Structural and Ionic Transport Properties of Protonic Conducting Solid

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Structural and Ionic Transport Properties of Protonic Conducting Solid Biopolymer Electrolytes Based on Carboxymethyl Cellulose Doped Ammonium Fluoride Muhamad Amirullah Ramlli, and Mohd Ikmar Nizam Mohamad Isa J. Phys. Chem. B, Just Accepted Manuscript • DOI: 10.1021/acs.jpcb.6b06068 • Publication Date (Web): 10 Oct 2016 Downloaded from http://pubs.acs.org on October 15, 2016

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The Journal of Physical Chemistry

Structural and Ionic Transport Properties of Protonic Conducting Solid Biopolymer

Electrolytes

Based

on

Carboxymethyl

Cellulose

Doped

Ammonium Fluoride M. A. Ramlli & M. I. N. Isa* Advanced Materials Team, Ionic State Analysis (ISA) Laboratory, School of Fundamental Sciences, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

ABSTRACT. Fourier Transform Infrared (FT-IR), X-Ray Diffraction (XRD) and Transference Number Measurement (TNM) techniques were applied to investigate the complexation, structural, ionic transport properties and dominant charge carrier species in carboxymethyl cellulose (CMC) doped with ammonium fluoride (NH4F) solid biopolymer electrolytes (SBEs) system, which were prepared via solution casting technique. The SBEs were partially opaque in appearance with no phase separation. The occurrence of interactions between the host polymer (CMC) and ionic dopant (NH4F) were proved by FT-IR analysis at C-O band. XRD spectrum were analyzed using Origin 8 software disclose the degree of crystallinity ( %) of the SBEs decreased with addition of NH4F content, indicates the increase of amorphous nature of the SBEs. Ionic transport properties analysis reveals that the ionic conductivity of the SBEs is dependent on the ionic mobility (µ) and diffusion of ions (D). TNM analysis confirms the SBEs are proton conductor.

1. INTRODUCTION Excellent properties of natural polymers have become the center of interest for many researchers to utilize them as polymer host in proton-conducting solid biopolymer electrolytes (SBEs) for many years now.1-7 Although proton conducting SBEs does not have high energy capacity as compared to Li+ based electrolytes, it have no safety issues plus with very affordable electrode and electrolyte materials, it can lower the cost of overall battery production.8 These properties made the proton batteries a good alternative to be used in low power electronic devices. A few example of natural polymers that can be used are, starch,9 cellulose,10,11 kappa-carrageenan12 and chitosan13. Carboxymethyl cellulose (CMC) is a natural cellulose that has been modified to be able to dissolve in water by introducing Sodium (Na) into the polymer structure. It has the 1 ACS Paragon Plus Environment


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advantages of a cellulose, plus with the great solubility in water and has been reported as a great polymer base for proton-conducting SBEs.14,15 In this work, CMC will be used as host polymer. Dissolving inorganic salt into the polymer matrix is the easiest, cheapest, yet efficient way to increase the ionic conductivity of the polymer. By dissolving salt (proton donor), it can enhance the conductivity of the host polymer by diffusing free mobile ions that can helps the conduction occurs more frequently in the polymer system, thus increasing the ionic conductivity.16,17 CMC will be doped with different content of ammonium fluoride (NH4F) which will acts as proton donor. In polymer-ammonium salt system, the conduction was done by either NH3+ or H+, but many works reported that the ionic conduction was due to the H+ that loosely bound to NH4+ in the system.18,19 We have previously reported20, the highest ionic conductivity obtained for CMC-NH4F polymer system is 2.68x10-7 S cm-1 at room temperature for sample CMCAF-9. The SBE has the lowest activation energy which contributes to the high ionic conductivity and from dielectric and modulus study, it shows an ionic conductor behavior. Thus in this work, we are going to investigate the other several properties that have been reported to also contributes to the ionic conductivity of SBE namely; the amorphousity, number of free mobile ions (n), percentage of free ions, ionic mobility (µ) and the diffusion coefficient of ions (D) in the polymer system.21 TNM will be used to support the claims from the previous report whether the SBEs are ionic conductor or not.

