Electron-microscopic and X-ray studies have revealed that the ability of lead-acid storage batteries to adopt charge due to physico-chemical processes occurring in the lead paste and on the border of the “shunt-paste” depends dramatically on both the initial moisture content in the lead paste and keeping enhanced humidity in the exposure chamber for plates.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3365

Dobromyslov, M.

Grechushnikov, E.

Kharseev, V.

Kuzmenko, A.

Electronic Sumy State University Institutional Repository

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ Vol. 5 No 4, 04026(3pp) (2013) Том 5 № 4, 04026(3cc) (2013)   The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013  2077-6772/2013/5(4)04026(3) 04026-1  2013 Sumy State University Short Communication  Kinetic Characteristics, Phase and Structural Changes in Electrical Materials and Devices  A. Kuzmenko1, E. Grechushnikov1, V. Kharseev1, M. Dobromyslov2  1 Southwest State University, 94, 50 Let Oktyabrya Str., 305040 Kursk, Russia 2 Pacific National University, 136, Tihookeanskaya Str., 680035 Khabarovsk, Russia  (Received 24 October 2013; published online 10 December 2013)  Electron-microscopic and X-ray studies have revealed that the ability of lead-acid storage batteries to adopt charge due to physico-chemical processes occurring in the lead paste and on the border of the “shunt-paste” depends dramatically on both the initial moisture content in the lead paste and keeping enhanced humidity in the exposure chamber for plates.  Keywords: Scanning electron microscopy, X-ray diffraction, Lead-acid batteries  PACS numbers: 61.10. – i, 61.72.Ff   1. INTRODUCTION  Chemical composition, phase structure of both elec-trode composition and active material influence greatly service properties of lead-acid storage battery along with operating practice of formation [1]. Despite a long histo-ry of using these power sources the consistent analysis of the interrelation of the triad “composition-structure-properties” has not been made. In the paper, in devel-opment of earlier investigations on this problem [2], structural and phase changes that accompany the sur-face formation and charge formation on electrode plates and their influence on functional and electric character-istics of storage batteries have been studied by electron microscopic (SEM) (JEOL JSM6610LV) and X-ray tech-niques (X-ray study) (GBC ЕMMA, CuK).  2. EXPERIMENTAL SECTION  Samples of lead mass were prepared according to the standard procedure from highly-oxidized lead powder – PbO (76  1 %) and sulfuric acid solution of 1.4 g/cm3 with mass ratio of compositions: 4.9 for positive and 4.5 % for negative sample. The negative active mass included 1 % carbon, barium sulphate and stretcher Vanisperse HT-1. Dried electrode plates were used to assemble storage bat-teries of rated capacity 60 Аh. The electrodes were manu-factured by stamping and stretching method from Pb-Ca-Sn melt. Studied were three groups of electrode plates produced in several stages in a soaking chamber with humidity that was prepared by various ways:  by steam generator – immediately after manufac-turing with exposure during 22 h at a temperature of 45  5 ºС and a  relative humidity of 95-65 % and with consecutive drying during 14 h at a temperature of 65  5 ºС and a relative humidity of 5-10 %;  by wetting the floor with water before loading plates and spraying water with injectors – at analogous modes. Studied were also electrode plates exposed during 2 h at a temperature of 25  1ºС and a relative humidi-ty of 80  2 %.       Fig. 1 – Paste structure of negative electrode plates after ex-posure and drying: a – the first group, b – the second group, c – the third group     a b c  A. KUZMENKO, E. GRECHUSHNIKOV, V. KHARSEEV, M. DOBROMYSLOV J. NANO- ELECTRON. PHYS. 5, 04026 (2013)   04026-2 3. RESULTS AND DISCUSSION  Investigations conducted by SE and X-ray techniques made it possible to establish structural differences in compositions of electrode pastes depending on the meth-od and conditions of their exposures in a chamber. The paste of plates of the first group (Fig. 1a) presents a well-formed skeleton that consisted of oblong crystal particles up to 3 m in length – according to X-ray technique tri-basic lead sulfate (3PbO∙PbSO4∙H2O) (Fig. 2) and small-er-sized particles of a rounded shape - lead oxide (-PbO) (Fig. 2). The composition of the second group plates (Fig. 1b) is of similar structure. However, there were unreacted free particles and aggregates the size smaller than 1 m. The third group (Fig. 1c) is characterized by a chaotic location and a different size and shape of un-structured particles. In all samples studied low content of lead oxide in the form -PbO was found (Fig. 2).   