J. Int. Sci. Technol. 2020, 8(1), 1‐5 . Article .

Journal of Integrated
SCIENCE & TECHNOLOGY

Development of Red Seaweed extracted film for energy saving Batteries

M. Nithya,1,2 M.Alagar,1,3 B. Sundaresan1
1
Centre for Research and Postgraduate studies in Physics, Ayya Nadar Janaki Ammal College, Sivakasi. TamilNadu, India.
2
Department of Physics, The S.F.R College for Women, Sivakasi, TamilNadu, India. 3Post graduate Department of Physics,
Mannar Thirumalai Naicker College, Madurai. TamilNadu, India.
Received on: 05-Jan-2020, Accepted and Published on: 01-May-2020

ABSTRACT

Red seaweed extract, kappa‐carrageenan (KC) is used to fabricate a flexible battery with an ammonium salt. A combination of the film was
successfully synthesized by the Solution Casting technique. The prepared eco‐friendly film is subjected to ionic conductivity study, transference
number studies, and then the high response film is used to fabricate battery. The highest ionic conductivity value for 1gm kappa‐carrageenan
with 200 mg NH4Cl is 2.99 × 10‐4S/cm. The highest conducting seaweed extract film transference numbers are very close to unity. By using this
biopolymer film, the fabricated biopolymer battery generates the maximum of open‐circuit voltage is 1.74V. By using this proton ion battery
we can replace liquid ion battery and solid ion battery. Also, the films are easily biodegradable and not at all generate e‐waste.
Keywords: Red seaweeds extract, Kappa-carrageenan, Flexible film, Conductivity, Battery fabrication

