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Accepted Manuscript

Title: Carboxymethyl Carrageenan Based Biopolymer Electrolytes

Author: N.N. Mobarak F.N. Jumaah M.A. Ghani M.P. Abdullah A. Ahmad

N.N. Mobarak F.N. Jumaah M.A. Ghani M.P. Abdullah A. Ahmad PII: S0013-4686(15)00522-8 DOI:

PII:

S0013-4686(15)00522-8

DOI:

http://dx.doi.org/doi:10.1016/j.electacta.2015.02.200

Reference:

EA 24479

To appear in:

Electrochimica Acta

Received date:

24-10-2014

Revised date:

24-2-2015

Accepted date:

24-2-2015

Please cite this article as: N.N.Mobarak, F.N.Jumaah, M.A.Ghani, M.P.Abdullah, A.Ahmad, Carboxymethyl Carrageenan Based Biopolymer Electrolytes, Electrochimica Acta http://dx.doi.org/10.1016/j.electacta.2015.02.200

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Carboxymethyl Carrageenan Based Biopolymer Electrolytes N.N. Mobarak * nadhratunnaiim@siswa.ukm.edu.my, F.N. Jumaah,

Carboxymethyl Carrageenan Based Biopolymer Electrolytes

N.N. Mobarak * nadhratunnaiim@siswa.ukm.edu.my, F.N. Jumaah, M.A. Ghani, M.P. Abdullah, A. Ahmad * azizan@ukm.edu.my

School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor Darul Ehsan, Malaysia

* Corresponding Author: Tel:60389287262; Fax:60389212115.

Highlights

The paper highlights the potential of carboxymethyl carrageenan based on iota and kappa to be utilized as host polymer.

The highest conductivity were achieved up to ~10 -3 S cm -1 by carboxymethyl carrageenan without the addition of plasticizer.

The electrochemical stability windows of the films were electrochemically stable up to 3.0 V.

Abstract A series of biodegradable carboxymethyl carrageenan based polymer electrolytes, which are carboxymethyl kappa carrageenan (sulphate per disaccharide) and carboxymethyl iota carrageenan (two sulphates per disaccharide), have been prepared by a solution casting technique with different ratios of lithium nitrate (LiNO 3 ) salts. Interestingly, the lithium ions tended to interact with the carbonyl group in the different modes of symmetry, as observed from reflection Fourier transform infrared (ATR-FTIR) spectroscopy analysis. In the carboxymethyl kappa carrageenan electrolytes, as the concentration of LiNO 3 increased, the asymmetric stretching peak of the carbonyl bond became dominant because it can be observed clearly with the shifting of the peak from 1592 to 1602 cm -1 due to the interaction between the lithium ion and the carbonyl group, while the broad O-H stretching peak became sharp and intense. However, for the carboxymethyl iota carrageenan, the asymmetry stretching mode of the carbonyl group shifted from 1567 to 1599 cm -1 , as the salt concentration increased. The shifting of the C-O-C peak also occurred in the iota-based electrolytes. However, the changes in the peak that represented SO 4 2- symmetric stretching were only detected when the ion pair formation was observed. It was proposed that the peak shifting was due to the presence of the lithium ion pathway, forming a dative bond between the lithium and oxygen in the carbonyl group. Accordingly, as more peak shifting was observed, the number of the ion pathways also increased. This hypothesis was supported by the impedance data, which demonstrated that the ionic conductivity of the 20 wt.% LiNO 3 iota-based electrolytes was highly similar with the 30 wt.% LiNO 3 kappa-based electrolytes, with values of 5.85 × 10 -3 S cm -1 and 5.51 x 10 -3 S cm -1 , respectively. The lithium transference number for the carboxymethyl kappa carrageenan was higher than for the carboxymethyl iota carrageenan. Additionally, the carboxymethyl iota carrageenan and

carboxymethyl kappa carrageenan films were electrochemically stable up to ~3.0 and 3.1 V, respectively, which

carboxymethyl kappa carrageenan films were electrochemically stable up to ~3.0 and 3.1 V, respectively, which indicates that these solid biopolymer electrolytes are promising candidates for utilization in electrochemical devices.

