EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE
Studies have shown the possibility of a long cycle of sulfur electrode with a high content of active material. The use of water-soluble binder material NV-1A leads to the realization of high current loads in the Li-S battery. Impedance spectroscopy has shown that the low coulombic efficiency in the...
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| author | Krushevskyi, Oleksandr Zhou, MiaoMiao Potapenko, Oleksandr Potapenko, Anna |
| author_facet | Krushevskyi, Oleksandr Zhou, MiaoMiao Potapenko, Oleksandr Potapenko, Anna |
| author_institution_txt_mv | [
{
"author": "Oleksandr\t Krushevskyi",
"institution": "Joint Department of Electrochemical Energy Systems NAS of Ukraine"
},
{
"author": "MiaoMiao Zhou",
"institution": "Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou, Jiangxi, P.R. China"
},
{
"author": "Oleksandr\t Potapenko",
"institution": "Joint Department of Electrochemical Energy Systems NAS of Ukraine"
},
{
"author": "Anna Potapenko",
"institution": "Joint Department of Electrochemical Energy Systems NAS of Ukraine"
}
] |
| author_sort | Krushevskyi, Oleksandr |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:47Z |
| description | Studies have shown the possibility of a long cycle of sulfur electrode with a high content of active material. The use of water-soluble binder material NV-1A leads to the realization of high current loads in the Li-S battery. Impedance spectroscopy has shown that the low coulombic efficiency in the cycling of the sulfur electrode is primarily due to the spontaneous dissolution of sulfur in the electrolyte, which requires high energy consumption when charging the Li-S battery. The reduction of the specific capacity during cycling is associated with the formation and accumulation of non-conductive films of short-chain polysulfides. On the basis of the conducted researches and the review of the literature sources ways of overcoming of this problem are offered. The ability of cycling the sulfur electrodes at the high current loads has been shown. The discharge capacity values of the sulfur electrodes at the current load 790 mA∙cm-2 are 500 і 420 mAh∙g-1 on the 5-th and 100-th cycles, accordingly. Using the method of impedance spectroscopy, it has been supposed that the formation and accumulation of unconductive Li2S2 / Li2S phases is the main process, which induce the quick capacity reduction of Li - S batteries upon cycling. |
| doi_str_mv | 10.33609/2708-129X.87.11.2021.55-59 |
| first_indexed | 2025-09-24T17:43:42Z |
| format | Article |
| fulltext |
55
УДК 544.63 doi: 10.33609/2708-129X.87.11.2021.55-59
EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL
PARAMETERS OF SULFUR ELECTRODE
О.V. Potapenko1,2, A.V. Potapenko 1,2, O.V. Krushevskyi1, M. Zhou2
1Joint Department of Electrochemical Energy Systems NAS of Ukraine
2Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology,
Ganzhou, Jiangxi, P.R. China
Email: avoloshka@ukr.net
Studies have shown the possibility of a long cycle of sulfur electrode with a high content
of active material. The use of water-soluble binder material NV-1A leads to the realization
of high current loads in the Li-S battery. Impedance spectroscopy has shown that the low
coulombic efficiency in the cycling of the sulfur electrode is primarily due to the spontaneous
dissolution of sulfur in the electrolyte, which requires high energy consumption when charg-
ing the Li-S battery. The reduction of the specific capacity during cycling is associated with the
formation and accumulation of non-conductive films of short-chain polysulfides. On the ba-
sis of the conducted researches and the review of the literature sources ways of overcoming of
this problem are offered. The ability of cycling the sulfur electrodes at the high current loads
has been shown. The discharge capacity values of the sulfur electrodes at the current load
790 mA∙cm-2 are 500 і 420 mAh∙g-1 on the 5-th and 100-th cycles, accordingly. Using the
method of impedance spectroscopy, it has been supposed that the formation and accumula-
tion of unconductive Li2S2 / Li2S phases is the main process, which induce the quick capacity
reduction of Li - S batteries upon cycling.
Key words: sulfur electrode, discharge capacity, coulombic efficiency, cyclability.
INTRODUCTION. The growing interest in
the Li-S system is due to its high energy densi-
ty (2567 Wh ∙ kg-1), low cost of sulfur and in-
creased safety [1–3]. Li-S batteries are of par-
ticular interest for stationary and electric ve-
hicles where high capacity and downsizing are
important. However, the efficiency and service
life of Li - S batteries need to be improved in
order for them to be used in practice [4].