their abundant in nature, low cost, friendliness to the environment

INTRODUCTION and potential as a substitute for some petrochemicals12. In this
In a green economy, the demands for biopower enhance the way, an ideal solid BPE in the polymer electrolyte system
technological interest in the field of solid biopolymer electrolyte contributes to free pollution and it has directly brought forward
(BPE). In recent years, this highly specialized field encompasses green nation, which fosters the interest in research to address the
to play a vital role in designing energy-based devices, replacing environmental crises. Several researchers are doing their research
liquid electrolyte in fuel cells, electrochemical sensors, batteries, in the field of biopolymer using starch13-14, cellulose, chitosan,
and electrochromic devices1-8. The Solid BPE provides good pectin, agar, and Kappa-carrageenan.
contact surface with electrodes, good shelf life, less problem with Kappa-carrageenan extracted from red seaweed alga to form
leakage or pressure distortion and also the BPE is easy to prepare complex arrangements. The use of this to form thin flexible film
and very affordable9,10,11. However, the synthetic polymer faces and is used to fabricate battery devices. Fabrication of thin-film
disadvantage and not being environmentally green. Hence, it is battery is an emergent field in the year 2019 to 2029.15
imperative to develop the biopolymer electrolytes by using natural Biopolymer films are mechanically behaving like a solid but
polymer, which has gained more and more attention, owing to the conductivity behavior is like a liquid state.16 The conductivity
of a material is the major property of electrical appliances. The
Corresponding Author: Mrs. Manikam Nithya conductivity of the material is different for different materials.
Department of Physics, SFR College for Women, Sivakasi. Production of electricity in the material depends on the dissolved
Tamilnadu.
impurities in the material. Depending upon the suspended ions the
Tel:
Email: nina07.muma@gmail.com electrical charge is transferred in the material. Based on
conductivity and resistivity, the conducting material is segregated
Cite as: J. Int. Sci. Technol., 2020, 8(1), 1-5. into two main categories. The first one is the highest conductivity
©IS Publications ISSN: 2321-4635 http://pubs.iscience.in/jist
Journal of Integrated Science and Technology J. Int. Sci. Technol., 20120, 8(1), 1‐5 1
 M. Nithya et. al.
or lowest resistivity materials and the second one are the lowest of the KC: NH4Cl biopolymer electrolyte is in the range of
conductivity or highest conductivity materials. In the field of 0.01265-0.01275 cm. These biopolymer electrolytes have been
electrical engineering applications, both the highest conducting characterized by different experimental techniques. The different
materials and the lowest conducting materials play a vital role. biopolymer electrolyte systems prepared are:
The low conducting materials like carbon, tungsten are useful to 1gm KC
fabricate the heating elements. The material of low resistivity and 1gm KC:100mg NH4Cl
high conductivity is useful for an electrical machine, transmission, 1gm KC:200mg NH4Cl
and distribution of electrical energy. 1gm KC:300mg NH4Cl
Here our aim is to find the highest conducting material for
battery fabrication. The Highest conducting materials have the
CHARACTERIZATION TECHNIQUES
properties of the lowest possible resistance, the highest possible X-RAY DIFFRACTION (XRD) ANALYSIS
conductivity, good mechanical strength, stability, corrosion-free, The amorphous nature of biopolymer electrolytes has been
low cost, long life, and a high elasticity17-19. Conducting materials investigated using XRD. The XRD patterns of the films were
are varying for various purposes. The present work is to find a recorded at room temperature by X’ pert pro diffractometer
flexible, high conducting solid biopolymer electrolyte. Because of system using the Cu-kα radiation in the range of 2θ= 10° to 50°.
the applications (electronics, fuel cells, solar cells, and batteries)
of bio-polymer membranes, researches are increasing day by day. DIFFERENTIAL SCANNING CALORIMETRY (DSC)
From my literature, there is less usage of red seaweed kappa- The thermal stability of the BPE's has been studied using DSC
carrageenan in the field of battery fabrication. But the property of Q20 V4.10 build 122 with a resolution of 0.01 mg. The films were
kappa carrageen is suitable for the current scenario. Because KC taken in an aluminum pan and heated upto 500 °C with the
is a biopolymer and it is biodegradable, eco-friendly and heating rate of 5 °C per minute under controlled air atmosphere
available. And also, KC has good electrical and mechanical and the films were purged using a nitrogen atmosphere during the
property. The conductivity of pure kappa-carrageenan is measurements. Dry nitrogen gas at the rate of 50 ml/min has been
increased by the best selection of added impurities. The selection purged through the cell during the thermal treatment.
of impurity is another target to achieve the highest conducting IMPEDANCE SPECTROSCOPY
flexible biopolymer. Proton conductors are difficult to achieve
Impedance analysis has been performed using impedance
because of its transport property discovered in 1990s20 even
spectrometer, which is a powerful method for characterizing the
though, we have selected a proton-conducting NH4Cl to achieve
ionic conductivity of freshly casted samples. Prior testing, the
the highest conducting electrolyte. As we expected, prepared
thickness of the films was measured by using a digital screw
biopolymer conductivity increased two order magnitudes by
gauge. Then, films with well known thickness (0.01265-0.01275
adding NH4Cl to kappa carrageenan.
cm) have been sandwiched between two stainless steel blocking
In this present work, we have synthesized the biopolymer film
electrodes and tested using HIOKI 3532 in the range of 42 Hz-1
by the new choice of red seaweed extracted biopolymer kappa
MHz with various temperatures from 303 k to 343 k.
carrageenan with different concentration of ammonium NH4Cl21.
Then the highest conducting electrolyte is used to fabricate the FABRICATION OF PROTON BATTERY
proton-conducting battery. Using the highest conducting BPE 1gm KC: 200mg NH4Cl a
proton battery have been constructed and their results are
EXPERIMENTAL
discussed.
CHEMICALS:
RESULTS AND DISCUSSION
Chemicals selected for this work is red seaweed extracted
kappa-carrageenan (KC)22 and NH4Cl were purchased from TCI X-RAY DIFFRACTION (XRD) ANALYSIS
chemicals. Figure 1 shows the XRD patterns of pure KC and KC with
different concentrations of NH4Cl. The XRD patterns indicate that
BIOPOLYMER FILM ELECTROLYTE PREPARATION
the solid polymeric films were contain amorphous phases, which
For Kappa Carrageenan+Ammonium Chloride (KC+NH4Cl)
make the polymeric films to be in flexible in nature.
biopolymer electrolyte film preparation, Kappa Carrageenan
The figure 1 indicates that the amorphous nature of doped
(C24H36O25S2-2) (M.W = 788.7 g/mol), salt ammonium chloride
polymer KC increases, when the NH4Cl salt is incorporated into
(NH4Cl) (M.W = 53.491 g/mol) purchased from TCI chemicals
the KC matrix. The XRD patterns also indicates that the broadness
private Ltd., Tamilnadu, India. And the solvent distilled water
of peak increases and its relative intensity decreases with increase
(H2O) (M.W = 18.015 g/mol) has been Used for this electrolyte
of NH4Cl concentration, which reveals that as ion concentration in
preparation. The biopolymer electrolyte has been prepared by
the electrolyte increases, both the fraction of amorphous phase and
dissolving KC and NH4Cl in distill water and mixtures are
charge carriers increases simultaneously23. From the XRD graph it
thoroughly stirred to obtain a homogenous mixture. The mixture
has been noted that 1gmKC:200mg NH4Cl has maximum
is then poured on a polypropylene dish and dried in the oven at 40
amorphous nature. The increase in the amorphous nature causes a
°C for 1 day to ensure the removal of solvent traces. After drying
reduction in the energy barrier to the segmental motion of the
the films have been peeled from Petri dishes. The film thickness

