Studies on nano ceramic filler doped Polyacrylonitirle based Polymer

Electrolytes and its applications in sodium ion battery

K.V.S.N Raju1*, A.Nagarjuna2, Shaik Salma Begum3 and B.M Praveen4
1
PDF Scholar, Department of Physics, Srinivas University, Mangalore, Karnataka-574146, India
2
Department of Physics, Teegala Krishna Reddy Engineering College, Meerpet, Hyd-500097,
India
3
Department of Physics, Krishna University, Machilipatnam – 521003, India
4
Director, Research and Innovation Council, Srinivas University, Mangalore, Karnataka- 574146,
India
Corresponding author: raju.kvsnr@gmail.com
Abstract: In the present work, we report innovative study on the prepared Polyacrylonitrile
complexed Polymer ion conducting electrolyte membranes is doped by different ratios of Al 2O3
ceramic filler in solution cast method. In this preparation N, N-dimethyl formamide (DMF) is used
as common solvent and dopant salt is Sodium fluoride (NaF). The analysis of phase complexation
of doped chemicals and nature of crystallinity with changing concentration of the nano filler with
the help of Energy Dispersive Spectroscopy (EDS). The UV-Visible Spectroscopy result has been
observed the structural changes of prepared electrolyte membranes with doping salts and ceramic
filler. The Differential Scanning Calorimetry (DSC) result has been ascertained the melting
temperature variations due to incorporation of ceramic fillers. The prepared films were exhibited
good mechanical strength. The electrochemical cell was prepared and calculated discharging
values at constant resistance of these electrolyte membranes. A fine correlation has been
established between the evaluated results compared with previous reports.
Keywords: Ceramic fillers, Transition temperature, ionic Conductivity, crystallinity, Discharge
profiles.

INTRODUCTION

Now a days there has been tremendous interest in the preparation of polymer systems with
maximum ionic conductivity, thermal stability and good mechanical strength due to play a major
role in solid state batteries fuel cells, electrochromic windows, sensors etc.[1-2]. Most of the
polymer electrolytes are solid Gel and Composite polymers have been developed to improve
battery performance. These polymers perform a vital role in battery technology [3]. The present
work aims to develop on Gel polymer matrixes. The base polymer membranes Poly acrylo nitrle
(PAN) was used to develop ceramic filler and which was an exceptional Polymer and dissolved in
high concentrations of wide variety of salts. Moreover, it has been revealed that –CN group in
PAN could interact with Na+ ions and PAN might provide rigidity to the polymer electrolytes with
high Sodium ion conduction. In this work we report both the Optical, Structural, Thermal
Mechanical and Discharge Characteristics of polymer electrolyte of PAN+NaF (70:30) doped
with different wt% ratio Al2O3 nano fillers.

EXPERIMENTAL

The solid polymer electrolyte films of Poly acrylonitrle (PAN) of average molecular weight
1, 50,000 g/mol (Aldrich chemical Co) and Al 2O3 nano fillers (Aldrich research grade, Particle size
5.8 nm) doped PAN, PAN+NaF (70:30) + Wt% Al2O3 were prepared by weight percent ratios wt
%,2wt%,3wt%,and 4wt% by solution cast technique using Dimethyl Formamide (DMF) as solvent
and Sodium Fluoride NaF (Fluka) salt with different ratios 100:0,90:10,80:20,70:30 and 60:40 and
Ethylene carbonate EC (Spectrum) as plasticizer. The mixture of PAN and NaF solutions was
stirred for 48 hours at room temperature to obtain a homogeneous solution. The solution then taken
into propylene dishes and evaporate slowly at vacuum hot air oven at 60 0C upto 48 hours for
obtaining transparent films.
Materials Characterization

The EDS Spectroscopy is one of the important techniques to explain structural and
chemical composition. The composition of doped materials was perfectly revealed by Energy
Dispersive Spectroscopy (EDS). This technique is used for elementary analysis and also perfectly
analyzed chemical properties of employed materials. Based on peaks the chemical composition
type perfectly revealed. Hewlett-Packard HP8452A diode array spectrometer was used to study the
optical properties. The optical property helps to know structural properties which lead to
conductivity nature of samples. The UV-Vis spectrum clearly determine optical band gap. The
structural property easily analyzed with the help of UV-Vis spectrum. To measure glass transition
temperature (Tg) and melting temperature (Tm) of prepared PAN – based electrolyte membranes by
using Instrument (Mettler) within the range of 50-300 0C conducted under a nitrogen flow rate of
ca. 20 mL/min. With the help of Universal Tensile Machine (Instron Model 5565, Canada) with
the constant cross head speed of 10 mm/min mechanical properties of the prepared polymer
electrolytes were determined. Electrochemical cells were fabricated with the help of prepared
samples and their discharge profiles were studied under constant load.
RESULTS AND DISCUSSIONS

Fig.1. Prepared Nano composite Gel polymer electrolyte film.