However, the practical application of Li-S
battery technology is hindered by several fac-
tors:
• sulfur and its discharge product Li2S are
not electrically conductive (5 ∙ 10-30 S ∙ cm-1
at 25 °C). This makes it necessary to combine
sulfur with various electrically conductive sub-
strates (activated carbon, nanotubes, graphene
oxide, leading polymers, metal oxides, etc., in
EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE
56 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
which the maximum sulfur concentration is
reached);
• the density of sulfur differs from the den-
sity of the product of its discharge Li2S, and the
volumetric expansion or contraction that oc-
curs during the charging-discharging process-
es reaches (76%).;
• dissolution and movement of long-chain
lithium sulfides (Li2Sx, 2 <x <8) in the electro-
lyte causes a loss of active sulfur, which leads
to a decrease in the capacity and Coulomb effi-
ciency of the battery [5–9].
One of the ways to improve the parame-
ters of a sulfur electrode can be the use of a
polymer binder with a large number of polar
functional groups, which makes it possible to
fix long-chain lithium sulfides and effectively
suppress the shuttle effect in Li-S batteries.
When a Li-S battery is discharged, sulfur
dissolves in the liquid electrolyte, which leaves
numerous voids in the S / C cathode, while at
the end of the discharge, dissolved polysulfides
precipitate back onto the cathode in the form
of Li2S2. і Li2S [10,11].
To ensure high electrochemical characte
ristics of the cathode during the cycling of the
Li / S element, a union capable of maintaining
a higher porous structure is needed. Conven-
tional unions such as polyvinylidene fluoride
and poly (ethylene oxide) cannot meet this
requirement due to swelling and gelation un-
der the action of electrolyte solvents [4]. In
addition, the reduction of sulfur as an inter-
mediate produces anionic polysulfide radicals
that react with many organic polymers, the
so-called vulcanization process [12]. There-
fore, the union for the cathode of the Li / S
element must be insoluble in the liquid elec-
trolyte and chemically resistant to all types of
sulfur.
In our work, we study the electrochemical
behavior of a Li-S battery with a new multi
functional water-soluble material NV-1A
[13]. Despite a large number of studies [14,15]
showing that the best results in the cycling of
Li-S batteries are observed at a mass sulfur
content of about 30%, from our point of view
for effective practical application the content of
inactive sulfur electrode components should
not exceed 30–40 %.
EXPERIMENT AND DISCUSSIONS OF
THE RESULTS. The positive electrode of
the Li-S battery consisted of sulfur (99.9%,
Ukraine), graphite (99.95%, GAK-1, Ukraine),
carbon black (Super P, Alfa Aesar China Limi
ted, China) and water-soluble binder NV-1A
(Zhejiang Casnovo New Materials Co. Ltd,
China) taken in a ratio of 70: 20: 5: 5, respec-
tively.
1M LiN(CF3SO2)2 (Sigma Aldrich) in a solu-
tion of 1,2-dimethoxyethane (G1): dioxolane
(DOL) (1:1) by volume (Aldrich) was used as
the electrolyte. Celgard 2325 acted as a sepa
rator. Lithium metal was used as an auxiliary
electrode in elements of dimensions of 2016.
Galvanostatic cycling (MTech G410-4, Uk
raine) and impedance spectroscopy (Autolab
PGSTAT302, Switzerland) were used to obtain
electrochemical parameters of the electrode.
Galvanostatic curves of the sulfur electrode
(Fig. 1) are characterized by the presence of
2 shelves of discharge / charge processes corre-
sponding to the following reactions:
S8 + 4е− → 2S4−
S4− + 8Li+ + 6е− → 4Li2S
S4− + 4Li+ + 2е− → 2Li2S2
(1-st plateau on
the discharge
curve)
(2-nd plateau
on the discharge
curve)
О.V. Potapenko, A.V. Potapenko, O.V. Krushevskyi, M. Zhou
57https://ucj.org.ua
UCJ № 11 / Vol. 87
Fig. 1. Galvanostatic charge/discharge curves
for the sulfur electrode at і = 790 μA ∙cm-2.