Keyword: carboxymethyl, electrochemical stability, ionic conductivity

1.

Introduction

Carrageenans are a family of anionic polymers that are extracted from certain marine red

algae and that share a common backbone of alternating (1 3)-linked β-D-galactopyranose

and (1 4)-linked α-D-galactopyranose [1]. There are three primary types of carrageenans:

kappa carrageenan (possesses one sulphate per disaccharide), iota carrageenan (two sulphates

per disaccharide) and lambda (three sulphates per disaccharide) [2]. Carrageenans are

extensively used in the food, pharmaceutical and cosmetic industries as viscosity builders,

gelling agents and stabilizers, [3] especially because carrageenans are regarded as safe

(GRAS) by The Food and Drug Administration in the US [1].

Recently, attention is given to polysaccharides based biopolymer as new polymer electrolyte

materials for electrochemical cell application. From the prospective of the solid-state

electrochemistry, anionic biopolymer could acts as polymer host which plays important roles

for coordination sites with metal cations in polymer electrolyte systems. The increase in the

number of coordination sites and functionality in the polymeric structure are expected to

increase the ion dissociation, which would increase the ionic conductivity [4]. Therefore, by

performing chemical modification on the pure polymer, more functional group can be

introduced. Based upon a review of the literature, research has been conducted regarding the

modification of natural polymers to improve their properties, and this research is anticipated

to bring about quite promising results. Modification can functionalize these biopolymers to

and impart desirable properties onto them, contributing towards their improved industrial

applications [5-7]. Several studies have been conducted to prepare derivatives of carrageenan.

Tranquilan-Aranilla et al. [8] prepared carboxymethyl kappa carrageenan for use as suitable

carriers for the targeted delivery of bioactive molecules into the intestines. The chemical

modification of carrageenan derivatives (iota and kappa) for host polymer applications

demonstrated that the carboxymethyl derivatives possessed conductivities values of 4.87×10 -6

S cm -1 and 2.0×10 -4 S cm -1 achieved by carboxymethyl iota carrageenan and carboxymethyl

kappa carrageenan, respectively [4, 9-11]. The high conductivity value of carboxymethyl carrageenan indicated a huge

kappa carrageenan, respectively [4, 9-11]. The high conductivity value of carboxymethyl carrageenan indicated a huge potential of biopolymer materials to be used as the host polymer electrolytes.

To enhance the potential of the carboxymethyl derivatives (iota and kappa) for electrochemical cell applications, such as with lithium batteries, lithium nitrate (LiNO 3 ) will be introduced as a dopant salt. From the literature, lithium salts, such as lithium perchlorate (LiClO 4 ) [12], lithium tetrafluoroborate (LiBF 4 ) [13], lithium bis(trifluoromethanesulfonyl) imide (LiTSFI) [14] and lithium hexafluorophosphate (LiPF 6 ), [15] are among the salts that have been utilized by other researchers. The potential of LiNO 3 was reported by Mohamed et al. (1995) [16]. They used acetylated chitosan as a polymer host that achieved an electrical conductivity of 2.7 × 10 -4 S cm -1 . Xiong et al. (2012) also demonstrated that the use of LiNO 3 was an effective additive that protected the lithium anode [17]. Because lithium-oxygen batteries are becoming increasingly attractive due to their high theoretical energy densities, proper cell voltages and utilization of environment-friendly components [18-21], the selection of lithium nitrate is a great choice. The unique properties of the nitrate electrolyte allows for it to serve as a secondary source for oxygen at the cathode as well as it providing a nitrate ion pathway for oxygen reduction [22].

In this work, the effects of the lithium ion on the ionic conductivity and the chemical stability of carboxymethyl carrageenan will be examined by using Electrochemical Impedance Spectroscopy (EIS) analysis and Linear Sweep Voltammetry (LSV). This paper will also investigate the interactions between the targeted functional groups, which are the carboxylate and sulphate groups, and the lithium ions by using reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy.

