Ionics (2011) 17:407–414 DOI 10.1007/s11581-010-0517-z ORIGINAL PAPER Electrochemical and mechanical properties of nanochitin-incorporated PVDF-HFP-based polymer electrolytes for lithium batteries N. Angulakshmi & Sabu Thomas & K. S. Nahm & A. Manuel Stephan & R. Nimma Elizabeth Received: 24 June 2010 / Revised: 19 November 2010 / Accepted: 28 December 2010 / Published online: 12 February 2011 # Springer-Verlag 2011 Abstract Nanocomposite polymer electrolytes (NCPE) composed of poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) and chitin for different concentrations of LiClO4 have been prepared by a hot-press technique. The prepared NCPE films were subjected to XRD, SEM, FTIR and tensile analyses. The thermal stability of NCPE membrane was investigated by TG-DTA. Ionic conductivity studies have also been made as a function of lithium salt concentration for different temperatures ranging from 0 to 80 °C. The polymeric membrane comprising PVDF-HFP/ chitin/LiClO4 of ratio 75:20:5 (wt.%) offered maximum ionic conductivity. Thermal study reveals that these membranes are stable up to 260 °C. Keywords Batteries . Electrochemical characterizations . Polymer electrolyte . Nanocomposite electrolytes . XRD . Mechanical properties . Thermal stability . Ionic conductivity N. Angulakshmi : R. N. Elizabeth Department of Physics, Lady Doak College, Madurai 652 002, India S. Thomas School of Chemistry, Mahatma Gandhi University, Kottayam, India K. S. Nahm School of Chemical Engineering and Technology, Chonbuk National University, Chonju, Chonbuk 561-756, South Korea A. M. Stephan (*) Central Electrochemical Research Institute, Karaikudi 630 006, India e-mail: arulmanuel@gmail.com Introduction More than three decades, polymer electrolytes have drawn the attention of many researchers as they find applications in not only lithium batteries but also in other electrochemical devices which include supercapacitors and electrochromic devices, etc. Unlike the liquid electrolytes, these polymer electrolytes have a number of advantages like high-energy density, no leakage of electrolytes and absence of non-combustible reaction products at the electrode surfaces [1–5]. The polymer electrolytes have gone through different developmental stages namely (1) dry polymer electrolytes, (2) gel polymer electrolytes and (3) composite polymer electrolytes. Dry solid polymer electrolytes do not possess any organic liquids, and the polymer host along with the Li salt acts as solid solvent. The ionic conductivity of these dry polymer electrolytes (PEO-LiX) have been found to be very low (of the order of 10−8 S/cm at ambient temperature) which excludes it from practical applications [6, 7]. On the other hand, the gel polymer electrolytes composed of low molecular weight liquid plasticizers (e.g. PC, DMC, DEC etc.) along with polymer hosts offer high ionic conductivity at ambient temperature. However, gel polymer electrolytes lose their mechanical robustness upon plasticization. Furthermore, the lithium metal undergoes severe passivation upon contact with gel polymer electrolytes. This phenomenon eventually leads the battery systems for poor safety aspects. In the case of composite electrolytes, the ionic conductivity has been enhanced by the incorporation suitable fillers that prevent recrystallization process [8–11]. In a sparking pioneer research, Weston and Steele [12] have successfully incorporated Al2O3 in the poly(ethylene oxide) PEO-matrix. By virtue of its appealing properties like low cost, high electrochemical stability and helical structure the 408 PEO has drawn the attention of many researchers and has been intensively studied. Recent studies revealed that the composite polymer electrolytes (CPE) alone can offer improved electrolytes/ electrode compatibility and prevent safety for Li-polymer batteries [13–15]. The addition of fillers