Energy Dispersive Spectroscopy (EDS)

Energy Dispersive Spectroscopy (EDS) is used to study structural properties

prepared polymer electrolyte. Which helps to Perfectly analyze the doped materials composition.
Fig.1.represents that prepared Gel Polymer Electrolyte film based on nano filler. Fig.2 and Fig.3
shows the comparative analysis of the chemical weight and atomic weight of the elements in the
samples. The analysis indicates the presence of Carbon(C), Nitrogen (N), sodium (Na), Fluoride
(F) oxygen (O) and Aluminum (Al) with chemical composition in the gel polymer electrolyte of
PAN+NaF (70:30) + Wt% Al2O3 & structural complexation studies revealed.

Table.1. chemical weight and atomic weight of PAN+NaF (70:30) + 1-4 wt% Al2O3

1Wt% Al2O3 2Wt% Al2O3 3Wt% Al2O3 4Wt% Al2O3

Element Weight Atomic Weight Atomic Weight Atomic Weight Atomic
% % % % % % % %
C 66.89 71.18 56.71 61.76 63.37 67.91 65.32 69.54
N 23.62 21.55 30.73 28.69 26.56 24.41 26.26 23.97
O 7.55 6.03 8.37 6.84 7.47 6.01 7.03 5.62
F 1.46 0.98 2.93 2.02 1.96 1.33 0.95 0.64
Na 0.42 0.24 0.94 0.53 0.45 0.25 0.31 0.17
Al 0.06 0.03 0.32 0.16 0.19 0.09 0.14 0.07
Total 100 100 100 100 100 100 100 100
Fig.2. Chemical Wt% of 70PAN: 30NaF complexed with 1-4 wt% of Al2O3,

Fig.3. Atomic Wt% of 70PAN: 30NaF complexed with 1-4 wt% of Al2O3

UV-Visible Spectroscopy

The UV-visible spectrometer was used to study the structural properties of prepared
PAN/NaF polymer electrolyte films. This property leads to explain the ionic conductivity of the
polymer electrolytes. The UV-visible spectra of the material provides an important information
about the details related with energy band gap. The energy band gap revealed by E g= hc/λ. Where
h=6.626 x 10-34 joules-sec. is the Planck’s constant, C=3 x 108 meter/sec. is the velocity of light in
space and λ is the cut off wavelength.

Plotting the graph between wavelength and energy for 70 PAN: 30NaF with (1-4) wt%
Al2O3 . It was cleared from these graphs and calculated energy band gap values the decrement of
energy gap with increasing concentration of nano wt% Al2O3. The variation of energy band gap with
wavelength is shown in Fig.4. The defects produces in the optical gap results in an increase in the
degree of disorder in the films due to presence of Al 2O3 [4-10]. From Table.2 the results are in good
agreement with those obtained from EDS and a conductivity study in the present work.
 Table 2: Eg for prepared polymer electrolytes based on 70/30/(1-4) PAN/NaF/Al2O3.

GPE Planks Constant Velocity of Light λ (Ǻ) Eg (ev)

(h) (C)

70PAN:30NaF 6.62 x 10-34 j-sec 3 x 108 m/sec 346.0 3.5876

70PAN:30NaF:1wt%Al2O3 6.62 x 10-34 j-sec 3 x 108 m/sec 341.0 3.6341

70PAN:30NaF:2wt%Al2O3 6.62 x 10-34 j-sec 3 x 108 m/sec 348.0 3.5664

70PAN:30NaF:3wt%Al2O3 6.62 x 10-34 j-sec 3 x 108 m/sec 354.0 3.5063

70PAN:30NaF:4wt%Al2O3 6.62 x 10-34 j-sec 3 x 108 m/sec 361.0 3.4383

Fig.4. Wavelength-Energy plots of 70PAN:30NaF with (1-4) wt% Al2O3.