Fig. 2 – X-ray pattern of negative paste after maturation and drying    Fig. 3 – Kinetic curves of moisture content changes in positive  ( ) and negative ( ) plates at their storage in the open air at a temperature of 25  1 ºС and a relative humidity of 80  2 %  Those structural differences in shape, size, and rela-tive position of the particles in the third group were due to changes in moisture content during 2 h, which is cor-roborated by kinetic curves (Fig. 3) from which the criti-cal value of humidity reducing recrystallization level was determined [1]. The deference in kinetic regularities of moisture evaporation from negative plates is explained by its lower initial content and existence of auxiliary additives in electrode pastes.      Fig. 4 – Structure of transverse cuts of “shunt – paste” for various ways of exposure of electrode plates: 1 – the first group; 2 – the third group    Fig. 5 – Dynamics of nominal capacity changes for storage batteries according to cycles: ( ) – the first group,  ( ) – the second group. ( ) – the third group  To analyze the state of the transitional layer “shunt – paste” transverse cuts were prepared with SEM. As SEM images show (Fig. 2) there exists an interphase transition in contrast – from light to solid dark, and in structure – from friable, which corresponds to a corro-sive layer (to 30 m), to uniform –lead-calcium alloy of the shunt. In the surface layer of the lead paste of the third group electrode plates many microcracks (on the order of 1 m) and detachments appeared (Fig. 4b). To establish functional and electric characteristics of storage batteries tests were conducted the results of which are shown in Fig. 5. It was found that the sam-ples of the first group at the second stage of “charging-discharging” had the maximum nominal capacity, the maximum of which reached 64.4 Аh, whereas for the third group – 61.9 Аh, which is in line with the analy-sis of phase and structural changes. Lower value of the nominal capacity for the third group’s batteries was  b a  KINETIC CHARACTERISTICS, PHASE AND STRUCTURAL CHANGES… J. NANO- ELECTRON. PHYS. 5, 04026 (2013)   04026-3         Fig. 6 – Kinetics of current changes in samples of various groups: ( ) – the first group, ( ) – the second group.  ( ) – the third group; (25  1ºС without cooling, 16 V at batteries charging); a – Imax  25 A; b – Imax  18 A; c – temperature changes as for b-case  obviously due to significant inhomogeneity of the sur-face structure (Compare Fig. 4a and Fig. 4b).  The fact that the capacity of the third group’s bat-teries was constant is indicative of a low activity of the charge-forming electrode surface. Charging capacity of batteries was checked when these charged at a constant voltage of 16 V after 20-h discharging. In the samples of the first group the elec-trodes have the lowest transitional resistance of “shunt-active mass” and hence, electric energy losses to overcome internal resistance were minimal.  The distinction among internal resistances was es-tablished by studying the kinetics of decreasing re-sistance (Fig. 6a, b), which is also supported by an ab-rupt increase in electrolyte temperature for samples of the third group. Two hours of discharging the current value remained constant and was equal to 25 A; elec-trolyte temperature of the samples of the first and se-cond group amounted to 40 ºС, while of the third group’s samples amounted to 45 ºС, which is obviously due to dramatically higher resistance.  4. CONCLUSIONS  Thus, functional and electric characteristics of stor-age batteries critically depend on physico-chemical pro-cesses occurring within the lead paste and on the bor-der of the “shunt-paste”, which are most dependent on both the initial moisture content in the lead paste and keeping enhanced humidity in the exposure chamber for plates.   REFERENCES  1. D. Pavlov, Lead-Acid Batteries Science and Technology (Elsevier science: 2011). 2. A.P. Kuzmenko, A.V. Stepanov, V.F. Niyazi, A.M. Ivanov, E.A. Grechushnikov, V. Kharseev, Proceedings of  Southwest State University. Physics-Chemistry 41, 2 (2012).  a b c 

Kinetic Characteristics, Phase and Structural Changes in Electrical Materials and Devices

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 5 No 4, 04026(3pp) (2013) Том 5 № 4, 04026(3cc) (2013) 
 
 
The article was reported at the International Conference «Physics and Technology of Nanomaterials and Structures», Kursk, 21-22 November, 2013 
 