dramatically improves the morphological and electrochemical properties of polymer electrolytes [13–16]. Investigations have also been carried out on highly conducting ceramic fillers ionites [17], zeolites [18] as well as electrically neutral ceramic fillers [19]. Results reveal that the addition of ceramic filler improves the conductivity of polymer hosts and their interfacial properties in contact with Li electrode [15]. Kumar et al. [20] have shown that nanosized ceramic fillers have better compatibility with Li metal than micronsized fillers. Extensive studies have been made with fillers like SiO2, TiO2, γ-Al2O3 and α-Al2O3 [4]. In the recent past, poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) has been identified as a potential candidate due to its appealing properties; the polymer host itself has a dielectric constant of 8.4 which aids higher dissociation ionic species. Also, the PVDF crystalline phase acts as mechanical support while HFP amorphous phase facilitates for higher ionic conduction [21]. In the present study [20], chitin, one the most abundant polymers, poly(β-(1-4)-N-acetyl-D-glucosamine is used as inert filler which is biodegradable, antibacterial and is less toxic. It is also reinforced to strengthen polymeric materials due to its crystalline micro-fibrils form [22]. Shin et al. [23] have shown that membranes prepared by conventional solvent casting method lead to poor interfacial properties, at the Li-polymer interfaces and the traces of solvent are trapped in the nanosized inert fillers due to their high surface area even after prolonged drying. Hence in the present study the hot-press technique is employed for preparation of nanocomposite polymer electrolyte. Ionics (2011) 17:407–414 20 min and hydrolyzed with 3 N HCl under stirring for 1.5 h. After hydrolysis, the suspension was transferred to a dialysis bag and dialyzed for 24 h until its pH reached a value of 6. The pH of the suspension was adjusted to 3.5 with HCl. The dispersed whiskers were treated ultrasonically and were filtered to remove residual aggregates. The resulting nanochitin was preserved in a refrigerator with sodium azoture as a protectant against microorganisms. The prepared nanochitin particles were of size between 400 and 500 nm of length and diameter of 1 nm, and its AFM picture is displayed in Fig. 1. Preparation of nanocomposite polymer electrolyte PVDF-HFP (Aldrich, USA) and LiClO4 (Merck, Germany) were dried under vacuum for 2 days at 80 and 100 °C, respectively. Nanochitin was also dried under vacuum at 50 °C for 5 days before use. Nanocomposite polymer electrolytes were prepared by dispersing appropriate amounts of chitin in (PVDF-HFP) LiClO4 as displayed (Table 1) and hot-pressing into films as described elsewhere [23, 24]. The nanocomposite electrolyte films had an average thickness of 30–50 μm. This procedure yielded homogenous and mechanically strong membranes, which were dried under vacuum at 50 °C for 24 h for further characterization. Electrochemical characterization The prepared films were sandwiched between the two stainless steel blocking electrodes of diameter 1 cm and the ionic conductivity of the membranes was measured using an electrochemical impedance analyzer (IM6 Bioanalytical Experimental Synthesis of nanochitin The chitin precursor was purchased from local sources in India and was boiled and stirred with a 5% aqueous solution of KOH for 6 h in order to remove most of the proteins. Subsequently, it was washed with distilled water and dried. This process was repeated three times. The sample was then bleached with 17 g of NaCl in 1 L of water containing 0.3 M sodium acetate buffer for 6 h at 80 °C. The bleaching solution was changed every 2 h. The chitin suspension was then kept in 5% KOH for 72 h to remove any residual protein, centrifuged at 3,000 rpm/min for Fig. 1 AFM image of nanochitin Ionics (2011) 17:407–414 409 Table 1 Compositions of polymer, chitin and LiClO4 Sample Results and discussion Polymer (wt.