2.

Experimental

2.1 Preparation of the membrane

Carboxymethyl carrageenan was prepared according to the method established by Sun et al. (2008) [23]. To prepare the polymer electrolyte films, carboxymethyl carrageenan was dissolved in a 1% acetic acid solution that was continuously stirred with a magnetic bar for 24 hours. Various weight percentages of LiNO 3 were dissolved separately in a 1% acetic acid

solution before it was added drop-wise into the carboxymethyl carrageenan solution. The solutions were further

solution before it was added drop-wise into the carboxymethyl carrageenan solution. The solutions were further stirred for 24 hours to achieve a homogenous mixture. The solutions were cast onto petri dishes and allowed to dry completely at room temperature until films were obtained. The samples were stored in a desiccator for future use. 2.2 Sample characterization

ATR-FTIR analysis was conducted by using a Perkin Elmer Spectrum 2000 for the range from 4000 to 400 cm 1 with a scanning resolution of 4 cm 1 . This analysis was conducted to observe the interactions between the polymer matrix and the lithium nitrate salts based upon the changes in the shapes and the wavenumbers of the peaks. Alternating current (AC) impedance measurements were conducted by using a high frequency response analyser (HFRA; Solartron 1260, Schlumberger) and an electrochemical interface (SI 1286) in the frequency range of 1Hz–10 MHz with a 10 mV amplitude at room temperature. The polymer electrolyte was sandwiched between the stainless steel blocking electrodes with a contact surface area of 2.0 cm 2 . The bulk resistance (R b ) was determined from the equivalent circuit analysis by using the Zview analyser software. The samples were also characterized via electrical impedance spectroscopy (EIS) using an HIOKI 3532 LCR Hi-Tester that was interfaced with a computer, and the experiments were conducted in the frequency range between 50 Hz to 1MHz. The temperature dependence of the AC conductivities for both systems were recorded between 30 - 65 °C with intervals of 5°C. The transference number of lithium ion, t Li+ , was determined at 303K by using a Zive mp2 multichannel electrochemical workstation. The electrolyte was placed between two lithium electrodes. A DC voltage (ΔV= 0.1V) was applied to these two electrodes until the current reached steady-state. The AC impedance measured the resistance of the polymer electrolyte and the interface before/after the voltage was applied. The transference number of lithium ion, t Li+ , was calculated with the following formula:

t Li+ = I S (ΔV-I 0 R i0 ) / I 0 (ΔV-I s R iS )

where I 0 and I S are the initial and steady-state currents during the polarization, respectively, and R i0 and R iS are the interfacial resistances at the initial state and the steady-state, respectively [24]. The linear sweep voltammetry of the electrolyte films was determined by the application of a D.C. potential (0.1 V) across the sample using stainless steel electrodes at 303K and a Zive mp2 multichannel electrochemical workstation.

3.

Results and Discussion

3. Results and Discussion 3.1 Physical Observations Fig. 1 shows the physical observations of the carboxymethyl

3.1 Physical Observations

Fig. 1 shows the physical observations of the carboxymethyl kappa carrageenan and carboxymethyl iota carrageenan films. It can be observed that the carboxymethyl kappa carrageenan was more transparent compared to the carboxymethyl iota carrageenan. The difference in term of colour between kappa carrageenan and iota carrageenan samples were caused by the source of raw materials. Kappa carrageenan powder which extracted from Eucheuma cottonii was whiter compared to iota carrageenan powder that extracted from Eucheuma spinosum.

