Abstract
In this present work, the investigation of solid biopolymer electrolytes (SBEs)-based alginate-doped NH4Br was carried out and prepared via casting technique. The SBEs system was characterized using Fourier transform infrared, thermal gravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscope, and electrical impedance spectroscopy. Based on IR-analysis, it was shown that the complexation between alginate and NH4Br has occurred based on the changes of peak at COO− group of alginate. The interaction led to the improvement in amorphous phase and thermal stability of SBEs system when NH4Br was added. The ionic conductivity of SBEs system was found to achieve maximum value at 4.41 × 10−5 S/cm when 20 wt. % of NH4Br was added and the value was comparable with other types of polymer electrolytes system. The temperature-dependence ionic conductivity of entire SBEs system obeys Arrhenius behavior where the R2 ~ 1 and present system are thermally assisted. From IR-deconvolution approach, it can be found that the ionic conductivity of alginate-NH4Br SBEs system was governed by ions mobility, μ and diffusion coefficient, D. All these findings imply that present alginate-based SBEs system is potential to be applied in electrochemical devices, i.e., proton battery, supercapacitor and fuel cell.
This is a preview of subscription content,
to check access.










References
Monisha S, Mathavan T, Selvasekarapandian S, Benial AMF, Aristatil G, Mani N, Premalatha M (2017) Investigation of bio polymer electrolyte based on cellulose acetate-ammonium nitrate for potential use in electrochemical devices. Carbohydr Polym 157:38–47
Tan G, Wu F, Zhan C, Wang J, Mu D, Lu J, Amine K (2016) Solid-state li-ion batteries using fast, stable, glassy nanocomposite electrolytes for good safety and long cycle-life. Nano Lett 16(3):1960–1968
Sohaimy MIH, Isa MIN (2017) Ionic conductivity and conduction mechanism studies on cellulose based solid polymer electrolytes doped with ammonium carbonate. Polym Bull 74(4):1371–1386
Rasali NMJ, Nagao Y, Samsudin AS (2019) Enhancement on amorphous phase in solid biopolymer electrolyte based alginate doped NH4NO3. Ionics 25(2):641–654
Samsudin AS, Kuan ECH, Isa MIN (2011) Investigation of the potential of proton-conducting biopolymer electrolytes based methyl cellulose-glycolic acid. Int J Polym Anal Charact 16(7):477–485
Ahmad NH, Isa MIN (2015) Structural and ionic conductivity studies of CMC based polymerelectrolyte doped with NH4Cl. Adv Mater Res 1107:247–252
Shukur MF, Kadir MFZ (2015) Hydrogen ion conducting starch-chitosan blend based electrolyte for application in electrochemical devices. Electrochim Acta 158:152–165
Chappalwar T, Ojha S (2018) Shelf life enhancement of muscle foods with biodegradable film packaging. J Anim Feed Sci Technol 6(33):39
Kumar R, Sharma RK, Singh AP (2018) Grafted cellulose: a bio-based polymer for durable applications. Polym Bull 75(5):2213–2242
Rosli NHA, Noor SAM, Ahmad KA, Winie T (2017) Effect of HNO3 on structual and electrical properties of hexanoyl chitosan/polystrene-LICF3SO3-TIO2. J Fundam Appl Sci 9(3S):141–153
Samsudin AS, Isa MIN, Mohamad N (2011) New types of biopolymer electrolytes: ionic conductivity study on CMC doped with NH4Br. J Curr Eng Res 1(1):7–11
Shukur MF, Kadir MFZ (2015) Electrical and transport properties of NH4Br-doped cornstarch-based solid biopolymer electrolyte. Ionics 21(1):111–124
Karthikeyan S, Selvasekarapandian S, Premalatha M, Monisha S, Boopathi G, Aristatil G, Arun A, Madeswaran S (2017) Proton-conducting I-Carrageenan-based biopolymer electrolyte for fuel cell application. Ionics 23(10):2775–2780
Vahini M, Muthuvinayagam M (2018) AC impedance studies on proton conducting biopolymer electrolytes based on pectin. Mater Lett 218:197–200
Singh R, Bhattacharya B, Tomar SK, Singh V, Singh PK (2017) Electrical, optical and electrophotochemical studies on agarose based biopolymer electrolyte towards dye sensitized solar cell application. Measurement 102:214–219