2. MATERIALS AND EXPERIMENTAL SECTION 2.1. Materials and SBEs Preparations. 2.0 g of carboxymethyl cellulose (CMC) powder (Acros Organics CO.) was dissolved in distilled water and doped with (3, 5, 7, 9, 11, 13 wt. %) amount of NH4F (R&M Chemicals). The mixtures were magnetically stirred until homogenous solutions were obtained. The solutions were dried in oven at 60oC until the thin film are formed and then stored in desiccator to prevent from moisture contamination. 2.2. Fourier Transform Infrared Technique. Fourier Transform Infrared (FT-IR) technique was done by using Thermo Nicolet 380 FT-IR spectrometer equipped with Attenuated Total Reflection (ATR) with germanium crystal to determine the complexation between the CMC and NH4F SBEs. The SBEs were cut into suitable sizes and placed in between the specimen holder and germanium crystal of the Thermo Nicolet. The infrared spectrum beamed 2 ACS Paragon Plus Environment

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through the SBE samples at frequency ranged from 700 cm-1 to 4000 cm-1 at ambient temperature. 2.3. X-Ray Diffraction Technique. X-Ray Diffraction (XRD) patterns were recorded using Rigaku Miniflex II Diffractometer. An X-ray beam (Cu) with wavelength λ (1.5406 Å) radiated at 2θ angles between 5 to 80 degrees. The degree of crystallinity (χ ) of the SBEs were determined using Origin 8 software by implemented deconvolution technique following.27 2.4. Ionic Transport Properties by FT-IR Deconvolution Technique. The transport properties of the SBEs were determined by using deconvolution of FT-IR technique which adapt the Gaussian-Lorentz function in Origin 8 fitting software following.26 In this technique, the region of interest must be converted into the absorbance mode before proceed to deconvolution analysis. 2.5. Transference Number Measurement Technique. Transference number measurements (TNM) was done using UNI-T UT803 True RMS bench multimeter interfaced with a computer and the set up following the DC polarization technique. The cations transference numbers, t+ in the SBE were determined by monitoring the current (I), as a function of time (t), on application of a fixed dc voltage (1.5 V) across the SBEs, which were sandwiched between two stainless steel electrodes.

3. RESULTS AND DISCUSSION 3.1 Fourier Transform Infrared Analysis. FT-IR analysis was done to acquire the information on the structure and to identify the functional groups in CMC and NH4F. Previously reported by (Ramlli et. al.,-2015)19 discussed the complexation of CMC-NH4F SBEs and they found that the characteristic bands in CMC spectra at ~3363 cm-1 was due to the stretching mode of O-H, whereas the stretching mode of C-H, C=O and O-H appeared at ~2895 cm-1, ~1585 cm-1 and ~1408 cm-1 respectively. The bending mode of C-H was found at ~1315 cm-1 and peaks at ~1084 cm-1, ~1047 cm-1 and ~1024 cm-1 were correspond to the bending mode of C-O. In NH4F spectra, the stretching mode of N-H were found at ~3176 cm-1 and ~3028 cm-1. Meanwhile, the peak at ~2823 cm-1 and ~1448 cm-1 were identified as bending mode of N-H. Figure 1 shows two regions of FT-IR spectrum of CMC-NH4F SBEs namely Region 1 (2600 3600 cm-1) and Region 2 (850 – 1600 cm-1).

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In Region 1, it can be seen that the peak intensity of hydroxyl band at ~3363 cm-1 has disappeared with the addition of NH4F content. This specifies strong interaction occurred between the polymer host and ionic dopant where H+ from N-H in NH4F interacts with the hydroxyl group in the CMC. In Region 2, the bending of mode of C-O at ~1047 cm-1 and ~1024 cm-1 have shifted to ~1055 cm-1 and ~1028 cm-1 with the addition of 9 wt. % NH4F respectively. The shifting of these bands vibrations was due to the protonation process where the attachment of proton (H+) to hydroxyl group (O-H) of CMC.

Figure 1: FT-IR spectra of CMC-NH4F SBEs: a) 0%, b) 3 %, c) 5 %, d) 7 %, e) 9 %, f) 11 %, g) 13 %. The changes to these band vibrations is foreseen in this work because of the exchanges between H+ of NH4+ and carbonyl group of CMC occurred. It is believed that the addition of salt content has increased the number of H+ in the polymer system and were denoted by the shifting of the band vibrations and intensities. Usually, the spectrum in FT-IR are always have sharp peaks, whereas for polymer sample which in amorphous state, the peaks are slightly broadened.29 This can be seen in the present work where the peaks of CMC broadened with the addition of 4 ACS Paragon Plus Environment

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ammonium salt content. The increased amorphous nature of the SBEs was further proved in XRD analysis. 3.2. X-Ray Diffraction analysis. The diffraction pattern of CMC and NH4F were shown in Figure 2. A broad peak at ~20.00o in CMC spectra was due to the strongest cellulose peak. It is also known as amorphous hump which is the characteristic of an amorphous material.30 The XRD spectra of NH4F (JCPDS no: 35-758) shows sharp poly-crystalline peaks at 2θ = ~23.66o, ~27.46o, ~41.50o, ~43.22o and ~62.06o with their orientations of (100), (101), (110), (103) and (203) respectively which reveals the crystalline nature of the NH4F.

