.
Table 3 shows the values of the resistances
Z΄ and Z΄΄ depending on the frequency for the stu-
died Sn electrodes. The electrodes obtained at a
current density of 1 mA·cm–2 (1, 3, 5) are charac-
terized by lower resistance of the active part of
the impedance than the electrodes obtained at a
current density of 1.5 mA·cm–2, with almost the
same mass of tin precipitation. All the studied
electrodes after the first lithiation cycle are cha-
racterized by an increase in resistance at a frequ-
ency of 50 kHz, which may be due to a change
in the porosity and thickness of the deposit be-
cause of the introduction of lithium. This is in go-
od agreement with the fact that with the introduc-
tion of lithium into tin and the formation of the
Li4.4Sn alloy its volume increases to ~ 300 % [26].
CONCLUSIONS. Thin electrolytic fine se-
diments were obtained from pyrophosphate elect-
rolyte under different electrolysis conditions and
its duration. Electrochemical tests of the obtai-
ned tin deposits as the anode material for LIB
showed that the samples under study have a high
initial specific capacity ranging from 860 to
1158 mAh∙g-1 and are characterized by different
stability during long-term cycling. Tin deposits with
a minimum mass deposited at a current density
of 1.0 mA·cm–2 demonstrate the best stability of
the specific capacity during long-term cycling,
including when discharged by different current
densities. For the remaining samples, the loss in
specific capacity increases with increasing mass
of tin sediment.
The impedance spectra recorded for the ini-
tial Sn electrodes and after the first lithiation
have different shapes and values of the corres-
ponding resistances, which indicates differences
in the passage of the main processes in a system
with a tin electrode depending on the mass of
the coating.
ACKNOWLEDGEMENTS. The authors are
grateful to Dr.Sc. K.D. Pershina for assistance in
the discussion of the results of impedance studies.
ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІ-
ВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-
ІОННИХ АКУМУЛЯТОРАХ
Ю.В. Шматок1, Н.І. Глоба1∗, В.М. Нікітенко2,
Є.А. Бабенков2, В.С. Кублановський2
1Міжвідомче відділення електрохімічної енер-
гетики НАН України, бульвар Вернадського, 38а,
Київ, 03680, Україна
2Інститут загальної та неорганічної хімії
Electrochemical characteristics of tin films in cycling in lithium-ion batteries
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 75
ім. В.І. Вернадського НАН України, просп. Ака-
деміка Палладіна, 32/34, Київ, 03142, Україна
* e-mail: gnl-n@ukr.net
Методами потенціодинамічного та гальва-
ностатичного циклування в 1М фторетиленкар-
бонат-диметилкарбонатному розчині біс-(три-
фторметан)сульфоніміду літію (LiTFSI) в еле-
ментах дискової конструкції з габаритами 2016
досліджено електрохімічні характеристики (пи-
тома ємність, густина заряд-розрядного струму,
корозійна стійкість, ефективність циклування) оло-
в’яних покриттів як анодних матеріалів літій-
іонних акумуляторів (ЛІА). Електролітичні тонкі
плівки олова отримано на мідній підкладці з
пірофосфатного електроліту при pH 7.2, різних
режимах електролізу та його тривалості. Вста-
новлено вплив властивостей покриттів, зокрема
їх маси, на величину питомої ємності та її ста-
більність, у тому числі при розряді різною густи-
ною струму. Показано, що процес інтеркаляції-
деінтеркаляції літію відбувається не на поверх-
ні електрода, а по всій товщині плівки. Дослід-
жувані плівки олова мають високу початкову
питому ємність, близьку до теоретично можливої
(994 мА·ч·г-1), і здатні без механічного руйну-
вання забезпечувати високу густину заряд-роз-
рядного струму. Максимальна стабільність пи-
томої ємності при циклуванні характерна для
олов'яних електродів з мінімальними масами оса-
дів. Кулонівська ефективність Sn-електродів на
першому циклі практично не залежить від тов-
щини плівки олова i становить 70 %, надалі
підвищується до 90 % . Проаналізовано спектри
імпедансу, зняті для досліджуваних електродів
у початковому стані та після першого циклу-
вання (літування). Спектри імпедансу, зняті для
початкових Sn-електродів і після першого літу-
вання, мають різну форму та значення відпо-
відних опорів, що вказує на відмінності в про-
ходженні основних процесів у системі з олов'я-
ним електродом залежно від маси покриття.