DSC Characteristics

The thermal effects of different wt% ratios of Al2O3 nano fillers on polymer electrolyte of
PAN+NaF (70:30) is investigated using Differential scanning calorimetry (DSC). In Fig. 5,
eat flow at various temperatures of pure PAN+NaF (70:30), 70PAN:30NaF doped by 1,2,3
and 4 wt% Al2O3 are presented. The peak corresponding to the melting temperature (Tm) and
crystallinity (χc) of PAN+NaF is discovered at 315.15°C and 98% respectively. Where ΔH m*
is the enthalpy of heat of sample, Poly acrylo nitrle has T m , Tg and ΔHm of 3150C, 1040C and
386.95 J/g respectively. When 1-4 wt% of Al2O3 nano was added to polymer matrix, the
melting temperature (Tm) was decreased. The polymer transition temperature (T m) moved
towards the lower temperature side when different amounts of Al 2O3 were added to the
prepared electrolyte membrane 70 PAN: 30NaF polymer electrolyte. The decrease in Tm of the
polymer electrolyte with increased Al 2O3 content. The least value proposed for 4wt% Al 2O3
nano powder content the Tm valve is 227.230C. Which suggests a weaker intermolecular
connection between the Al2O3, Sodium Floride salt, and PAN, allowing the polymer network
to move more segmentally by making the polymer matrix more segmental by making the
polymer matrix more Flexible [12-15].

The percentage of crystallinity was measured with the help following the equation [11].

χc =∆Hm*/398.6jg-1 (1)

Table .3: Tm, ∆Hm , χc of 70PAN/30NaF/ (1-4) wt% Al2O3.

Sample Tm(0C) ∆Hm*((j/g) Crystallinity (%)

Pure (Filler free) 315.14 386.95 98

1 wt% Al2O3 308.61 334.82 84

2 wt% Al2O3 302.25 289.71 72

3 wt% Al2O3 293.73 243.14 61

4 wt% Al2O3 281.12 227.20 57

 Fig.5. The DSC Thermographs of 70PAN:30NaF with (1-4) wt% Al2O3.

Al2O3 nano action produces a reduction in the T m and (ΔHm) of polymer gel electrolyte
membranes when it is added. The speed of sodium ions effected at polymer interaction in the
polymer chain and good agreement with TGA results [16-18]. Crystallinity and melting
temperature was successfully controlled by the addition of Al 2O3 and achieved the lowest
value (approximately 10.79%) for the membrane contains a higher amount of Al2O3 (4 wt %).

Fig.6 .Temperature V/S Crystallinity of 70PAN:30NaF with (1-4) wt% Al2O3.

Mechanical Properties

Mechanical behavior is mainly depends on the geometry, particle size distribution and
concentration of the filler. Stress and Strain are the two principle parameters used to describe the
mechanical property of polymer. This behavior of polymer electrolytes is useful for storage
manner and fabrication of cell assembly. At the initial stage of all the samples follows Hooks
law so strain increases linearly with stress. The ratio of stress to strain in the region of the stress
strain curve is Modulus. It is well known that the modulus increases for a polymer when nano
filler is incorporated into it. The exact nature of the tensile response of a polymer material
depends on molecular weight distribution, the chemical structure and conditions of the
sample preparation [19]. At normal temperature and pressure, polymer electrolytes exhibit an
increase in stress with increasing strain up to the point of sample failure. The stress at failure is
called ultimate stress or stress at break. Table 4 reports the typical value of modulus and ultimate
stress of the polymer electrolyte composites. A very good linear fit is obtained for all the curves
in Figure 7, with 99% correctness by origin plot indicates that with increasing of ceramic filler
ratio the mechanical properties enhanced. The dimension of stability was strengthening with
effect of ceramic fillers to the polymer electrolytes [20].

Table .4: Normal stress - strain of 70PAN/30NaF/ (1-4) wt% Al2O3.

Normal Stress (MPa)

Normal Strain 1 wt% Al2O3 2 wt% Al2O3 3 wt% Al2O3 4 wt% Al2O3

1 0.12 0.41 0.72 0.90

2 0.63 0.92 1.64 2.25

3 1.11 1.59 2.42 3.62

4 1.61 2.19 3.37 5.16

5 1.98 2.58 3.84 6.04

6 2.19 2.76 4.26 6.53

Table .5: Modulus of 70PAN/30NaF/ (1-4) wt% Al2O3.

 Name of the Sample Ultimate Stress Young’s modulus
(MPa) (GPa)
1 wt% Al2O3 2.19 ± 0.05 0.0365 ± 0.004
2 wt% Al2O3 2.76 ± 0.03 0.0460 ± 0.002
3 wt% Al2O3 4.26 ± 0.04 0.0710 ± 0.004
4 wt% Al2O3 6.53 ± 0.02 0.1089 ± 0.005

Fig. 7. Tensile Test of 70PAN:30NaF with (1-4) wt% Al2O3 (stress-strain Curve).