Figure 2: XRD diffraction of CMC and NH4F. The XRD spectrum for all SBEs were depicted in Figure 3. From the figure, it can be seen that the poly-crystalline peaks which originated from the NH4F have appeared in all the SBEs. The amorphous hump at 2θ = ~20o has broadened with the addition of NH4F content until sample with 9wt. % NH4F which has been conveyed in our previous report.19 This phenomenon implies the increase in amorphous nature of the SBEs.25 In order to prove the increased in amorphous nature of the SBE, the degree of crystallinity of the SBEs were determined. The XRD deconvolution method was implemented and the percentage of crystallinity of each SBE was calculated using Equation 1.27, 31 %

100

(1)



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Here Ac = area under the peak representing the total crystalline region, Aa = area under the peak representing the total amorphous region and = is the percentage of crystallinity (%). The calculated value of was tabulated in Table 1.

Figure 3: XRD diffraction of all SBEs at ambient temperature. Table 1: Degree of crystallinity for selected SBE samples. (%) Sample Ac Aa CMCAF-3 3060 7097 43.12 CMCAF-5 5407 12772 42.33 CMCAF-7 4124 9885 41.72 CMCAF-9 2225 6414 34.69 CMCAF-11 2537 5606 45.26 From Table 1, it can be seen that the degree of crystallinity, of the SBEs decreased with the addition of NH4F content. According to (Rahaman et al.,-2014),27 the percentage of crystallinity is inversely proportional to the amorphousity of the SBE, which means that the decreased of indicates the increase of the amorphousity of the SBEs. In this work, CMCAF-9 shows the highest amorphousity due to the lowest value of . This further supports the FT-IR 6 ACS Paragon Plus Environment

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analysis where the addition of the ammonium salt has increased the amorphous nature of the SBEs. From our previous report,19 sample with 9 wt. % NH4F records the highest ionic conductivity. This can be explained by the amorphous nature of the SBE contributes in ease the diffusions of ions and also reduce the energy barrier to the segmental motion of the polymer system allowing easier movement to the free ions hence increased the ionic conductivity.24 3.3. Ionic Transport Analysis. The number of free mobile ions (n), ionic mobility (µ) and diffusion coefficient of ions (D) were determined by deconvoluting the FT-IR spectrum. The value of n, µ and D were calculated using Equation 2, 3 and 4 respectively.

! %

(2)

#

(3)

'()

(4)

" $% &

%

Here M is the number of moles of salt used in each electrolyte, NA is Avogadro’s number (6.02 × 1023), σ is the dc conductivity, e is the electric charge (1.602 × 10-19 C), k is the Boltzmann constant (1.38 × 10-23 JK-1) and T is the absolute temperature. The percentage of free ions and VTotal were determined from Equation 5 and Equation 6 respectively. Percentage of free ions %

=%>?@8

6

6

100%

=%>?@8

7898:; 8C DEDF + 8C HIJ KF

(5) (6)

Af is the area under the peak representing the free ions region and Ac is the total area under the peak representing the contact ions. VTotal is the total volume of the SBE. The area of interest are in between 950 cm-1 and 1200 cm-1 wavenumbers because the bands representing the free ions and contact ions pair are within this region.32 The deconvoluted FTIR spectra of CMCAF-9 at wavelength 900 cm-1 to 1200 cm-1 were depicted in Figure 4. From the figure, the free ions represents the free mobile ions (~1035 cm-1) and contact ions pair (~1106 cm-1 & ~1066 cm-1) represents the contact ions and ions aggregate in the polymer system. The determined value of n, µ, D and ionic conductivity of the SBEs were depicted in Figure 5. The ionic conductivity were calculated using Equation 7. 7 ACS Paragon Plus Environment


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L

M NO P

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(7)

Here, t is the thickness of the SBE, Rb is the bulk resistance and A is the contact area of the electrodes and SBE.

Figure 4: FT-IR deconvolution of selected SBE samples at C-O band. From Figure 5, it can be seen that the value of n increases with the increment of NH4F content. According to (Samsudin et. al.,-2012)23 the highest conductive sample should have the highest number of mobile ions. However, in this work, the highest conductive SBE (CMCAF-9) does not has the highest number of n compared to CMCAF-11 and CMCAF-13 which has higher number of n. This is because the optimum value of n was at 9 wt.%, any salt contents higher than that, it will be too much in the polymer system where it overcrowded with n which tends to become ion clusters, hence decreased the ionic mobility and the diffusions of ions. The reduced value of µ and D lead to the decreased of ionic conductivity of the SBEs. The event can be seen at sample CMCAF-11 and CMCAF-13 where both have higher number of n but low value for µ and D, therefore it can be concluded that the ionic conductivity of the CMC-NH4F SBEs were influenced more by the number of µ and D. Similar behavior was also observed by (Ahmad & Isa-2015)3 where their ionic conductivity was influenced by µ and D in their polymer system.