Journal of Integrated Science and Technology J. Int. Sci. Technol., 20120, 8(1), 1‐5 2
 M. Nithya et. al.
24
polymer electrolyte resulting in high ionic conductivity . On increases ionic conductivity. There are two factors involved in the
further addition of NH4Cl concentration, the intensity of peaks increase of Tg with the salt content: (1) interaction of H+ with the
increases for 1gm KC: 300mg NH4Cl, which indicates the polar group of the polymer increases the micro viscosity of the
increase in crystallinity. This is because the polymer host was solid biopolymer electrolyte, and (2) the polymer chain is
unable to accommodate the salt, which leads to the recombination expanded by the introduction charges on the polymer chain
of the ions.25 because of the electrostatic repulsion. This behavior has been
interpreted as a consequence of a reduction in segmental motion
caused by an increase in intermolecular and intermolecular co-
ordinations between H+ cations and the oxygen atoms in the
polymer chain.26

Figure 2. DSC thermo grams of (a) pure KC, (b) 1gm KC: 100mg
Figure 1. XRD pattern for (a) pure KC, (b) 1gm KC: 100mg NH4Cl, NH4Cl, (c) 1gm KC: 200mg NH4Cl, (d) 1gm KC: 300mg NH4Cl.
(c) 1gm KC: 200mg NH4Cl, (d) 1gm KC: 300mg NH4Cl.
IMPEDANCE SPECTROSCOPY
DIFFERENTIAL SCANNING CALORIMETRY (DSC)
Generally, the impedance plot consists of a distorted semicircle
DSC analysis was carried out to measure the glass transition in the high-frequency region followed by an inclined spike in the
temperature (Tg) of polymer electrolytes. The change in Tg of KC low-frequency region. The high-frequency semicircle is due to the
due to the addition of salt (NH4Cl) as shown in Figure 2. The Tg of parallel combination of bulk resistance (due to migration of ions)
pure KC was obtained at 41.59 °C. The Tg value was obtained as and bulk capacitance (due to immobile polymer chain). The low-
36.95°C, 29.16°C and 38.40°C for the membrane 1gmKC: frequency spike represented by a constant phase element is due to
100mgNH4Cl, 1gmKC:200mgNH4Cl and 1gmKC:300mgNH4Cl the formation of double-layer capacitance at the electrode-
respectively. The Tg values of prepared polymer electrolytes are electrolyte interface. The electrolytic conductivity of NH4Cl in
tabulated in Table 1. kappa-carrageenan was analyzed by the formula of

Table 1 Glass Transition Temperature of prepared polymer σ = t/ARb (S/cm)

electrolytes
Where‘t’ and ‘A’ are the thickness and area of the polymer
Polymer composition Tg (°C) electrolyte film respectively. Rb is the bulk resistance of the
1gm Pure KC 41.59 polymer membrane27. The Cole-Cole plots of the pure kappa-
carrageenan and ammonium salts doped kappa-carrageenan
1gm KC:100mg NH4Cl 36.95
biopolymer electrolytes are shown in figure 3.
1gm KC:200mg NH4Cl 29.16 The bulk resistance values were obtained from Cole - Cole plot
1gm KC:300mg NH4Cl 38.40 which were listed in Table 2.
In Table 2, the resistance value of pure KC was obtained as
The DSC curve in figure 2 indicates that the Tg value of KC 1.75×103Ω, whereas for 200mg of NH4Cl doped with 1gm KC
increases corresponding to the increase in the concentration of polymer electrolyte the value of resistance was decreased from
(100mg) NH4Cl and decreases with the concentration of 200mg 1.75×103Ω to 351Ω. The highest conductivity polymer electrolyte
NH4Cl. In general, the decrease in glass transition temperature 1gm KC:200mg NH4Cl has Rb = 351Ω.