К л ю ч о в і с л о в а: електроосадження, пі-
рофосфатні електроліти, плівки олова, питома
ємність, оборотність, літій-іонний акумулятор.
ЭЛЕКТРОХИМИЧЕСКИЕ ХАРАКТЕРИСТИКИ
ПЛЕНОК ОЛОВА ПРИ ЦИКЛИРОВАНИИ В
ЛИТИЙ-ИОННЫХ АККУМУЛЯТОРАХ
Ю.В. Шматок1, Н.И. Глоба1∗, В.Н. Никитенко2,
Е.А. Бабенков2, В.С. Кублановский2
1 Межведомственное отделение электрохими-
ческой энергетики НАН Украины, бульвар
Вернадского, 38а, Киев, 03680, Украина
2 Институт общей и неорганической химии
им. В.И. Вернадского НАН Украины, просп.
Академика Палладина, 32/34, Киев, 03142,
Украина
e-mail: gnl-n@ukr.net
Электролитические тонкие осадки олова полу-
чены из пирофосфатного электролита при раз-
ных режимах электролиза и его длительности.
Методами потенциодинамического и гальвано-
статического циклирования исследованы элек-
трохимические характеристики оловянных по-
крытий как анодных материалов литий-ионных
аккумуляторов. Установлено влияние свойств по-
крытий, в частности их массы, на величину уде-
льной емкости и ее стабильность, в том числе
при разряде разными плотностями тока. Пока-
зано, что исследуемые осадки олова имеют вы-
сокую начальную удельную емкость, близкую к
теоретически возможной. Максимальная стаби-
льность удельной емкости при циклировании ха-
рактерна для электродов с минимальными мас-
сами осадков. Проанализированы спектры импе-
данса, снятые для исследуемых электродов в ис-
ходном состоянии и после первого литиирования.
К л ю ч е в ы е с л о в а: электроосаждение, пи-
рофосфатный электролит, пленки олова, удель-
ная емкость, обратимость, литий-ионный акку-
мулятор.
REFERENCES
1. Schalkwijk W.A., Scrosati В. Advanced in Li-
thium-ion Batteries. (New York: Plenum pub-
lishers, 2002).
2. Pridatko K.I., Churikov A.V. Anode non-carbon
lithium-accumulating composite materials. Elekt-
rokhimicheskaya Energetica. 2005. 5 (1): 16. [in
Russian].
mailto:gnl-n@ukr.net�
mailto:gnl-n@ukr.net�
Yu.V. Shmatok, N.I. Globa, V.M. Nikitenko, E.A. Babenkov, V.S. Kublanovsky
76 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10
3. Kamali A.R., Fray D.J. Tin-based materials as
advanced anode materials for lithium ion batte-ries.
Rev. Adv. Mater. Sci. 2011. 27: 14.
4. Maroni F., Bruni F., Suzuki N., Aihara Tu., Croce F.
Electrospun tin-carbon nanocomposits as anode
material for all solid state lithium-ion batteries. J.
Solid State Electrochem. 2019. 23: 1697.
5. Zhao H., Jiang C., He X., Ren J. Advanced stru-
ctures in electrodeposited tin base anodes for
lithium ion batteries. Electrochim. Acta. 2007.
52: 7820.
6. Hadsoun J., Pacero S., Scrosati B. Electrodepo-sited
Ni-Sn intermetallic electrodes for advan- ced
lithium ion batteries. J. Power Sources. 2006.
160: 1336.
7. Huang L., Wei H.B., Ke F.S., Fan X.Y., Li J.T.,
Sun S.G. Electrodeposition and lithium storage
performance of three-demension porous reticular
Sn-Ni alloy electrodes. Electrochem. Acta. 2009.