Rahmani V, Sheardown H (2018) Protein-alginate complexes as pH-/ion-sensitive carriers of proteins. Int J Pharm 535(1–2):452–461
Obot IB, Onyeachu IB, Kumar AM (2017) Sodium alginate: a promising biopolymer for corrosion protection of API X60 high strength carbon steel in saline medium. Carbohydr Polym 178:200–208
Merakchi A, Bettayeb S, Drouiche N, Adour L, Lounici H (2019) Cross-linking and modification of sodium alginate biopolymer for dye removal in aqueous solution. Polym Bull 76(7):3535–3554
Gondaliya N, Kanchan DK, Sharma P, Joge P (2011) Structural and conductivity studies of poly (ethylene oxide)–silver triflate polymer electrolyte system. Mater Sci Appl 2(11):1639
Ahmad NH, Bakar NY, Isa MIN (2017) Structural and ionic conductivity studies on proton conducting solid biopolymer electrolyte based on 2hydroxyethyl cellulose incorporated DTAB. In: AIP conference proceedings, vol 1. AIP Publishing, p 020080
Wu X, Xu Y, Jiang H, Wei Z, Hong JJ, Hernandez AS, Du F, Ji X (2018) NH4+ topotactic insertion in Berlin green: an exceptionally long-cycling cathode in aqueous ammonium-ion batteries. ACS Appl Energy 1(7):3077–3083
Zainuddin NK, Rasali NMJ, Samsudin AS (2018) Study on the effect of PEG in ionic transport for CMC-NH4Br-based solid polymer electrolyte. Ionics 24(10):3039–3052
Chai MN, Isa MIN (2016) Novel proton conducting solid bio-polymer electrolytes based on carboxymethyl cellulose doped with oleic acid and plasticized with glycerol. Sci Rep 6:27328
Rameshbabu N, Kumar TSS, Rao KP (2010) Influence of microwave power, irradiation time and polymeric additions on synthesis of nanocrystalline hydroxyapatite. Mater Res Innov 14(1):45–50
Parvin F, Yeasmin F, Islam JMM, Molla E, Khan MA (2013) Effect of gamma irradiated sodium alginate on Malabar spinach (Basella alba) and spinach (Spinacia oleracea) as plant growth promoter. Am Acad Sch Res J 5(5):63
Hema M, Selvasekerapandian S, Hirankumar G, Sakunthala A, Arunkumar D, Nithya H (2009) Structural and thermal studies of PVA: NH4I. J Phys Chem Solids 70(7):1098–1103
Aprilliza M (2017) Characterization and properties of sodium alginate from brown algae used as an ecofriendly superabsorbent. In: IOP conference series: materials science and engineering, vol 1. IOP Publishing, p 012019
Zhang N, Xu J, Gao X, Fu X, Zheng D (2017) Factors affecting water resistance of alginate/gellan blend films on paper cups for hot drinks. Carbohydr Polym 156:435–442
Treenate P, Monvisade P (2017) In vitro drug release profiles of pH-sensitive hydroxyethylacryl chitosan/sodium alginate hydrogels using paracetamol as a soluble model drug. Int J Biol Macromol 99:71–78
Fawzy MA, Gomaa M, Hifney AF, Abdel-Gawad KM (2017) Optimization of alginate alkaline extraction technology from Sargassum latifolium and its potential antioxidant and emulsifying properties. Carbohydr Polym 157:1903–1912
Tong Z, Chen Y, Liu Y, Tong L, Chu J, Xiao K, Zhou Z, Dong W, Chu X (2017) Preparation, characterization and properties of alginate/poly (γ-glutamic acid) composite microparticles. Mar Drugs 15(4):91
Ramlli MA, Kamarudin KH, Isa MIN (2015) Ionic conductivity and structural analysis of carboxymethyl cellulose doped with ammonium fluoride as solid biopolymer electrolytes. Am-Eurasian J Sustain Agric 46–52
Ahmad NH, Isa MIN (2015) Proton conducting solid polymer electrolytes based carboxymethyl cellulose doped ammonium chloride: ionic conductivity and transport studies. Int J Plast Technol 19(1):47–55
Samsudin AS, Khairul WM, Isa MIN (2012) Characterization on the potential of carboxy methylcellulose for application as proton conducting biopolymer electrolytes. J Non-Cryst Solids 358(8):1104–1112
Kadir MFZ, Salleh NS, Hamsan MH, Aspanut Z, Majid NA, Shukur MF (2018) Biopolymeric electrolyte based on glycerolized methyl cellulose with NH4Br as proton source and potential application in EDLC. Ionics 24(6):1651–1662
Zainuddin NK, Samsudin AS (2018) Investigation on the effect of NH4Br at transport properties in K–carrageenan based biopolymer electrolytes via structural and electrical analysis. Mater Today Comm 14:199–209