3.2 FTIR spectrum studies of the carboxymethyl carrageenan films

FTIR spectroscopy was utilized to identify the interactions that occurred between the lithium ions and the oxygen atoms in the chemical structure of the carboxymethyl carrageenan. The characteristic band regions of hydroxyl stretching, carbonyl and C-O-C stretching were the main focus in the detection of the ionic interactions. Fig. 2 and 3 show the infrared spectra of the carboxymethyl kappa carrageenan and the carboxymethyl iota carrageenan at different weight percentages of salt. As previously reported, the peak that represents the O-H stretching at 3436 cm -1 shifted to 3386 cm -1 when the powder of the carboxymethyl kappa carrageenan was dissolved in 1% acetic acid [4]. The shifting of the wavenumber to the lower frequency was due to the protonation of the hydroxyl group with the addition of acetic acid. The protonated hydroxyl group will form electrostatic interactions with the acetate ions, as shown in Scheme 1. However, as the concentration of the lithium nitrate was increased, the peaks that represented the O-H became more intense. This proved that there were ion dipole interactions between the oxygen atoms in the hydroxyl groups of the carboxymethyl kappa carrageenan with the lithium ions, as shown in Scheme 1. These changes were also observed in the carboxymethyl iota carrageenan- LiNO3 films, as shown in Scheme 2.

The lithium ions also tended to interact with the carbonyl group in the different symmetry modes, as observed from the ATR-FTIR spectra for both systems. It was observed that the

peak that represented the asymmetric stretching of the carbonyl shifted to a higher wavenumber, from

peak that represented the asymmetric stretching of the carbonyl shifted to a higher wavenumber, from 1592 to 1602 cm -1 for carboxymethyl kappa carrageenan and from 1562 to 1602 cm -1 for carboxymethyl iota carrageenan. As it is known, asymmetric stretching can explain the bond stretching in different directions. Because the electrostatic interactions between the C-O- in the acetate ions and the carboxymethyl ions are stronger compared to the ion dipole interactions that form between the oxygen atom in C=O with the lithium ion, it was expected that C=O peak would become shorter, which is shown in Fig. 4. On the other hand, the symmetric stretching was shifted to lower wavenumbers for both systems. However, as the concentration of lithium nitrate increased up to 30 wt.% for the carboxymethyl kappa carrageenan and 20 wt.% for the carboxymethyl iota carrageenan, the complexation between the lithium ions and the nitrate ions were detected by the appearance of a new peak at 1630 cm -1 . This confirmed that the appearance of ion pairs influenced the conductivity that was achieved by the system, and the optimum conductivity was achieved by the carboxymethyl iota carrageenan with 20 wt.% LiNO 3 .

The asymmetric stretching of the nitrate was also observed when the concentration of lithium salt increased; this was observed as a shift in the peak from 1379 cm -1 to 1355 cm -1 for the carboxymethyl kappa carrageenan and by the appearance of new peak at 1358 cm -1 for the carboxymethyl iota carrageenan. For the carboxymethyl kappa carrageenan, it was also observed that the peak at 1065 and 1041 cm -1 , which represented the C-O-C stretching, changed in terms of the wavenumber and intensity. The intensity of the peaks at 1065 cm -1 increased while the peak at 1044 cm -1 decreased as the salt concentration increased. Based upon previous research, the peak at 1044 cm -1 only appeared when the carboxymethyl kappa carrageenan was dissolved in 1% acetic acid [4]. This finding may be due to the transient intermolecular hydrogen bonds that were formed between the oxygen atoms (C=O) in the acetate ions or the carboxylate ions with a hydrogen atom from a protonated hydroxyl group. However, as the number of lithium ions increased, the interactions between the lithium ions and the oxygen atoms (C=O) in the acetate ions or the carboxylate ions became more dominant, and therefore the intensity of the peak at 1044 cm -1 decreased. It was also observed that the intensity of the hydroxyl peak became sharper as the concentration of the lithium nitrate increased. For the carboxymethyl iota carrageenan, both peaks at 1069 and 1023 cm -1 decreased in their intensity with the addition of lithium nitrate due to the interactions between the Li + cations and the ether oxygen atoms [25]. However, the changes in the wavenumbers

that represent the sulphate stretching peak were only observed for the 25 wt.% LiNO 3