Journal of Integrated Science and Technology J. Int. Sci. Technol., 20120, 8(1), 1‐5 3
 M. Nithya et. al.
IONIC TRANSPORT ANALYSIS:
Ionic transference numbers are calculated by the below-
mentioned equation, and it is determined by the Wagner
procedure.29
Tion = (I initial - I final)/ I initial
In this procedure, A fixed DC voltage of 1.8 V is applied across
the cell. The initial polarization current (110 μA) of the membrane
is decreased with time due to the depletion of the ionic species in
the electrolyte and finally, it is constant in the fully depleted
situation. This is because the ionic current through an ion-
blocking electrode falls rapidly with time. Calculated transference
numbers are very close to unity. That means the prepared film for
battery fabrication is highly polarized. Figure 4 shows the
Polarization current versus time plot for 1gm KC:200mg NH4Cl.
Figure 3. Cole - Cole plot of red seaweed extract kappa carrageenan
with NH4Cl

Table 2 Resistance value for all polymer electrolytes

Polymer composition R, (Ω)
1gm Pure KC 1.75×103
1gm KC:100mg NH4Cl 6.81×102
1gm KC:200mg NH4Cl 3.51×101
1gm KC:300mg NH4Cl 9.89×102
The calculated ionic conductivity for different concentrations of
KC:NH4Cl polymer electrolytes were listed in Table 3 for various
temperatures.

Table 3 Ionic conductivity data and activation energy values for

KC:NH4Cl polymer electrolyte for different temperature.
Polymer σ303 σ313 σ323 k σ333 σ343 Activation
composition k k k k energyEa Figure 4. Polarization current vs time plot for 1gm KC:200mg
(ev) at room NH4Cl.
temperature
FABRICATION OF SOLID PROTON BATTERY
Pure KC 6.03 6.11 7.37 7.38 9.78 0.01273
× × × 10- × × For a battery fabrication Anode is formed by zinc sulfate,
10-6 10-6 6 10-6 10-6 graphite, and zinc powder. The cathode is formed by vanadium
1gm 1.55 1.59 1.63× 1.84 2.08 0.06558 pentaoxide, graphite, lead oxide, 1gm kappa carrageenan and 200
KC:100mg × × 10-5 × ×10-
NH4Cl 10-5 10-5 10-5 4

1gm 2.99 3.10 3.18 3.27 3.30 0.02295

KC:200mg × × × 10- × ×
NH4Cl 10-4 10-4 4
10-4 10-4
1gm 1.07 1.08 1.13 1.16 1.22 0.029840
KC:300mg × ×10- × 10- × ×
NH4Cl 10-5 5 5
10-5 10-5

Table 3 indicates that among the various concentrations of

KC:NH4Cl polymer electrolyte the 1gm KC:200mg NH4Cl
polymer electrolyte has highest ionic conductivity (2.99 × 10-4S
cm-1) at room temperature, which also has a greater conductivity
than that of pure KC (6.03 × 10-6 S cm-1). The higher ionic
conductivity of 1gm KC:200mg NH4Cl may be arises due to the
transition from semicrystalline phase to an amorphous phase of
Figure 5. Open circuit voltage and discharge curve for the cell as a
the polymer complex and increase in charge carrier
function of time for 1gmKC:200mgNH4Cl polymer electrolyte.
concentration.28