Samsudin AS, Lai HM, Isa MIN (2014) Biopolymer materials based carboxymethyl cellulose as a proton conducting biopolymer electrolyte for application in rechargeable proton battery. Electrochim Acta 129:1–13
Wei J (2019) Proton-conducting materials used as polymer electrolyte membranes in fuel cells. In: Song K, Liu C, Guo JZ (eds) Polymer-based multifunctional nanocomposites and their applications. Elsevier, Amsterdam, pp 245–260
Miyake T, Rolandi M (2017) Grotthuss mechanism: from proton transport in ion channels to bioprotonic devices. In: Irimia-Vladu M, Glowacki ED, Sariciftci NS, Bauer S (eds) Green materials for electronics. Wiley, Hoboken
Bakhtin S, Shved E, Bespal’ko Y (2017) Nucleophile-electrophile interactions in the reaction of oxiranes with carboxylic acids in the presence of tertiary amines. J Phys Org Chem 30(12):e3717
Rasali NMJ, Samsudin AS (2018) Ionic transport properties of protonic conducting solid biopolymer electrolytes based on enhanced carboxymethyl cellulose-NH4Br with glycerol. Ionics 24(6):1639–1650
Fu G, Dempsey J, Izaki K, Adachi K, Tsukahara Y, Kyu T (2017) Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks. J Power Sources 359:441–449
Mazuki NF, Fuzlin AF, Saadiah MA, Samsudin AS (2019) An investigation on the abnormal trend of the conductivity properties of CMC/PVA-doped NH4Cl-based solid biopolymer electrolyte system. Ionics 25(6):2657–2667
Rikukawa M, Sanui K (2000) Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers. Prog Polym Sci 25(10):1463–1502
Liew C-W, Ramesh S (2013) Studies on ionic liquid-based corn starch biopolymer electrolytes coupling with high ionic transport number. Cellulose 20(6):3227–3237
Ahmad NH, Isa MIN (2016) Characterization of un-plasticized and propylene carbonate plasticized carboxymethyl cellulose doped ammonium chloride solid biopolymer electrolytes. Carbohydr Polym 137:426–432
Swamy TMM, Ramaraj B, Lee JH (2008) Sodium alginate and its blends with starch: thermal and morphological properties. J Appl Polym Sci 109(6):4075–4081
Cheong M, Zhitomirsky I (2008) Electrodeposition of alginic acid and composite films. Colloids Surf A 328(1–3):73–78
Huq T, Salmieri S, Khan A, Khan RA, Le Tien C, Riedl B, Fraschini C, Bouchard J, Uribe-Calderon J, Kamal MR (2012) Nanocrystalline cellulose (NCC) reinforced alginate based biodegradable nanocomposite film. Carbohydr Polym 90(4):1757–1763
Liew C-W, Ramesh S, Arof AK (2014) A novel approach on ionic liquid-based poly (vinyl alcohol) proton conductive polymer electrolytes for fuel cell applications. Int J Hydrogen Energy 39(6):2917–2928
Ma X-H, Xu Z-L, Liu Y, Sun D (2010) Preparation and characterization of PFSA–PVA–SiO2/PVA/PAN difunctional hollow fiber composite membranes. J Membr Sci 360(1–2):315–322
Li X, Xie H, Lin J, Xie W, Ma X (2009) Characterization and biodegradation of chitosan–alginate polyelectrolyte complexes. Polym Degrad Stab 94(1):1–6
Perumal P, Selvin PC, Selvasekarapandian S (2018) Characterization of biopolymer pectin with lithium chloride and its applications to electrochemical devices. Ionics 24(10):3259–3270
Báez GD, Piccirilli GN, Ballerini GA, Frattini A, Busti PA, Verdini RA, Delorenzi NJ (2017) Physicochemical characterization of a heat treated calcium alginate dry film prepared with chicken stock. J Food Sci 82(4):945–951
Soazo M, Báez G, Barboza A, Busti PA, Rubiolo A, Verdini R, Delorenzi NJ (2015) Heat treatment of calcium alginate films obtained by ultrasonic atomizing: physicochemical characterization. Food Hydrocolloids 51:193–199
Sampathkumar L, Selvin PC, Selvasekarapandian S, Perumal P, Chitra R, Muthukrishnan M (2019) Synthesis and characterization of biopolymer electrolyte based on tamarind seed polysaccharide, lithium perchlorate and ethylene carbonate for electrochemical applications. Ionics 25(3):1067–1082
Sikkanthar S, Karthikeyan S, Selvasekarapandian S, Pandi DV, Nithya S, Sanjeeviraja C (2015) Electrical conductivity characterization of polyacrylonitrile-ammonium bromide polymer electrolyte system. J Solid State Electrochem 19(4):987–999