54: 2693.
8. Bersirova O., Kublanovskii V. Crystalline Rough-
ness as a Morphological Characteristic of the
Surface of Electroplated Silver Coatings. Russ. J.
Appl. Chem. 2009. 82: 1944.
9. Bersirova O., Kublanovsky V., Cesiulis H. Elec-
trochemical Formation of Functional Silver Co-
atings: Nanostructural Peculiarities. ECS Trans-
actions. 2013. 50: 155.
10. Orekhova V.V., Andryushchenko F.K. Issledo-
vanie kineticheskih zakonomernostei electrod-nyh
reakcii v poliligandnyh electrolitah. Elect-
rohimiya. 1974. 10 (3): 363. [in Russian].
11. Orekhova V.V., Andryushchenko F.K. Polyli-gand
electrolytes plating. (Kharkov: Vishcha shkola,
1979). [in Russian].
12. Kublanovsky V.S., Nikitenko V.N. Mechanism of
the electrodeposition of palladium coatings from
glycinate electrolytes. J. Electroanal. Chem. 2013.
699: 14.
13. Kublanovsky V.S., Nikitenko V.N. Electrochemi-
cal properties of palladium(II) trans- and cis-
diglycinate complexes. Electrochim. Acta. 2011.
56: 2110.
14. Kublanovsky V.S., Nikitenko V.N., Globa N.I.
Effect of the nature of a ligand on electrochemical
characteristic of tin films in cycling in lithium-ion
batteries. Russ. J. Appl. Chem. 2015. 88: 407.
15. Kublanovsky V.S., Nikitenko V.N., Globa N.I.
Electrochemical Deposition of Corrosion-Resi-
stant Coatings from Tin-Nickel Alloys. Mater. Sci.
2017. 52: 687.
16. Idota Y., Kubota T., Matsufuji A., Maekawa Y.,
Miyasaka T. Tin-based amorphous oxide: a high-
capacity lithium-ion-storage material. Science.
1997. 276: 1395.
17. Aifantis K.E., Hackney S.A., Dempsey J.P. De-
sign criteria for nanostructured Li-ion batteries. J.
Power Sources. 2007. 165: 874.
18. Amadei I., Panero S., Scrosati B., Cocco G. Schif-fini
L. The Ni3Sn4 intermetallic as novel electro-de in
lithium cells. J. Power Sources. 2005. 143: 227.
19. Beattie S.D., Hatchard T., Bonakdarpour A.,
Hewitt K.C., Dahn J.R. Anomalous, high-voltage
irreversible capacity in tin electrodes for lithium
batteries. J. Electrochem. Soc. 2003. 150: A701.
20. Winter M., Besenhard J.O. Electrochemical lithi-
ation of tin and tin-based intermetallics and
composites. Electrochim. Acta. 1999. 45: 31.
21. Globa N.I., Shmatok Y.V., Milovanova O.I., Sirosh
V.A., Kirillov S.A. Electrolytic Double-Layer
Supercapacitors Based on Sodium-Ion Sy-stems,
with Activated-Carbon Electrodes. Russ. J. Appl.
Chem. 2018. 91: 187.
22. Churikov A.V., Nimon E.S., Lvov A.L. Impedan-
ce of Li—Sn, Li—Cd and Li—Sn—Cd alloys in
propylene carbonate solution. Electrochim. Acta.
1997. 42: 179.
23. Churikov A.V., Gamayunova I.M., Shirokov A.V.
Ionic processes in solid-electrolyte passivating
films on lithium. J. Solid State Electrochem. 2000.
4: 216.
24. Churikov A.V., Pridatko K.I., Ivanishchev A.V.,
Ivanishcheva I.A., Gamayunova I.M., Zapsis K.V.,
Sycheva V.O. Impedance spectroscopy of lithium-
tin film electrodes. Russ. J. Electrochem. 2008. 44
(5): 550.
25. Churikov A.V., Ivanishchev A.V., Ivanishcheva
Electrochemical characteristics of tin films in cycling in lithium-ion batteries
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2019, т . 85, № 10 77
I.A., Gamayunova I.M., Zapsis K.V., Sycheva V.O.