During the cycling of the Li-S battery there
is a decrease in discharge / charging capacity,
which indicates the degradation of the elec-
trode due to partial loss of active substance due
to migration of soluble polysulfides from the
cathode material to the electrolyte, followed
by their reduction on the carbon surface of the
working electrode and lithium counter elec-
trode as a result of the solubility of long-chain
lithium polysulfides in DOL and glim solvents,
this process can occur spontaneously (the so-
called "polyshatl effect").
Li2Sn + Li2S → Li2Sn-m + Li2S1+m
(n-1)Li2Sn + 2Li → nLi2Sn-1
This in turn has a negative effect on the pres-
ervation of the Li-S battery and requires addi-
tional electricity when it is charged, which in
turn leads to low coulombic efficiency (Fig. 2),
which does not exceed 80% at specified modes
of galvanostatic cycling (i = 790 μA ∙ cm-2).
The reduction of the current load by 2 and
4 times practically does not change the spe-
cific capacity during discharge and is 420 and
450 mAh∙g-1, respectively.
Fig. 2. Changes in the specific capacity and cou-
lombic efficiency of the sulfur electrode upon cycling.
The main parameters of the cell were cal-
culated by impedance spectroscopy, and it was
proved that the greatest contribution to the total
resistance of the Li - S battery is made by the
resistance corresponding to the charge trans-
fer process through the SEI film on the lithi-
um anode (Fig. 3). Moreover, a sharp increase
in this resistance is observed at the end of the
discharge of the sulfur electrode, which is asso-
ciated with the formation of poorly soluble Li2S2
and Li2S films on its surface. At a lower degree
of discharge of the electrode, the increase in
the resistance to charge transfer at the lithium
anode is practically not observed, in contrast to
the resistance of the electrolyte in the pores of
the separator. This behavior of the Li-S element
is due to the solubility of long-chain sulfides
Sn
2- (n ≥ 4), the accumulation of which in the
electrolyte leads to a change in its specific electri-
cal conductivity. When the degree of discharge
of the sulfur electrode is more than 50%, lithium
sulfides Sn
2- (n ≥ 4) begin to be converted into
Li2S2 and Li2S, which have low solubility, which
leads to their crystallization from the electrolyte
solution. Therefore, no further increase in elec-
trolyte resistance is observed.
EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE
58 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
Fig. 3. Change in the resistance of the electrolyte
and SEI depending on the degree of discharge of
the electrode.
The presence of the above factors leads to
the need to optimize the composition of the
components of the sulfur electrode in order to
create a porous surface that is able to hold lithi-
um polysulfides (in liquid and solid state) in the
structure of the electrode. As well as the use of
electrolyte systems that inhibit the migration of
soluble polysulfides in Li - S batteries.
CONCLUSIONS. Studies have shown the
possibility of a long cycle of sulfur electrode
with a high content of active material. The use
of water-soluble binder material NV-1A leads to
the realization of high current loads in the Li-S
battery. Impedance spectroscopy has shown
that the low coulombic efficiency in the cycling
of the sulfur electrode is primarily due to the
spontaneous dissolution of sulfur in the electro-
lyte, which requires high energy consumption
when charging the Li-S battery. The reduction
of the specific capacity during cycling is asso-
ciated with the formation and accumulation
of non-conductive films of short-chain poly-
sulfides. On the basis of the conducted research-
es and the review of the literature sources ways
of overcoming of this problem are offered.
ACKNOWLEDGEMENT.
The authors are grateful to Zhejiang
Casnovo New Materials Co., Ltd. for
the provided samples of water-soluble
binders.
ВПЛИВ ВОДОРОЗЧИННОГО ПОЛІМЕРУ NV-1А
НА ЕЛЕКТРОХІМІЧНІ ПАРАМЕТРИ СІРЧАНОГО
ЕЛЕКТРОДА
О. В. Потапенко, Г. В. Потапенко,
О. В. Крушевський, M. Чжоу
1Міжвідомче відділення електрохімічної
енергетики НАН України
2Факультет металургії та хімії матері-
алів Цзянсінського університету науки і
техніки,
Ганьчжоу, Цзянсі, Китай
Email:avoloshka@ukr.net
Дослідження показали можливість три-
валого циклування сірчаного електрода з
високим вмістом активного матеріалу. Ви-
користання водорозчинного сполучного
NV-1А призводить до реалізації високих
струмових навантажень у Li-S батареї. Імпе-
дансна спектроскопія показала, що низька
кулонівська ефективність при циклуванні
сірчаного електрода насамперед пов’язана
зі спонтанним розчиненням сірки в елек-
троліті, що вимагає високого споживання
енергії при зарядженні Li-S акумулятора.