Kadir MFZ, Hamsan MH (2018) Green electrolytes based on dextran-chitosan blend and the effect of NH4SCN as proton provider on the electrical response studies. Ionics 24(8):2379–2398
Moniha V, Alagar M, Selvasekarapandian S, Sundaresan B, Hemalatha R, Boopathi G (2018) Synthesis and characterization of bio-polymer electrolyte based on iota-carrageenan with ammonium thiocyanate and its applications. J Solid State Electrochem 22(10):3209–3223
Iwaki YO, Escalona MH, Briones JR, Pawlicka A (2012) Sodium alginate-based ionic conducting membranes. Mol Cryst Liq Cryst 554(1):221–231
Manjuladevi R, Selvin PC, Selvasekarapandian S, Shilpa R, Moniha V (2018) Lithium ion conducting biopolymer electrolyte based on pectin doped with Lithium nitrate. In: AIP conference proceedings, vol 1. AIP Publishing, p 140075
Yang J-M, Wang N-C, Chiu H-C (2014) Preparation and characterization of poly (vinyl alcohol)/sodium alginate blended membrane for alkaline solid polymer electrolytes membrane. J Membr Sci 457:139–148
Zhang Y, Wang C, Liu Y, Jiang W, Han G (2019) Preparation and characterization of composite scaffold of alginate and cellulose nanofiber from ramie. Text Res J 89(16):3260–3268
Hodge RM, Edward GH, Simon GP (1996) Water absorption and states of water in semicrystalline poly (vinyl alcohol) films. Polymer 37(8):1371–1376
Basha SKS, Rao MC (2018) Spectroscopic and electrochemical properties of PVP based polymer electrolyte films. Polym Bull 75(8):3641–3666
Basha SKS, Sundari GS, Kumar KV, Rao MC (2018) Preparation and dielectric properties of PVP-based polymer electrolyte films for solid-state battery application. Polym Bull 75(3):925–945
Kumar LS, Selvin PC, Selvasekarapandian S, Manjuladevi R, Monisha S, Perumal P (2018) Tamarind seed polysaccharide biopolymer membrane for lithium-ion conducting battery. Ionics 24(12):3793–3803
Boopathi G, Pugalendhi S, Selvasekarapandian S, Premalatha M, Monisha S, Aristatil G (2017) Development of proton conducting biopolymer membrane based on agar–agar for fuel cell. Ionics 23(10):2781–2790
Hafiza MN, Isa MIN (2017) Solid polymer electrolyte production from 2-hydroxyethyl cellulose: effect of ammonium nitrate composition on its structural properties. Carbohydr Polym 165:123–131
Kadir MFZ, Majid SR, Arof AK (2010) Plasticized chitosan–PVA blend polymer electrolyte based proton battery. Electrochim Acta 55(4):1475–1482
Monisha S, Mathavan T, Selvasekarapandian S, Benial AMF (2017) Preparation and characterization of cellulose acetate and lithium nitrate for advanced electrochemical devices. Ionics 23(10):2697–2706
Alboofetileh M, Rezaei M, Hosseini H, Abdollahi M (2018) Morphological, physico-mechanical, and antimicrobial properties of sodium alginate-montmorillonite nanocomposite films incorporated with marjoram essential oil. J Food Process Preserv 42(5):e13596
Sundaramahalingam K, Muthuvinayagam M, Nallamuthu N, Vanitha D, Vahini M (2019) Investigations on lithium acetate-doped PVA/PVP solid polymer blend electrolytes. Polym Bull 76(11):5577–5602
Kadir MFZ, Aspanut Z, Yahya R, Arof AK (2011) Chitosan–PEO proton conducting polymer electrolyte membrane doped with NH4NO3. Mater Res Innov 15(sup2):s164–s167
Rani MSA, Ahmad A, Mohamed NS (2018) A comprehensive investigation on electrical characterization and ionic transport properties of cellulose derivative from kenaf fibre-based biopolymer electrolytes. Polym Bull 75(11):5061–5074
Saadiah MA, Zhang D, Nagao Y, Muzakir SK, Samsudin AS (2019) Reducing crystallinity on thin film based CMC/PVA hybrid polymer for application as a host in polymer electrolytes. J Non-Cryst Solids 511:201–211
Rasali NMJ, Samsudin AS (2018) Characterization on ionic conductivity of solid bio-polymer electrolytes system based alginate doped ammonium nitrate via impedance spectroscopy. In: AIP conference proceedings, vol 1. AIP Publishing, p 020224
Fuzlin AF, Rasali NMJ, Samsudin AS (2018) Effect on Ammonium Bromide in dielectric behavior based Alginate Solid Biopolymer electrolytes. In: IOP conference series: materials science and engineering, vol 1. IOP Publishing, p 012080