%) Chitin (wt.%) LiClO4 (wt.%) S1 S2 S3 S4 S5 S6 S7 S8 95 90 85 75 70 94 93 92 0 5 10 17 20 5 5 5 5 5 5 8 10 1 2 3 S9 91 5 4 System, USA) in the 50 mHz to 100 kHz frequency and ac amplitude was 10 mV at various temperature viz., 0, 15, 30, 45, 60, 70 and 80 °C. The bulk resistance of polymer electrolyte was found from the impedance spectrum. Thus, the ionic conductivity was calculated based on the equation: s ¼ ‘=A 1=Rb Where σ is the ionic conductivity, Rb the bulk resistance; ℓ and A are the thickness and area of the specimen, respectively. Morphological study of the films was made by a scanning electron microscopy (SEM; Hitachi S-4700 FESEM) under a vacuum condition (10−1 Pa) after sputtering gold on one side of the films. The thermal property of the nanocomposite polymer electrolytes (NCPE) film was investigated with SDT Q 600 instrument. Differential scanning calorimetry (DSC) measurements were performed at a rate of 10 °C/min between 20 and 250 °C, and in thermogravimmetry-differential thermal analysis (TG-DTA) the temperature range was 20–500 °C. The lithium/polymer electrolyte interface was analysed using Fourier transform infrared (FTIR; Thermo NICOLET Corporation, Nexus model 670) by using single internal reflection mode. The infrared spectra were obtained at ambient temperature with an 8 cm−1 resolution. The mechanical strength of the NCPE was determined using a tensile machine (Tinius Olsen) with a constant cross-head speed of 10 mm/min. The sample dimensions were 20×50×0.1 mm. X-ray diffraction (XRD) measurements were conducted on a Bruker D8 X-ray diffractometer with Cu-Kα radiation (λ=1.54178 Å) at 50 kV and 250 mA with a scanning rate of 2 °/min. LiFePO4 was synthesised by a simple sol–gel method as described earlier [24]. The composite cathode was prepared by blending LiFePO4 active material (70%) with super-P carbon electronic conductor (20%) and PVDF binder (10%). All preparations were performed in an argonfilled glove box (MBRAUN, Germany) having a humidity content below 10 ppm. XRD analysis X-ray diffraction analysis is very useful in determining the structure of materials. Figure 2(a–d) shows the X-ray diffraction patterns of samples PVDF-HFP, chitin, PVDFHFP+LiClO4 (S1) and PVDF-HFP+LiClO4 +chitin (S5), respectively. The diffraction peaks at 2θ=18.4, 20 and 26.6 correspond to (1 0 0), (0 2 0) and (1 1 0) reflections of crystalline PVDF [25].This confirms partial crystallisation of the PVDF units in the copolymer to give an over-all semicrystalline morphology for PVDF-HFP [26]. Since LiClO4 is complexed in the polymer matrix, peaks corresponding to LiClO4 are not observed which also indicate that the lithium salt is completely dissolved in the polymer matrix (Fig. 2(c)). Figure 2(d) shows that the intensity of crystalline peaks decreased and broadened upon incorporation of chitin. However the chitin peaks remain unaltered. These observations apparently reveal that the polymer undergoes significant structural reorganisation while adding inert fillers and salts. Upon the addition of nanochitin and lithium salt, the crystallinity of the polymer has been considerably reduced. This reduction in crystallinity is attributed to small particles of inert filler, which changes the chain reorganisation and facilitates higher ionic conduction [27]. Thermal analysis Figure 3 shows the DSC thermograms of samples PVDFHFP+LiClO4 (S1) and PVDF-HFP+chitin+LiClO4 (S5), (e) (d) (c) (b) (a) 10 20 30 40 50 60 70 80 2 Theta (Degree) Fig. 2 XRD spectra of polymer membranes: a PVDF-HFP, b chitin, c PVDF-HFP+LiClO4+5% chitin, d PVDF-HFP+LiClO4+17% chitin and e PVDF-HFP+LiClO4+20% chitin Ionics (2011) 17:407–414 Endo 410 (a) 0% Chitin (b) 5% Chitin (c) 17% Chitin (d) 20% Chitin