that represent the sulphate stretching peak were only observed for the 25 wt.% LiNO 3 - carboxymethyl iota carrageenan and for carboxymethyl kappa carrageenan at 30 wt.% LiNO 3 . The appearance of a new peak at 1248 cm -1 , which was representative of the interactions between the lithium ions and the sulphate ions (RSO 4 - Li + ), were detected [26]. This finding demonstrated that the lithium ion more favourable interacted with the carboxylic ions because they were more basic compared to the sulphate ions. Therefore, this finding also supported the fact that the optimum ionic conductivity was able to be achieved by carboxymethyl kappa carrageenan at 30 wt.% LiNO3 compared to 20 wt.% LiNO 3 for the carboxymethyl iota carrageenan; this was possible because the carboxymethyl kappa carrageenan possesses one sulphate per disaccharide and the carboxymethyl iota carrageenan possesses two sulphates per disaccharide. Schemes 1 and 2 show the proposed mechanism that explains the interactions between the lithium ions and the electronegativity atoms in the carboxymethyl carrageenans.

3.3 Ionic conductivity

The ionic conductivities of the polymer electrolytes with different concentrations of LiNO 3 salts at room temperature for the carboxymethyl kappa carrageenan and carboxymethyl iota carrageenan are presented in Fig. 5. The recorded conductivity of the carboxymethyl kappa carrageenan increased with a corresponding increase in the concentration of the LiNO 3 salts. The highest conductivity that was obtained was 5.51 × 10 -3 S cm -1 with a concentration of 30 wt.% of the LiNO 3 salt. The ionic conductivity for the carboxymethyl iota carrageenan increased when up to 20 wt.% of the LiNO 3 salt was added.

As seen in the FTIR analysis, interactions occurred between the LiNO 3 and the COO - and C- O-C groups in both host polymers, and these interactions promoted the dissociation of LiNO 3 and increased the free charge carriers in the electrolyte systems, which lead to an increase in the conductivity. This was similar to what had previously been reported in the literature [27], where it was stated that the increase in the ionic conductivity along with increase in the salt concentration could be understood in terms of the number density of the charge carriers. However, as seen from the FTIR spectra, the decrease of the conductivity for the carboxymethyl iota carrageenan was attributed to the re-association of ions to form ion clusters. Therefore, there were fewer mobile charge carriers and the larger sized ion clusters

limited the ion mobility. The optimum conductivity for the carboxymethyl iota carrageenan was achieved at

limited the ion mobility. The optimum conductivity for the carboxymethyl iota carrageenan was achieved at a 20 wt.% salt concentration.

To evaluate the ionic conduction mechanisms, the ionic conductivities of the solid polymer electrolyte based carboxymethyl kappa carrageenan- 30 wt.% LiNO 3 and carboxymethyl iota carrageenan- 20 wt.% LiNO 3 complexes were measured at different temperatures, as shown in Fig. 5. As illustrated in Fig. 5, typical behaviour for a polymer electrolyte was observed where the ionic conductivity increased with increasing temperature. Higher temperatures not only promoted the migration of the carrier ions but also resulted in the expansion of the polymers [28]. This expansion produced local empty space and increased the free volume, which promoted the motion of the polymer segments and carrier ions. The highest ionic conducting samples of the carboxymethyl kappa carrageenan- 30 wt.% LiNO 3 and the carboxymethyl iota carrageenan- 20 wt.% LiNO 3 complexes possessed ionic conductivities of 7.42 x 10 -3 and 1.51 x 10 -2 S cm -1 , respectively.

As shown in Fig. 6, the regression values were close to unity, which indicated that the temperature-dependent ionic conductivities for this SPE system obeyed Arrhenius’s rule in the temperature range between 30 and 60°C. Based upon the calculations, the activation energy for the carboxymethyl kappa carrageenan- 30 wt.% LiNO 3 and the carboxymethyl iota carrageenan- 20 wt.% LiNO 3 complexes were 0.18 and 0.38 eV, respectively. The low activation energy values indicated that a low amount of energy was needed for the formation of ions [29]. The low apparent activation energies may also be related to the easy transformation of the polymer conformations [30].