Perumal P, Selvasekarapandian S, Abhilash KP, Sivaraj P, Hemalatha R, Selvin PC (2019) Impact of lithium chlorate salts on structural and electrical properties of natural polymer electrolytes for all solid state lithium polymer batteries. Vacuum 159:277–281
Sundaramahalingam K, Vanitha D, Nallamuthu N, Manikandan A, Muthuvinayagam M (2018) Electrical properties of lithium bromide poly ethylene oxide/poly vinyl pyrrolidone polymer blend elctrolyte. Physica B: Condens Matter 553:120–126
Kalaiselvimary J, Prabhu MR (2019) Fabrications and investigation of physicochemical and electrochemical properties of heteropoly acid-doped sulfonated chitosan-based polymer electrolyte membranes for fuel cell applications. Polym Bull 76(3):1401–1422
Saadiah MA, Samsudin AS (2018) Study on ionic conduction of solid bio-polymer hybrid electrolytes based carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA) doped NH4NO3. In: AIP conference proceedings, vol 1. AIP Publishing, p 020223
Fuzlin AFA, Ismail NS, Nagao Y, Samsudin AS (2019) Electrical properties of a novel solid biopolymer electrolyte based on algi-nate incorporated with citric acid. Makara J Technol 23(1):48–52
Mazuki NF, Rasali NMJ, Saadiah MA, Samsudin AS (2018) Irregularities trend in electrical conductivity of CMC/PVA-NH4Cl based solid biopolymer electrolytes. In: AIP conference proceedings, vol 1. AIP Publishing, p 020221
Kurapati S, Gunturi SS, Nadella KJ, Erothu H (2019) Novel solid polymer electrolyte based on PMMA: CH3COOLi effect of salt concentration on optical and conductivity studies. Polym Bull 76(10):5463–5481
Shukur MF, Ithnin R, Illias HA, Kadir MFZ (2013) Proton conducting polymer electrolyte based on plasticized chitosan–PEO blend and application in electrochemical devices. Opt Mater 35(10):1834–1841
Samsudin AS, Isa MIN (2012) Structural and ionic transport study on CMC doped NH4Br: a new types of biopolymer electrolytes. J Appl Sci 12(2):174–179
Zainuddin NK, Saadiah MA, Abdul Majeed APP, Samsudin AS (2018) Characterization on conduction properties of carboxymethyl cellulose/kappa carrageenan blend-based polymer electrolyte system. Int J Polym Anal Charact 23(4):321–330
Ramlli MA, Isa MIN (2016) Structural and ionic transport properties of protonic conducting solid biopolymer electrolytes based on Carboxymethyl cellulose doped with ammonium fluoride. J Phys Chem B 120(44):11567–11573
Ramlli MA, Bashirah NAA, Isa MIN (2018) Ionic conductivity and structural analysis of 2-hyroxyethyl cellulose doped with glycolic acid solid biopolymer electrolytes for solid proton battery. In: IOP conference series: materials science and engineering, vol 1. IOP Publishing, p 012038
Woo HJ, Majid SR, Arof AK (2011) Conduction and thermal properties of a proton conducting polymer electrolyte based on poly (ε-caprolactone). Solid State Ionics 199:14–20
Majid SR, Arof AK (2007) Electrical behavior of proton-conducting chitosan-phosphoric acid-based electrolytes. Physica B: Condens Matter 390(1–2):209–215
Fuzlin AF, Nagao Y, Misnon II, Samsudin AS (2019) Studies on structural and ionic transport in biopolymer electrolytes based on alginate-LiBr. Ionics 26:1923–1938
Ramesh S, Ng KY (2009) Characterization of polymer electrolytes based on high molecular weight PVC and Li2SO4. Curr Appl Phys 9(2):329–332
Acknowledgements
The authors would like to thank MOHE for FRGS (RDU1901114) and (RDU170115), UMP for internal grant RDU1703189, Faculty of Industrial Sciences & Technology, Universiti Malaysia Pahang, for the help and support given for the completion of this work. The authors would also like to thank members of Ionic Materials Team, which are N.M.J. Rasali, M.A. Saadiah and N.F. Mazuki for kindly help in completing this research.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Fuzlin, A.F., Samsudin, A.S. Studies on favorable ionic conduction and structural properties of biopolymer electrolytes system-based alginate. Polym. Bull. 78, 2155–2175 (2021). https://doi.org/10.1007/s00289-020-03207-2
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-020-03207-2