Cell Discharge Profile

Electrochemical cells were fabricated with the configuration Na-PAN: NaF: Al 2O3 (70:30:4)/
(I2+C+Electrolyte). Figure 8 shows the discharge characteristics of the cells at ambient temperature
for a constant load of 100 kΩ. The initial sharp decrease in the voltage of the cells may be due to
the polarization and formation of a thin layer of sodium salt at the electrode/electrolyte interface.
The discharging time for this prepared cell based on 1-4 wt% of Al 2O3 at different voltages are
clearly noted in Table.5. The short circuit current, open circuit voltage, current density power
density and other cell parameters for these cells are given in Table 6. The results of present
investigations support the possible practical application of the polymer electrolytes in solid-state
batteries.

Table 5. Discharge time for the prepared cell based on 1-4 wt% of Al2O3

Voltages
 1wt%Al2O3 2wt%Al2O3 3wt%Al2O3 4wt%Al2O3
Time (hrs)
0 3.7 3.4 3.2 2.85
10 3.5 3.1 2.7 2.5
20 3.2 2.7 2.45 2.2
30 2.8 2.3 2.1 1.9
40 2.4 1.9 1.7 1.6
50 2.2 1.75 1.5 1.3
60 1.9 1.55 1.4 1.2
70 1.7 1.2 1 0.8
80 1.5 1.1 0.9 0.75
90 1.3 1 0.8 0.6
100 1.1 0.8 0.7 0.5
110 0.9 0.7 0.6 0.5
120 0.8 0.7 0.6 0.5
130 0.6 0.5 0.4 0.25
140 0.5 0.4 0.3 0.25

Fig.8. Discharge characteristics of Filler free complexed with 1-4 wt% of Al2O3 nano
filler polymer electrolyte electrochemical cell (load =100KΩ).

Table 6: Cell parameters of PAN: NaF+ Al2O3 /( I2+C+Electrolyte) polymer

electrolyte battery

Different Profiles of Cell Na-PAN:NaF-Al2O3

(70:30:4)/(I2+C+Electrolyte)
 Open circuit voltage (V) 1.98
Short circuit current (A) 1.5
Effective area of the cell (cm2) 1.20
Weight of the cell (gm) 1.60
Discharge time in plateau region (h) 140
Current density (µA /cm2) 2.36
Power density (W /Kg) 2.94
Energy density (Wh/ Kg) 325
Discharge capacity (µA/ h) 167.9

Conclusions

The PAN based polymer electrolyte PAN: NaF: Al2O3 films successfully prepared
with the help of Sol-Gel techniques. The maximum ionic conductivity was to be found 6.82 x
10-3 S/cm at 373K temperature. The structural properties perfectly obtained by EDS, UV-Vis
and Mechanical properties. The glass transition temperature of polymer films perfectly
revealed from DSC studies. The electrochemical cell study explains perfectly for fabrication
of solid state battires.