3.4 Transference number Analysis

Fig. 7 depicts the lithium transference numbers of the solid polymer electrolytes based upon carboxymethyl kappa carrageenan and carboxymethyl iota carrageenan. The value of lithium transference number, t Li+ , was calculated from the normalized polarization current versus time. Based on the graph, the initial total current decreased with time due to the depletion of the ionic species in the electrolyte, and became constant in the fully depleted situation. At steady-state, the cell was polarized and the current was allowed to flow because of the electron migration across the electrolyte and interfaces [31]. The lithium transference numbers for the studied carboxymethyl kappa carrageenan and carboxymethyl iota

carrageenan complexes were calculated to be 0.54 and 0.42, respectively. These results were supported by

carrageenan complexes were calculated to be 0.54 and 0.42, respectively. These results were supported by the E a value, which was lower for the carboxymethyl kappa carrageenan than for the carboxymethyl iota carrageenan. The lithium transference numbers for these biopolymers possessed better results compared to the system of polyethylene oxide (PEO) /LiPBSi, where the calculated lithium transference number was 0.39 [32].

3.5 Linear Sweep Voltammetry

Fig. 8 depicts the linear sweep voltammetry curves for the iota and kappa carboxymethyl carrageenan. From Fig. 8, a small current was observed through the working electrode until the applied voltage reached a potential of 3.0 and 3.10 V for carboxymethyl iota carrageenan and carboxymethyl kappa carrageenan, respectively [33]; this was marked with arrows in Fig. 8. The current increased sharply with the applied voltage, which can be attributed to the decomposition of the polymer electrolyte. This indicated that the carboxymethyl iota carrageenan–20 wt.% LiNO 3 electrolyte was electrochemically stable up to 3.0 V while the carboxymethyl kappa carrageenan–30 wt.% LiNO 3 electrolyte was electrochemically stable up to 3.10 V.

4.

Conclusions

The effects of lithium nitrate (LiNO 3 ) salts on the carboxymethyl iota carrageenan and carboxymethyl kappa carrageenan based solid polymer electrolytes were investigated. The highest ionic conductivities were achieved for the carboxymethyl kappa and iota carrageenan were 5.85 × 10 -3 S cm -1 and 5.51 × 10 -3 S cm -1 at 30 wt.% and 20 wt.% of the lithium salts addition, respectively. FTIR spectra demonstrated that the lithium ion more favourably interacted with the carbonyl and ether groups compared to the sulphate group. The formation of the ion pair was observed the appearance of new peaks at 1630 and 1375 cm -1 for 25 wt.% and 30 wt.% LiNO 3 salts, respectively. The ion pair might cause a decrease in the ionic conductivity for carboxymethyl iota carrageenan. The activation energies for the carboxymethyl kappa carrageenan and the carboxymethyl iota carrageenan were calculated to be 0.18 and 0.38 eV, respectively. The activation energy results were supported by the lithium transference number analysis, where the values were reported as 0.54 and 0.42. From the LSV analysis, it was demonstrated that both samples were stable up to 3.0 V. These results indicated that both systems were suitable to be used in lithium-ion battery applications.

Acknowledgments The authors would like to thank UKM and the Fisheries Department for the provisions

Acknowledgments

The authors would like to thank UKM and the Fisheries Department for the provisions

provided by the grants FRGS/2/2013/TK04/UKM/02/4 and STGL-007-2010, respectively,

and to Syarikat Tacara Sdn Bhd.

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Scheme and Figure Caption

Scheme 1 Interaction between lithium nitrate and the carboxymethyl kappa carrageenan

Scheme 2 Interaction between lithium nitrate and the carboxymethyl iota carrageenan

Fig. 1 Physical observations of A (i) and A (ii) for the carboxymethyl kappa carrageenan at 5 wt.% and 30wt.% LiNO 3; B (i) and B (ii) for the carboxymethyl iota carrageenan at 5 wt.% and 25 wt.% LiNO 3 .