Journal of Integrated Science and Technology J. Int. Sci. Technol., 20120, 8(1), 1‐5 4
 M. Nithya et. al.
mg NH4Cl. Both anode and cathode compounds are pelletized to 12. L. Ponez, F.C. Sentanin, S.R. Majid, A.K. Arof, A. Pawlicka, Ion
form a thin pellet. Prepared solid biopolymer electrolyte is Conducting Membranes Based on Gelatin and Containing Li/I2 for
Electrochromic Devices, Mol.Cryst. Liq. Cryst. 2012, 554, 239-251.
positioned between prepared anode and cathode, and this 13. M Selvakumar, DK Bhat, LiClo4 doped cellulose acetate as biodegradable
arrangement is situated in the battery holder30. In this work the polymer electrolyte for supercapacitors. J Appl Polym Sci 2008, 110, 594-
cell gave voltage of E = 1.74 V. The open-circuit voltage (OCV) 602
and discharge behavior of the cell with time was shown in figure 14. V. Vijayalekshmi, D. Khastgir, Eco-friendly methane sulfonic acid and the
5, which indicates that the cell potential decreases during sodium salt of dodecyl nensene sulfonic acid doped crosslinked chitosan
based green polymer electrolyte membranes for fuel cell applications. J.
discharge. The initial sharp decrease in voltage may be due to Membr Sci 2017, 523, 45-59.
polarization and it remains constant of 1.69 V for a particular 15. D. Li, G. Chang, L. Zong, P. Xue, Y. Wang, Y. Xia, C. Lai, D. Yang. From
duration after. The region in which the voltage remains constant is double-helix structured seaweed to S-doped carbon aerogel with ultra-high
called the plateau region. surface area for energy storage. Energy Storage Materials, 2019, 22-30.
16. P. Balaji Bhargav, V. Madhu Mohan, A.K Sharma. Structural and
CONCLUSION electrical properties of pure and NaBr doped poly (vinyl alcohol) (PVA)
polymer electrolyte films for solid state battery applications, Ionics 2007,
Red seaweed extract Kappa Carrageenan has unique physical
13, 441-446.
properties, powerful water reaction, plentiful functional groups. 17. M. Nithya, M. Alagar, B. Sundaresan. Eco-friendly biopolymer kappa
Worldwide use of non-toxic kappa carrageenan, research has carrageenan with NH4Br application in energy saving battery. Mater. Lett.
focused to make it versatile biopolymer for blending it with other 2020, 263, 127295.
ammonium salts to explore novel applications in solid-state 18. J.B. Goodenoough, K.S Park. The Li-Ion Rechargeable Battery: A
Perspective, J. Am. Chem. Soc. 2013, 135, 1167-1176.
polymer battery6. Due to the better conductivity and mobility,
19. D.Y. Park, D.Y. Park, Y. Lan, Y.S Lim, M.S.Kim, High rate capability of
these biodegradable kappa-carrageenan based flexible solid carbonaceous composites as anode electrodes for lithium-ion secondary
electrolytes in association with conducting salts were used in battery, J. Ind. Eng. Chem. 2009, 15, 588-594.
different biopolymer battery11 assemblies. The highest conducting 20. N.K. Zainuddin, A.S. Samsudin. Investigation on the effect of NH4Br at
biopolymer electrolyte kappa carrageenan with NH4Cl film is used transport properties in k–carrageenan based biopolymer electrolytes via
structural and electrical analysis, Mat. Today Commun. 2018, 14, 199-209.
to construct the power saving battery.
21. D.V Jamkar, B.J. Lokhande, S.B. Kondawar. Improved electrochemical
Conflict of Interest: Authors declare no conflict of interest. performance of free standing electrospun graphene incorporated carbon
nanofibers for supercapacitor. J. Mater. Nanosci. 2019, 6 (1), 32–37.
REFERENCES 22. V. Moniha, M. Alagar, S. Selvasekarapandian, B. Sundaresan, R.
1. A. Karmakar, A. Ghosh, Dielectric permittivity and electric modulus of Hemalatha, G. Boopathi, Synthesis and characterization of bio-polymer