REFERENCES

1. Anji Reddy Polu and Ranveer Kumar, Chinese J. Poly. Sci, Vol. 31, No. 4, 641−648 (2013).
2. M. Jaipal Reddy, Peter P. Chu, T. Sreekanth & U. V. Subba Rao, J.Mat.Sci.Mat.Ele. Vol
12, 153–156 (2001).
3. J. Ramesh Babu , K. Ravindhranath , and K. Vijaya Kumar, Int.J.Pol.Sci.Vol. 2018, 9(2018).
https://doi.org/10.1155/2018/7906208
4. Fatama Ahmad, Moukhtar A. Hassan, Poly.Comp, Vol.40.No. 1, E647-E653(2019).
5. Qingguo Chi, Xubin Wang,Changhai Zhang,Qingguo Chen,Minghua Chen,Tiandong Zhang,
Liang Gao,Yue Zhang,Yang Cui, Xuan Wang and Qingquan Lei, ACS Sust.Chem.Eng.Vol.6,
8641-8649 (2018).
6. Rasha Al-Bayer, Awwad Zihlif, Bashar Lahlouh, Ziad Elimat, Giuseppe Ragosta, J.Mater.Sci:
Mater Elec, Vol.24, 2866-2872 (2013).
7. D.Ravindran, T.Sornakumar, D.S Pritviraja Durai and V.Varatharajan, International Journal of
ChemTech ResearchCODEN (USA): IJCRGG ISSN: 0974-4290 Vol.7, No.3, pp 1323-1328,
(2015).
8. Ahmad A. Ahmad, Mais H. Khazaleh, Ahmad M. Alsaad,Qais M. Al-Bataineh, Ahmad D.
Telfah, Poly.Bult,Vol.79, 9881–9905, (2022).
9. Kim. Minfyeong, Lee. Lyungyu, Jung. Yongju, Kim. Seok, J.N. Sci.N.tech. Vol.13, No.12,
7865-7869(2013)
10.Sangita Chavda, Nehanshi Limbasiya, Poonam Vamja, Ajay Vaishnani, Kush Vachhani,
Bharavi Hirpara, Manjula Kandoliya, Keval Gadani, Davit Dhruv, A. D. Joshi, P. S. Solanki &
N. A. Shah Journal of Sol-Gel Science and Technology,Vol.104, 169–177 (2022).
11. F. Kanwal A. Batool M. Adnan Materials Research Innovations, Vol. 19 (8), 354 – 358 (2015)
12. Evangelia Tarani, Ioannis Arvanitidis, Dimitrios Christofilos, Dimitrios N. Bikiaris,
Konstantinos Chrissafis and George Vourlias, J.Mat.Sci, Vol. 58 1621-1639 (2023).
13. Osiris W. Guirguis, Manal T. H. Moselhey, Sci.Res. Vol .4 No.1 (2012)
DOI:10.4236/ns.2012.41009.
14. C. Subbu, Chithra M. Mathew, K.Kesavan, S. Rajendran, Int. J. Electrochem. Sci.,Vol. 9, 4944
– 4958 (2014).
15. K.K. Wimalaweera, V.A. Seneviratne and M.A.K.L. Dissanayake, Pro. Eng, Vol. 215, 109-114 (2017).
16. Prajakta Jogea, Dinesh Kumar Kanchan, Poonam Sharmaa and Nirali Gondaliyaa, Ind.J. P. App.Phy.
Vol. 51, 350-353 (2013).
17. C. C. Sun, A. H. You, L. L. Teo, and L. W. Thong, AIP. Conf.Pro.Vol. 1958, 020028 (2018);
https://doi.org/10.1063/1.5034559.
18. Mingyeong Kim, Lyungyu Lee, Youngju Jung, Seok Kim, J.N.Sci.N.tech. Vol.13,No.12 7865-
7869 (2013).
19. R. Abraham, S. P. Thomas, S. Kuryan, J. Isac, K. T. Varughese, S. Thomas, eXPRESS Poly.
Lett. Vol.3, No.3 (2009) 177–189
20. John Ojur Dennis, Mohammed Khalil Mohammed Ali, Khalid Hassan Ibnaouf, Osama
Aldaghri , Naglaa F. M. Abdel All, Abdullahi Abbas Adam, Fahad Usman, Yarima Mudassir
Hassan and Bashir Abubakar Abdulkadir, Mol. Vol.27, No.5528, 1-27(2022).
21.Shvera Malhotra and Pradeep K. Varshney Int.J.Appl.Eng. Res.vol.10, No.94, 108-112 (2015).
22. Kaikai Li, Jun Zhang, Dongmei Lin, Da-Wei Wang, Baohua Li, Wei Lv, Sheng Sun, Yan-Bing
He,Feiyu Kang, Quan-Hong Yang, Limin Zhou and Tong-Yi Zhang. Nature.Com. Vol.10,
No.725,1-10 (2019).
23. Vo Pham Hoang Huy, Seongjoon So and Jaehyun Hur, Nano.mat, Vol.11, No.3, 614 (2021).24.
Karlsson, C.; Best, A.; Swenson, J.; Howells, W.; Börjesson, L. Polymer dynamics in 3PEG–
LiClO4–TiO2 nanocomposite polymer electrolytes. J. Chem. Phys. 118, 4206–4212 (2003).

25. Yarmolenko, O.; Yudina, A.; Marinin, A.; Chernyak, A.; Volkov, V.; Shuvalova, N.; Shestakov, A.
Nanocomposite network polymer gel-electrolytes: TiO 2-and Li2TiO3-nanoparticle effects on their structure
and properties. Russ. J. Electrochem. 51, 412–420,( 2015).
26. Sivakumar, M.; Subadevi, R.; Muthupradeepa, R. Studies on the effect of dispersoid (ZrO 2) in PVdF-co-
HFP based gel polymer electrolytes. Am. Inst. Phys. 2013, 1536, 857–858.
27. Zhou, D.; Shanmukaraj, D.; Tkacheva, A.; Armand, M.; Wang, G. Polymer electrolytes for lithium-
based batteries: Advances and prospects. Chem. Rev. 2019, 5, 2326–2352.
28. Penghui Yao, Haobin Yu, Zhiyu Ding, Yanchen Liu, Juan Lu, Marino Lavorgna, Junwei Wu
and Xingjun Liu, Front. Chem. Vol.7 ( 2019).