Fig. 2 FTIR spectra of the carboxymethyl kappa carrageenan at different weight percentages of lithium nitrate salts where (a) is the hydroxyl band region, (b) is the carbonyl stretching and (c) is the C-O-C band region

Fig. 3 FTIR spectra of the carboxymethyl iota carrageenan at different weight percents of lithium nitrate salts where (a) is the hydroxyl band region, (b) is the carbonyl stretching and (c) is the C-O-C band region

Fig. 4 Modes of the carbonyl bond stretching: (A) Symmetric stretching (B) Asymmetric Stretching

Fig. 5 Ionic conductivities of the solid polymer electrolytes based upon carboxymethyl carrageenan at ambient

Fig. 5 Ionic conductivities of the solid polymer electrolytes based upon carboxymethyl carrageenan at ambient temperature

Fig. 6 Effect of the temperature on the ionic conductivities of the solid polymer electrolytes based upon carboxymethyl carrageenan

Fig. 7 Normalized current using Li metal as the electrode for the solid polymer electrolytes based upon carboxymethyl carrageenan

Fig. 8 Linear sweep voltammetry of the carboxymethyl carrageenan

O H 2 C C O 6 OSO 3 O 6' 5 O 5' O
O H 2 C C O 6 OSO 3 O 6' 5 O 5' O
O
H 2 C
C
O
6
OSO
3 O
6'
5
O
5'
O
4'
O
1
1'
O
3
2
2'
4
3'
O
O
O
n
H
H
Li +
NO 3

O

O 3 2 2' 4 3' O O O n H H Li + NO 3

Li +

+Li H 2 C C O 6 OSO 3 O 6' 5 O 5' 1
+Li
H 2 C
C
O
6
OSO
3 O
6'
5
O
5'
1
4'
O
O
1'
3
2
O
4
2'
3'
O
O
O
H
n
+
H
H
Li
H
(iii)
(i)
CH 3 CH2(O)O
CH 3 C(O)O
(ii)
H
H
H H
O
O
O
+
Li
O
O
O
O
O
O 3 SO
O
C
CH 2
O
Li +
6
'6
5
'4
'5
1
'1
3
'2
4
2
'3
n

Scheme 1

Li +

O O - OSO 3 n - HOOCH 2 C O OSO 3 - C
O O - OSO 3 n
O
O
-
OSO 3
n

-

HOOCH 2 C O OSO 3 - C 2 H O O O H
HOOCH 2 C
O
OSO 3 -
C 2 H
O
O
O
H

Li +

NO 3

O

+Li - NO 3 + Li O(O)HCH 2 C + Li O Li + O
+Li
-
NO 3
+
Li
O(O)HCH 2 C
+
Li
O
Li +
O
OSO 3 -
CH 2
O
O
O
O
O
H
OSO 3 -
H
n
(ii)
CH3C(O)O
+Li
LI +
(i)
H
H
O
O
O
O
O
C
H
-
2
OSO 3
O
O
CH 2 C(O)O
-
OSO
3
n

Li +

A A (ii) (i) B B (ii) (i) Fig. 1
A A (ii) (i) B B (ii) (i)
A
A (ii)
(i)
B
B
(ii)
(i)

Fig. 1

100 100 90 90 80 80 70 70 60 60 5% LiNO3 5% LiNO3 10%
100 100 90 90 80 80 70 70 60 60 5% LiNO3 5% LiNO3 10%
100
100
90
90
80
80
70
70
60
60
5% LiNO3
5% LiNO3
10% LiNO3
10% LiNO3
15% LiNO3
50
50
15% LiNO3
20% LiNO3
20% LiNO3
25% LiNO3
25% LiNO3
30% LiNO3
30% LiNO3
40
40
1600
1500
1400
1300
4000
3600
3200
2800
Wavenumber/cm -1
Wavenumber/cm -1
(a)
(b)
% T
% T

Fig. 2

100 90 80 70 60 5% LiNO3 10% LiNO3 50 15% LiNO3 20% LiNO3 25%
100
90
80
70
60
5% LiNO3
10% LiNO3
50
15% LiNO3
20% LiNO3
25% LiNO3
30% LiNO3
40
1200
1100
1000
% T