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Figure 5: Ionic conductivity and the transport properties of the SBEs. 3.4. Transference Number Measurement Analysis. The determination of dominant charge carrier species in the SBEs were determined from Transference Number Measurement (TNM). The current through the circuit was recorded until it reaches saturation and the graph of normalized polarization current against time at ambient temperature for CMCAF-9 was depicted in Figure 6. The measurement of the polarization current should gives the cationic transference value after the polarization current saturated, since the electron conduction in SBEs can be neglected.23, 33 From the figure, the observed initial total current decreased with time because of the reduction of the ionic species in the SBE and became constant in fully depleted situation. Here, the ion migration occurred when the voltage, V was applied and the cell was polarized after it achieved steady state was. In polarized state, the migration of electrons between the interfaces and electrolyte was caused by the remaining current flow which can be ignored.32 The rapidly fall ionic currents through ion-blocking electrodes indicates that the SBE samples was ionically conducting species.



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Figure 6: Normalized polarization current (A) against time (s) for selected CMCAF-9 at ambient temperature. The ionic mobility of cation, µ+ and anion, µ- and diffusion coefficient of cations, D+ and anions, D- were calculated from the measured values of conductivity and cation transference number, t+ by using the following equations:34, 35 M

QRS

(7)

Q

& & + &T M V

()#

(8)

$% U

VW

(9)

W VX

D+ and D- is the diffusion coefficient of cation and anion. The ionic mobility, µ can be defined according to the following equation: " " + "T M '

#

(10)

$Y

'W

(11)

W 'X

Here µ+ and µ- is the ionic mobility of cation and anion respectively. The value of D+, D-, µ+ and µ- of selected SBE samples were calculated and tabulated in Table 2. From the table, it is observed that the value of cationic diffusion coefficient (D+) and cationic mobility of ions (µ+) is higher than the value of anionic diffusion coefficient (D-) and anionic mobility of ions (µ-) for all the SBEs. This concludes that the CMC-NH4F SBE samples were predominantly proton conductor, thus in agreement with the FT-IR analysis. 10 ACS Paragon Plus Environment

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Table 2: The value of D+, D-, µ+ and µ- of selected samples. Sample

D+ (cm2s-1) (×10-19)

D- (cm2s-1) (×10-19)

µ+ (cm2 V-1s-1) (×10-12)

µ- (cm2 V-1s-1) (×10-12)

CMCAF-3 CMCAF-5 CMCAF-7 CMCAF-9

139 8.25 4.77 6.76

8.89 0.62 1.19 2.90

162 9.58 5.54 7.85

10.3 0.721 1.38 3.36

4. CONCLUSION A series of a new type of solid biopolymer electrolytes based on CMC doped with NH4F have been prepared via solution casting technique. From FT-IR analysis, the interactions between CMC and NH4F have occurred at bending mode of C-O (1029 cm-1) of CMC. The addition of NH4F has increased the amorphous nature of the SBEs as the degree of crystallinity decreased as analyzed in XRD technique. With the deconvolution of FT-IR spectrum, the transport properties of the SBEs were determined and it can be concluded as the ionic conductivity is more dependent to the ionic mobility and diffusion coefficient of ions. Lastly, TNM analysis confirms that the SBEs are protonic conductors where the value of anionic of µ and D is higher than the value of cationic of µ and D. In the final analysis, the addition of NH4F content has significantly increased the ionic conductivity of CMC by enhancing the amorphous nature, transport properties as proven in FT-IR and XRD analysis. AUTHOR INFORMATION Corresponding Author E-mail: [email protected]. Tel: +609-668 3111 ACKNOWLEDGEMENT The author would like to appreciate the Malaysia Ministry of Higher Education for the financial aid through FRGS grant and School of Fundamental Sciences, Universiti Malaysia Terengganu, Malaysia for providing the facilities.



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Table of Figures Figure 1: FT-IR spectra of CMC-NH4F SBEs: a) 0%, b) 3 %, c) 5 %, d) 7 %, e) 9 %, f) 11 %, g) 13 %. Figure 2: XRD diffraction of CMC and NH4F. Figure 3: XRD diffraction of all SBEs at ambient temperature. Figure 4: FT-IR deconvolution of selected SBE samples at C-O band. Figure 5: Ionic conductivity and the transport properties of the SBEs. Figure 6: Normalized polarization current (A) against time (s) for selected CMCAF-9 at ambient temperature.


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TOC graphic


Structural and Ionic Transport Properties of Protonic Conducting Solid

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