2077-6772/2013/5(4)04026(3) 04026-1  2013 Sumy State University 
Short Communication 
 
Kinetic Characteristics, Phase and Structural Changes in Electrical Materials and Devices 
 
A. Kuzmenko1, E. Grechushnikov1, V. Kharseev1, M. Dobromyslov2 
 
1 Southwest State University, 94, 50 Let Oktyabrya Str., 305040 Kursk, Russia 
2 Pacific National University, 136, Tihookeanskaya Str., 680035 Khabarovsk, Russia 
 
(Received 24 October 2013; published online 10 December 2013) 
 
Electron-microscopic and X-ray studies have revealed that the ability of lead-acid storage batteries to 
adopt charge due to physico-chemical processes occurring in the lead paste and on the border of the “shunt-
paste” depends dramatically on both the initial moisture content in the lead paste and keeping enhanced 
humidity in the exposure chamber for plates. 
 
Keywords: Scanning electron microscopy, X-ray diffraction, Lead-acid batteries 
 
PACS numbers: 61.10. – i, 61.72.Ff 
 
 
1. INTRODUCTION 
 
Chemical composition, phase structure of both elec-
trode composition and active material influence greatly 
service properties of lead-acid storage battery along with 
operating practice of formation [1]. Despite a long histo-
ry of using these power sources the consistent analysis of 
the interrelation of the triad “composition-structure-
properties” has not been made. In the paper, in devel-
opment of earlier investigations on this problem [2], 
structural and phase changes that accompany the sur-
face formation and charge formation on electrode plates 
and their influence on functional and electric character-
istics of storage batteries have been studied by electron 
microscopic (SEM) (JEOL JSM6610LV) and X-ray tech-
niques (X-ray study) (GBC ЕMMA, CuK). 
 
2. EXPERIMENTAL SECTION 
 
Samples of lead mass were prepared according to the 
standard procedure from highly-oxidized lead powder – 
PbO (76  1 %) and sulfuric acid solution of 1.4 g/cm3 with 
mass ratio of compositions: 4.9 for positive and 4.5 % for 
negative sample. The negative active mass included 1 % 
carbon, barium sulphate and stretcher Vanisperse HT-1. 
Dried electrode plates were used to assemble storage bat-
teries of rated capacity 60 Аh. The electrodes were manu-
factured by stamping and stretching method from Pb-Ca-
Sn melt. Studied were three groups of electrode plates 
produced in several stages in a soaking chamber with 
humidity that was prepared by various ways: 
 by steam generator – immediately after manufac-
turing with exposure during 22 h at a temperature of 
45  5 ºС and a  relative humidity of 95-65 % and with 
consecutive drying during 14 h at a temperature of 
65  5 ºС and a relative humidity of 5-10 %; 
 by wetting the floor with water before loading 
plates and spraying water with injectors – at analogous 
modes. 
Studied were also electrode plates exposed during 
2 h at a temperature of 25  1ºС and a relative humidi-
ty of 80  2 %. 
 
 
 
 
 
 
Fig. 1 – Paste structure of negative electrode plates after ex-
posure and drying: a – the first group, b – the second group, c 
– the third group 
 
 
 
 
a 
b 
c 
 A. KUZMENKO, E. GRECHUSHNIKOV, V. KHARSEEV, M. DOBROMYSLOV J. NANO- ELECTRON. PHYS. 5, 04026 (2013) 
 
 
04026-2 
3. RESULTS AND DISCUSSION 
 
Investigations conducted by SE and X-ray techniques 
made it possible to establish structural differences in 
compositions of electrode pastes depending on the meth-
od and conditions of their exposures in a chamber. The 
paste of plates of the first group (Fig. 1a) presents a well-
formed skeleton that consisted of oblong crystal particles 
up to 3 m in length – according to X-ray technique tri-
basic lead sulfate (3PbO∙PbSO4∙H2O) (Fig. 2) and small-
er-sized particles of a rounded shape - lead oxide (-PbO) 
(Fig. 2). The composition of the second group plates 
(Fig. 1b) is of similar structure. However, there were 
unreacted free particles and aggregates the size smaller 
than 1 m. The third group (Fig. 1c) is characterized by a 
chaotic location and a different size and shape of un-
structured particles. In all samples studied low content 
of lead oxide in the form -PbO was found (Fig. 2). 
 