Heat Flow (mW) 14 S5 12 S1 50 100 150 Stress (MPa) 10 200 8 (a) 6 4 Temperature (ºC) 2 Fig. 3 DSC thermograms of PVDF-HFP+LiClO4 (S1), PVDF-HFP+ chitin+LiClO4 (S5) (b) 0 0 respectively. The melting endotherm peak of PVDF-HFP+ LiClO4 (S1) (140 °C) gets broadened, and the melting temperature gets reduced upon incorporation of nanochitin and lithium salt in the polymer matrix (S5). The broadening of the endotherm also takes place with an apparent decrease in the heat of fusion (ΔHf) with increasing concentration of filler [28]. In order to evaluate the thermal stability of polymer electrolytes, the thermogravimetric analysis of the NCPE was performed under nitrogen atmosphere. The TG-DTA traces of PVDF-HFP+ LiClO4 (S1) and a PVDF-HFP + chitin + LiClO4 (S5) membranes are displayed in Fig. 4a, b, respectively. A weight loss of about 3% was observed about 116 °C for sample (S1) and is attributed to the release of water absorbed at the time of loading the sample [29, 30]. Furthermore, no weight loss was observed up to 304 °C which indicates that no decomposition was induced by the thermal steps of the hot-press process [24]. A peak exhibited in DTA curve at about 140 °C is attributed to the eutectic transition in the electrolytes [28]. Upon addition of chitin in the polymer matrix (Fig. 4b), the 5 10 20 25 30 35 40 Fig. 5 Stress vs Strain curves of polymer electrolytes PVDF-HFP+ LiClO4+ x% chitin: (a) x=0, (b) x=5, (c) x=17 and (d) x=20 decomposition temperature is reduced to 260 °C which is attributed to the decomposition of chitin. Tensile measurements In order to quantify the mechanical strength, the stress–strain properties have been measured and are shown in Fig. 5. The stress–strain behaviour gives fundamental information about the load Vs deformation characteristics of polymer composites. In the case of unfilled system (0% chitin), the sample shows two distinct regions: the initial linear region reflects the elastic characteristic and then nonlinear region shows the plastic deformation. As expected, the neat sample (sample S1) has high elongation at break (21%) and low tensile strength (12 MPa) as compared with the filled nanocomposites [31]. Upon the addition of chitin, we can see that the moduli and tensile strength 0.8 1.4 90 0.8 0.6 85 0.4 0.6 95 Weight (%) 1.0 Temperature Difference (oC) 1.2 TGA 100 90 0.4 85 0.2 80 DTA DTA 0 50 100 150 200 250 300 350 400 0.2 450 75 0 o Temperature ( C) Fig. 4 TG-DTA traces of a PVDF-HFP+LiCIO4 and b PVDF-HFP+chitin+LiCIO4 100 200 300 o Temperature ( C) 400 0.0 500 Temperature Difference (oC) TGA 80 45 S5-Kynar+chitin+LiClO 4 95 Weight (%) 15 Strain (%) S1 -Kynar+LiClO4 100 (d) (c) Ionics (2011) 17:407–414 411 Fig. 6 SEM images of a PVDFHFP+LiClO4, PVDF-HFP+ LiClO4+chitin, b 5% chitin and c, d 20% chitin increases (to 13 MPa) with dramatic decrease in strain at break (4.2%). The maximum tensile strength and moduli are obtained at 5% addition of chitin. At higher concentration of chitin, the decrease in tensile strength is attributed to the aggregation of chitin particles in the polymeric membrane. Scanning electron microscope analysis Figure 6a–d shows typical SEM images of samples S1, S3 and S5, respectively. Figure 6a shows a smooth surface with different pore sizes. According to Chu et al. [32, 33], the morphology of the electrolyte surface can be modified/ tailored by the incorporation of both ionic salts and fillers. The SEM image (Fig. 6b) of PVDF-HFP+5% chitin+ LiClO4 (sample S3) shows a relatively smooth surface with inhomogeneous morphology. Although it was intended to prepare a uniform distribution of nanochitin in PVDF matrix, the aggregation of nanoparticles with increasing concentration of nanochitin could not be achieved in the a Figure 7a, b shows the variation of ionic conductivity as a function of temperature for different concentrations of lithium