Lithium intercalation into thin-film lithium-tin and
lithium-carbon electrodes: an impedance spect-
roscopy study. Elektrokhimi-cheskaya Energetica.
2007. 7 (4): 169. [in Russian].
26. Aravindan V., Lee Y.S., Madhavi S. Research
progress on negative electrodes for practical Li-
ion batteries: beyond carbonaceous anodes. Adv.
Energy Mater. 2015. 5: 1402225.
Received 18.09.2019
( e-mail: gnl-n@ukr.net
( e-mail: gnl-n@ukr.net
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-88 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:04:32Z |
| publishDate | 2019 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/4f/dfba878d064399437041dca11b53f34f.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-882026-07-22T08:23:41Z ELECTROCHEMICAL CHARACTERISTICS OF TIN FILMS IN CYCLING IN LITHIUM-ION BATTERIES ЭЛЕКТРОХИМИЧЕСКИЕ ХАРАКТЕРИСТИКИ ПЛЕНОК ОЛОВА ПРИ ЦИКЛИРОВАНИИ В ЛИТИЙ-ИОННЫХ АККУМУЛЯТОРАХ ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ Shmatok, Yurii Globa, Natalia Nikitenko, Vasyl Babenkov, Eugen Kublanovsky, Valeriy electrodeposition, pyrophosphate electrolyte, tin films, specific capacity, reversibility, lithium-ion battery. Thin electrolytic fine tin sediments were obtained from pyrophosphate electrolyte under different electrolysis conditions and duration. The electrochemical characteristics of tin coatings as anode materials of lithium-ion batteries are studied using potentiodynamic and galvanostatic cycling methods. The effect of the properties of coatings, in particular their mass, on the value of specific capacitance and its stability, including during discharge with different current densities, has been established. It is shown that the studied tin sediments have high initial specific capacity that is close to theoretically possible. The maximum stability of the specific capacity during cycling is characteristic of electrodes with minimal masses of precipitation. The impedance spectra recorded for the studied electrodes in the initial state and after the first lithiation are analyzed. V.I.Vernadsky Institute of General and Inorganic Chemistry 2019-10-16 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/88 10.33609/0041-6045.85.10.2019.67-77 Ukrainian Chemistry Journal; Vol. 85 No. 10 (2019): Ukrainian Chemistry Journal; 67-77 Украинский химический журнал; ##issue.vol## 85 ##issue.no## 10 (2019): Украинский химический журнал; 67-77 Український хімічний журнал; Том 85 № 10 (2019): Український хімічний журнал; 67-77 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/88/58 Copyright (c) 2019 Yurii Shmatok, Natalia Globa, Vasyl Nikitenko, Eugen Babenkov, Valeriy Kublanovsky https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Shmatok, Yurii Globa, Natalia Nikitenko, Vasyl Babenkov, Eugen Kublanovsky, Valeriy ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title | ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title_alt | ELECTROCHEMICAL CHARACTERISTICS OF TIN FILMS IN CYCLING IN LITHIUM-ION BATTERIES ЭЛЕКТРОХИМИЧЕСКИЕ ХАРАКТЕРИСТИКИ ПЛЕНОК ОЛОВА ПРИ ЦИКЛИРОВАНИИ В ЛИТИЙ-ИОННЫХ АККУМУЛЯТОРАХ |
| title_full | ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title_fullStr | ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title_full_unstemmed | ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title_short | ЕЛЕКТРОХІМІЧНІ ХАРАКТЕРИСТИКИ ПЛІВОК ОЛОВА ПРИ ЦИКЛУВАННІ В ЛІТІЙ-ІОННИХ АКУМУЛЯТОРАХ |
| title_sort | електрохімічні характеристики плівок олова при циклуванні в літій-іонних акумуляторах |
| topic_facet | electrodeposition pyrophosphate electrolyte tin films specific capacity reversibility lithium-ion battery. |
| url | https://ucj.org.ua/index.php/journal/article/view/88 |
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