polyethylene oxide (PEO)-LiClO4 composite electrolytes, Curr. Appl. electrolyte based on iota- carrageenan with ammonium thiocyanate and its
Phys. 2012, 12, 539-543. applications J. Solid State Electro chem. 2018, 22(10), 1-15.
2. W.H Meyer, Polymer electrolytes for lithium-ion batteries, Adv. Mater, 23. M.P. Aji, S. Masturi, Bijaksana, Khairurrijal, M. Abdullah, A General
1998, 10 (6):439-448. Formula for Ion Concentration-Dependent Electrical Conductivities in
3. I. Arockia Mary, S. Selvanayagam, S. Selvasekarapandian, S.R. Srikumar, Polymer Electrolytes, A.J. Appl. Sci. 2012, 9, 946–954.
T. Ponraj, V. Moniha, Lithium ion conducting membrane based on K- 24. M. V. Bhute, Y.P. Mahant, S.B. Kondawar. Titanium dioxide /
carrageenan complexed with lithium bromide and its electrochemical poly(vinylidene fluoride) hybrid polymer composite nanofibers as
applications, Ionics 2019, 10.1007/s11581-019-03150-x. potential separator for lithium ion battery. J. Mater. Nanosci. 2017, 4 (1),
4. M. Premalatha, T.M. Athavan, S. Selvasekarapandian, S. Monisha, S. 6–12.
Selvalakshmi, D. Vinoth Pandi, Ionics 2017, 10.1007/s11581-017-1989-x. 25. M.F.Z Kadir, S.R. Majid, A.K. Arof, Plasticized chitosan-PVA blend
5. M.X. Li, X.W. Wang, Y.Q. Yang, Z. Chang, Y.P. Wu, R. Holze, A dense polymer electrolyte based proton battery, Electrochimica Acta 2010, 55,
cellulose-based membreane as a renewable host for gel polymer 1475-1482.
electrolyte of lithium ion batteries, J. Memb. Sci 2015, 476, 112-118. 26. C.A. Angell, K. Xu, S.S. Zhang, N. Videa, Variations on the salt-polymer
6. R. Juliana .A.E. Raphael, A. Pawlicka, Plasticized pectin-based gel electrolyte theme for flexible solid electrolytes, Solid State Ionics 1996,
Electrolytes, Eletrochim. Acta 2009, 54, 6479-6483. 17, 17-28.
7. R. Singh, A.R. Polu, B. Bhattacharya, H.W. Rhee, C. Varlikli, P.K. Singh. 27. V. Moniha, M. Alagar, S. Selvasekarapandian, B. Sundaresan, G.Boopathi,
Perspectives for solid biopolymer electrolytes in dye sensitized solar cell G. Boopathi. Conductive bio-polymer electrolyte iota-carrageenan with
and battery application, Renew Sust Energ Rev 2016, 65, 1098-1117. ammonium nitrate for application in electrochemical devices, J. Non –
8. M.F. Shunkur, M.F.Z. Kadir, Hydrogen ion conducting starch-chitosan Crystalline Solids 2018, 481, 424-434.
blend based electrolyte for application in electrochemical devices, 28. H. Nithya, S. Selvasekarapandian, P. ChristopherSelvin, D. ArunKumar,
Electrochim. Acta 2015, 158, 152-165. M. Hema, D. Prakash, Physica B 2011, 406, 3367–3373.
9. S. Ramesh, C.W. Liew, A.K. Arof, Ion conducting corn starch biopolymer 29. S. Selvalakshmi, N. Vijaya, S. Selvasekarapandian, M. Premalatha.
electrolytes doped with ionic liquid 1-butyl-3-methylimidazolium Biopolymer agar-agar doped with NH4SCN as solid polymer electrolyte
hexafluorophosphate. J. Non- Cryst Saolids 2011, 357, 3654-3660. for electrochemical cell application. J. Appl. Polym. Sci. 2017, 134 (15),
10. A.S. Ahmad Khiar, A.K. Arof, Conductivity studies of starch based 44702.
polymer electrolytes. Ionics, 2010, 16, 123- 129. 30. P. Perumal, S. Selvasekarapandian, K.P. Abhilash, et al. Impact of lithium
11. K.P. Varshney, S. Gupta, Natural polymer-based electrolytes for chlorate salts on structural and electrical properties of natural polymer
electrochemical devices: a review, Ionics 2011, 17, 479-483. electrolytes for all solid state lithium polymer batteries. Vacuum 2019,
159, 277–281.

Journal of Integrated Science and Technology J. Int. Sci. Technol., 20120, 8(1), 1‐5 5