salt and nanochitin, respectively. It is well known that Li ions migrate in two ways: (a) move along the molecular chains of polymer, and (b) move in the amorphous phase of polymer electrolyte [34]. The former is slow transport where as the latter is fast. Figure 7a illustrates that the ionic conductivity increases with the increase of temperature and salt concentration. The ionic conductivity S1 S2 S3 S4 S5 1E -6 Ionic Conductivity (S/cm) Ionic Conductivity (S/cm) Ionic conductivity b S1 S6 S7 S8 S9 1E -6 porous PVDF-HFP-based electrolytes, as evidenced in Fig. 6c (PVDF-HFP+LiClO4 +20% chitin, sample S5). This relatively smooth morphology (sample S1, Fig. 6a) is attributed to a reduction in the crystallinity of PVDF-HFP due to cross-linking with cations [32]. However at high contents of nanochitin (20%), the membrane is seen to have a rough surface with an inhomogeneous morphology with islands of aggregated particles [31]. 1E -7 1E -8 1E -9 1E -7 1E -8 1E -9 1E -10 1E -10 2.8 3.0 3.2 3.4 -1 1000/ T ( K ) 3.6 3.8 2. 8 3.0 3. 2 3.4 3. 6 -1 1000/ T ( K ) Fig. 7 Ionic Conductivity as a function of temperature for the various a lithium salt concentrations and b chitin concentrations 3.8 412 Ionics (2011) 17:407–414 Fig. 8 FTIR spectra of a PVDF-HFP, b chitin, c PVDFHFP+LiClO4 and d PVDFHFP+LiClO4+chitin d d d Transmittance (%) c c c b b b a a a 4000 3800 3600 3400 3200 3000 1800 1700 1600 1500 1400 1300 1200 1000 800 600 400 Wavenumber (cm -1 ) gradually increases from 1.0×10−9 to 4.8×10−9 S/cm with the increase in LiClO4 content for the samples S6 and S9, respectively at 30 °C. Similarly, it increases from 3.2×10−7 to 3.5×10−5 S/cm respectively for the samples S6 and S9. Apparently, at 80 °C the ionic conductivity of S6, S7 and S8 are lower than the S1 but S9 is higher than the S1. These results are in accordance with those reported on PEO-based polymer electrolytes with SiO2 lithium imide anion system [35]. The ionic conductivity increases with the rise of amount of nanochitin in the polymer film can be seen in Fig. 7b. The volume of the interfacial layers, which possesses a higher ionic conductivity, increases with the amount of nanochitin filling in the polymer film so the number of tunnels for lithium ions migration enhances. On (c) the other hand, the competition between nanochitin and F atoms with respect to lithium ions facilitates the migration for lithium ions in polymer electrolyte. So, the ionic conductivity of polymer electrolyte increases with the addition of nanochitin into polymer matrix. According to Scrosati and co-workers [36], the Lewis acid groups of the added inert filler may compete with the Lewis acid lithium cations for the formation of complexes with the PEO chains as well as the anions of the added lithium salt. In the present study, the Lewis acid group of the added filler (e.g. –OH group of chitin) may quite likely compete with the Lewis acid lithium cation for the formation of complexes in the PVDF-HFP chains as well as with the anion of the LiX salts. This in turn results in structural modifications and promotes “free” ions and this accounts for the observed enhancement in ionic conductivity. 100 90 1491 405 1579 (b) 938 (a) 4000 3500 3000 2500 2000 1500 1000 500 Wave number (cm -1 ) Discharge Capacity (mA-h/g) % Transmittance 1754 80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16 18 20 Cycle number Fig. 9 FTIR spectrum of a sample S5; in situ from a lithium surface in contact with b PVDF-HFP+LiClO4 and c PVDF-HFP+LiClO4+ chitin (S5) Fig. 10 Discharge capacity as a function of cycle number for Li/ NCPE/LiFePO4 at 80 °C (C/10 rate) Ionics (2011) 17:407–414 FTIR analysis FTIR has been used as a powerful to characterise the molecular and structural changes in the polymer electrolyte systems. Figure 8(a–d) shows the FTIR spectra of pure PVDF-HFP, chitin, PVDF-HFP+LiClO4 and