Wavenumber/cm -1

(c)

100 100 90 90 80 80 70 70 60 60 0% LiNO3 0% LiNO3 5%
100 100 90 90 80 80 70 70 60 60 0% LiNO3 0% LiNO3 5%
100
100
90
90
80
80
70
70
60
60
0% LiNO3
0% LiNO3
5% LiNO3
5% LiNO3
10% LiNO3
50
10% LiNO3
50
15% LiNO3
15% LiNO3
20% LiNO3
20% LiNO3
25% LiNO3
25% LiNO3
30% LiNO3
40
30% LiNO3
40
4000
3500
3000
1700
1600
1500
1400
1300
Wavenumber/cm -1
Wavenumber/cm -1
%T
%T

Fig. 3

(a)

(b)

100

90

80

%T

70

60

50

40

30

0% LiNO3 5% LiNO3 10% LiNO3 15% LiNO3 20% LiNO3 25% LiNO3 30% LiNO3 1200
0% LiNO3
5% LiNO3
10% LiNO3
15% LiNO3
20% LiNO3
25% LiNO3
30% LiNO3
1200
1100
1000

Wavenumber/cm -1

(c)

Li + A) O C H 3 C
Li +
A)
O
C
H 3 C

O -

B)

Li + O C H 3 C
Li +
O
C
H 3 C

O -

Fig. 4 Modes of the carbonyl bond stretching: (A) Symmetric stretching (B) Asymmetric Stretching

-2.0 -2.5 -3.0 -3.5 -4.0 carboxymethyl iota carrageenan carboxymethyl kappa carrageenan -4.5 0 5 10
-2.0 -2.5 -3.0 -3.5 -4.0 carboxymethyl iota carrageenan carboxymethyl kappa carrageenan -4.5 0 5 10
-2.0
-2.5
-3.0
-3.5
-4.0
carboxymethyl iota carrageenan
carboxymethyl kappa carrageenan
-4.5
0
5
10
15
20
25
30
35
log(conductivity/S cm -1 )

Fig. 5

LiNO 3 salt concentration (wt.%)

-1.6 carboxymethyl kappa carrageenan carboxymethyl iota carrageenan -1.8 -2.0 y= -1.914x +3.88 r 2 =0.987
-1.6 carboxymethyl kappa carrageenan carboxymethyl iota carrageenan -1.8 -2.0 y= -1.914x +3.88 r 2 =0.987
-1.6
carboxymethyl kappa carrageenan
carboxymethyl iota carrageenan
-1.8
-2.0
y= -1.914x +3.88
r 2 =0.987
-2.2
y= -0.9496x +0.69
-2.4
r 2 =0.923
-2.6
3.00
3.05
3.10
3.15
3.20
3.25
3.30
log (conductivity/S cm -1 )

Fig. 6

(1000/T)/K -1

1.2 1.0 carboxymethyl kappa carrageenan-30% lithium nit carboxymethyl iota carrageenan-20% lithium nitr 0.8 0.6 0.4
1.2 1.0 carboxymethyl kappa carrageenan-30% lithium nit carboxymethyl iota carrageenan-20% lithium nitr 0.8 0.6 0.4
1.2
1.0
carboxymethyl kappa carrageenan-30% lithium nit
carboxymethyl iota carrageenan-20% lithium nitr
0.8
0.6
0.4
0.2
0.0
0
2000
4000
6000
8000
10000
12000
14000
16000
Current /µA

Fig. 7

time/s

0.10 0.08 30% LiNO3-carboxymethyl kappa carrageenan 20% LiNO3-carboxymethyl iota carrageenan 0.06 0.04 0.02 0.00
0.10
0.08
30% LiNO3-carboxymethyl kappa carrageenan
20% LiNO3-carboxymethyl iota carrageenan
0.06
0.04
0.02
0.00
-0.02
-0.04
-2
-1
0
1
2
3
Applied potential/V
3.0 V
3.1 V
Fig. 8
Current/µA