Зниження питомої ємності під час циклу-
вання пов'язане з утворенням і накопи-
ченням непровідних плівок на основі ко-
ротколанцюгових полісульфідів. На основі
проведених досліджень та огляду літера-
О.V. Potapenko, A.V. Potapenko, O.V. Krushevskyi, M. Zhou
59https://ucj.org.ua
UCJ № 11 / Vol. 87
турних джерел запропоновано шляхи по-
долання цієї проблеми. Показано здатність
циклування сірчаних електродів при ви-
соких струмових навантаженнях. Значен-
ня розрядної ємності сірчаних електродів
при струмовому навантаженні 790 мА∙см-2
становлять 500 і 420 мАг∙г-1 на 5-му і 100-му
циклах відповідно. Використовуючи метод
імпедансної спектроскопії, висунуто при-
пущення, що утворення та накопичення
непровідних фаз Li2S2/Li2S є основним про-
цесом, який спричиняє швидке зниження
ємності Li-S акумуляторів при циклуванні.
Ключові слова: сірчаний електрод, роз-
рядна ємність, кулонівська ефективність,
циклічність.
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Стаття надійшла 30.11.2021.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-382 |
| institution | Ukrainian Chemistry Journal |
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| language | English |
| last_indexed | 2026-07-23T01:07:24Z |
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| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
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| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3822026-07-22T08:23:47Z EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE Krushevskyi, Oleksandr Zhou, MiaoMiao Potapenko, Oleksandr Potapenko, Anna sulfur electrode, discharge capacity, coulombic efficiency, cyclability. Studies have shown the possibility of a long cycle of sulfur electrode with a high content of active material. The use of water-soluble binder material NV-1A leads to the realization of high current loads in the Li-S battery. Impedance spectroscopy has shown that the low coulombic efficiency in the cycling of the sulfur electrode is primarily due to the spontaneous dissolution of sulfur in the electrolyte, which requires high energy consumption when charging the Li-S battery. The reduction of the specific capacity during cycling is associated with the formation and accumulation of non-conductive films of short-chain polysulfides. On the basis of the conducted researches and the review of the literature sources ways of overcoming of this problem are offered. The ability of cycling the sulfur electrodes at the high current loads has been shown. The discharge capacity values of the sulfur electrodes at the current load 790 mA∙cm-2 are 500 і 420 mAh∙g-1 on the 5-th and 100-th cycles, accordingly. Using the method of impedance spectroscopy, it has been supposed that the formation and accumulation of unconductive Li2S2 / Li2S phases is the main process, which induce the quick capacity reduction of Li - S batteries upon cycling. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-12-24 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/382 10.33609/2708-129X.87.11.2021.55-59 Ukrainian Chemistry Journal; Vol. 87 No. 11 (2021): Ukrainian Chemistry Journal; 55-59 Украинский химический журнал; ##issue.vol## 87 ##issue.no## 11 (2021): Ukrainian Chemistry Journal; 55-59 Український хімічний журнал; Том 87 № 11 (2021): Український хімічний журнал; 55-59 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/382/203 Copyright (c) 2021 Oleksandr Krushevskyi, MiaoMiao Zhou, Oleksandr Potapenko, Anna Potapenko https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Krushevskyi, Oleksandr Zhou, MiaoMiao Potapenko, Oleksandr Potapenko, Anna EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title | EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title_full | EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title_fullStr | EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title_full_unstemmed | EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title_short | EFFECT OF WATER-SOLUBLE POLYMER NV-1A ON ELECTROCHEMICAL PARAMETERS OF SULFUR ELECTRODE |
| title_sort | effect of water-soluble polymer nv-1a on electrochemical parameters of sulfur electrode |
| topic_facet | sulfur electrode discharge capacity coulombic efficiency cyclability. |
| url | https://ucj.org.ua/index.php/journal/article/view/382 |
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