PVDF-HFP+ LiClO4 +chitin. The vibrational bands at 490 cm−1 (Fig. 8a) are assigned to the wagging vibrations of CF2 group. The frequencies of 1,071,759 and 607 cm−1 belongs to the vibration of crystalline phase of (PVDF-HFP) whereas the frequencies of 883 and 841 cm−1 are assigned to the vibration of amorphous phase of (PVDF-HFP) [26]. The CH2 ring and CH groups absorb in the regions of 3,100– 2,990 cm−1. The peaks appearing at 1,192 and 2,923 cm−1 are assigned to the asymmetrical stretching vibrations of CF2 and CH2 groups, respectively [37]. The deformation vibration of CH2 group which appears at the frequency 1,402 cm−1 [38] will move to a higher frequency/position with the weakening of interaction between H atoms of CH2 groups and F atoms of CF2 groups. The vibration bands at 1,647 and 3,418 cm−1 can be assigned to the stretching and bending vibrations of OH bonds of the absorbed water. Several IR spectral studies have been made on chitin [37, 38]. The amide I band is split into two at 1,659 and 1,626 cm−1. The band at 1,659 cm−1 is commonly assigned to stretching of the C=O group hydrogen bonded to N–H of the neighbouring intra-sheet chain of (polyamides) and proteins [35].The band at 1,626 cm−1 is attributed to a specific hydrogen bond of C= O in the hydroxyl methyl group of the next chitin residue of the same chain [39]. Upon incorporation of LiClO4 in polymer host, the peak at 758 cm−1 shift to 748 cm−1 attributed to wagging band of CH2Cl. Frequencies 840–560 cm−1 are assigned to C–Cl stretching vibrations. The characteristic absorption vibrations of LiClO4: 1,150–1,080 cm−1, 941 cm−1 are assigned to symmetrical vibration of ionic pairs between Li+ and ClO4− [39], 624 cm−1 is stretching vibration of ClO4− and the sharp peaks 3,597 and 1,637 cm−1 are stretching and bending vibrations of OH bonds of the absorbed water. The absorption peaks at 2,983 and 3,025 cm−1, which are assigned to the symmetrical and non-symmetrical stretching vibration of CH2 groups, appear after addition of LiClO4 to polymer film, because of the interaction between lithium ions and F atoms. It is found that the intensity of these two absorptions decreases with the addition of nanochitin (Fig. 8(d)) in polymer matrix. Figure 8(d) shows that the deformed vibration of CH2 group moves to 1,407 cm−1 after addition of nanochitin into polymer matrix from 1,402 cm−1 (Fig. 8(c)). Interfacial property of Li/NCPE Figure 9(a) shows the FTIR spectrum of NCPE (sample S5) consisting PVDF-HFP+LiClO4 +chitin. The FTIR spectra 413 obtained on a lithium electrode in contact with PVDF-HFP+ LiClO4 and PVDF-HFP+LiClO4 +chitin polymer membranes (through KBr window) are displayed in Fig. 9(b) and (c), respectively. In Fig. 9(c), the original features belonging to the polymer electrolytes not only disappeared, but new peaks have arisen. When a nanochitin-incorporated composite electrolyte comes in contact with the lithium metal anode, new peaks appear at 1,754, 1,579, 1,492,938 and 405 cm−1. The peak that appears at 405 cm−1 is attributed to Li–N and 938 cm−1 is assigned to unconjugated cyclic anhydrides. The peaks at 1,754, 1,579 and 1,491 cm−1 are attributed to C=O, CH2 stretching and C–C skeletal vibrations. [40, 41] It is significant that no predominant peak appears around 1,100 cm−1 and is attributed to the fact that LiClO4 is reduced to LiClOy species thus confirming its presence [42]. Charge–discharge studies The discharge capacity as a function of cycle number of the polymer cell composed of Li/NCPE (sample S5)/LiFePO4 performed at C/10 rate is depicted in Fig. 10. The cell delivered an initial discharge capacity of 80 mAh/g during its first three cycles and decreased to 68 and 43 mAh/g at its 10th and 20th cycle, respectively. The fade in capacity has been calculated as 0.54 mAh per cycle. 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