 
Fig. 2 – X-ray pattern of negative paste after maturation and 
drying 
 
 
 
Fig. 3 – Kinetic curves of moisture content changes in positive  
( ) and negative ( ) plates at their storage in the open 
air at a temperature of 25  1 ºС and a relative humidity of 
80  2 % 
 
Those structural differences in shape, size, and rela-
tive position of the particles in the third group were due 
to changes in moisture content during 2 h, which is cor-
roborated by kinetic curves (Fig. 3) from which the criti-
cal value of humidity reducing recrystallization level was 
determined [1]. The deference in kinetic regularities of 
moisture evaporation from negative plates is explained 
by its lower initial content and existence of auxiliary 
additives in electrode pastes. 
 
 
 
 
 
Fig. 4 – Structure of transverse cuts of “shunt – paste” for 
various ways of exposure of electrode plates: 1 – the first 
group; 2 – the third group 
 
 
 
Fig. 5 – Dynamics of nominal capacity changes for storage 
batteries according to cycles: ( ) – the first group,  
( ) – the second group. ( ) – the third group 
 
To analyze the state of the transitional layer “shunt – 
paste” transverse cuts were prepared with SEM. As 
SEM images show (Fig. 2) there exists an interphase 
transition in contrast – from light to solid dark, and in 
structure – from friable, which corresponds to a corro-
sive layer (to 30 m), to uniform –lead-calcium alloy of 
the shunt. In the surface layer of the lead paste of the 
third group electrode plates many microcracks (on the 
order of 1 m) and detachments appeared (Fig. 4b). 
To establish functional and electric characteristics 
of storage batteries tests were conducted the results of 
which are shown in Fig. 5. It was found that the sam-
ples of the first group at the second stage of “charging-
discharging” had the maximum nominal capacity, the 
maximum of which reached 64.4 Аh, whereas for the 
third group – 61.9 Аh, which is in line with the analy-
sis of phase and structural changes. Lower value of the 
nominal capacity for the third group’s batteries was  
b 
a 
 KINETIC CHARACTERISTICS, PHASE AND STRUCTURAL CHANGES… J. NANO- ELECTRON. PHYS. 5, 04026 (2013) 
 
 
04026-3 
     
 
 
 
Fig. 6 – Kinetics of current changes in samples of various groups: ( ) – the first group, ( ) – the second group.  
( ) – the third group; (25  1ºС without cooling, 16 V at batteries charging); a – Imax  25 A; b – Imax  18 A; c – temperature 
changes as for b-case 
 
obviously due to significant inhomogeneity of the sur-
face structure (Compare Fig. 4a and Fig. 4b).  
The fact that the capacity of the third group’s bat-
teries was constant is indicative of a low activity of the 
charge-forming electrode surface. 
Charging capacity of batteries was checked when 
these charged at a constant voltage of 16 V after 20-h 
discharging. In the samples of the first group the elec-
trodes have the lowest transitional resistance of 
“shunt-active mass” and hence, electric energy losses to 
overcome internal resistance were minimal.  
The distinction among internal resistances was es-
tablished by studying the kinetics of decreasing re-
sistance (Fig. 6a, b), which is also supported by an ab-
rupt increase in electrolyte temperature for samples of 
the third group. Two hours of discharging the current 
value remained constant and was equal to 25 A; elec-
trolyte temperature of the samples of the first and se-
cond group amounted to 40 ºС, while of the third 
group’s samples amounted to 45 ºС, which is obviously 
due to dramatically higher resistance. 
 
4. CONCLUSIONS 
 
Thus, functional and electric characteristics of stor-
age batteries critically depend on physico-chemical pro-
cesses occurring within the lead paste and on the bor-
der of the “shunt-paste”, which are most dependent on 
both the initial moisture content in the lead paste and 
keeping enhanced humidity in the exposure chamber 
for plates. 
 
 
REFERENCES 
 
1. D. Pavlov, Lead-Acid Batteries Science and Technology 
(Elsevier science: 2011). 
2. A.P. Kuzmenko, A.V. Stepanov, V.F. Niyazi, A.M. Ivanov, 
E.A. Grechushnikov, V. Kharseev, Proceedings of  
Southwest State University. Physics-Chemistry 41, 2 
(2012). 
 
a b 
c 


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