PDADMAC and application in wide temperature range

Materials Letters 269 (2020) 127657

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Multi-adaptability supercapacitor electrolyte based on Na-MMT/PDADMAC and application in wide temperature range Bin Huang, Xinming Wu ⇑ School of Materials Science and Chemical Engineering, Xi’an Technological University, Xi’an 710032, PR China

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Article history: Received 14 January 2020 Received in revised form 1 March 2020 Accepted 14 March 2020 Available online 14 March 2020 Keywords: Functional Structural Polyelectrolyte Multi-adaptability Electrolyte

a b s t r a c t Polyelectrolyte is widely used in supercapacitors, but its poor matching with electrodes and narrow operating temperature range limit its further application. Here, Na-Montmorillonite/Poly dimethyl diallyl ammonium chloride (Na-MMT/PDADMAC) composite polyelectrolyte was prepared by solution intercalation and assembled into solid supercapacitor with three different electrodes (carbon, NiCo(OH)2 and Polypyrrole electrode). The result shows that Na-MMT/PDADMAC polyelectrolyte has a good matching performance with the three kinds of electrode. After 1000 cycles at 15℃, 35℃ and 50℃, the capacitance of all electrodes basically remain above 90%, showing wide operating temperature range. More interestingly, with the increase of Na-MMT, the combustion resistance of Na-MMT/PDADMAC solid polyelectrolyte film gradually increases, and the maximum flame resistance time can reach 50 s, indicating that the solid electrolyte film has good heat resistance. The good matching and wide temperature adaptation range with electrodes are mainly attributed to the addition of Na-MMT, which not only increases the ion migration rate, but also limits the thermal decomposition of PDADMAC molecular chain. Ó 2020 Elsevier B.V. All rights reserved.

1. Introduction In recent years, supercapacitor has become a research hotspot in new energy storage devices due to its high power density, short charging time and long cycle life. As one of the main components of the supercapacitor, electrolyte is directly affects the comprehensive electrochemical performance [1–3]. Among many electrolyte materials, polyelectrolyte is easily to be prepared into solid electrolyte, however, its further application is limited by its narrow temperature application range and poor matching with electrode [4,5]. As a strong cationic polyelectrolyte, poly dimethyl diallyl ammonium chloride (PDADMAC) has advantages of noninflammability and excellent hydrolysis stability, and has great potential as a supercapacitor electrolyte [6,7]. However, pure PDADMAC polyelectrolyte has some disadvantages such as relatively poor mechanical strength and a narrow operative temperature range. In order to solve this defect, Na-Montmorillonite (Na-MMT) with two-dimensional layered structure has attracted our attention. On account of the inorganic components in Na-MMT lamellar, it has fine thermal stability. In addition, Na-MMT has strong cation exchange property [8]. Here, we

proposed an aqueous solution intercalation method for preparing Na-MMT/PDADMAC composite polyelectrolyte. Na-MMT/ PDADMAC composite polyelectrolyte was assembled into a solid state supercapacitor with three different electrodes (carbon, NiCo (OH)2 and Polypyrrole electrode). After 1000 cycles at 15℃, 35℃ and 50℃, the capacitance retention of three kinds of electrode was basically maintained above 90%. 2. Experimental section 2.1. Fabrication of Na-MMT/PDADMAC composite polyelectrolyte First, add 10 ml deionized water and 10 ml of PDADMAC solution to the beaker to form a mixed solution. Secondly, a certain amount of Na-MMT was added to the mixed solution and stirred for 0.5 h to form the dispersed solution. Finally, the dispersion was placed in a magnetic stirrer and stirred at 1000 revolutions per minute for 6 h (at 80℃) until a gelatinous mixture was formed. (The preparation methods of the three electrodes can be found in the Supporting information). 2.2. Electrochemical performance measurements

⇑ Corresponding author. E-mail address: [email protected] (X. Wu). https://doi.org/10.1016/j.matlet.2020.127657 0167-577X/Ó 2020 Elsevier B.V. All rights reserved.

A series of electrochemical performance tests were performed on CHI660E electrochemical workstation (Shanghai CH instrument

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B. Huang, X. Wu / Materials Letters 269 (2020) 127657

Co., LTD.). A symmetrical supercapacitor was composed of two identical electrodes with an electrolyte sandwiched between them. Its electrochemical performance was tested using a two-electrode system, and the two electrodes of the symmetrical supercapacitor were used as the positive electrode and the negative electrode, respectively. 2.3. Solid composite polyelectrolyte films combustion test Firstly, placed alcohol lamp where there was no wind and ignited. Secondly, the solid electrolyte film was held by tweezers and placed 6 cm away from the alcohol lamp. Finally, the combustion resistance time of the solid electrolyte film with different Na-MMT contents were recorded. 3. Results and discussions Fig. 1(a) was a schematic diagram of the preparation process of solid composite polyelectrolyte film. According to Fig. 1(b, c),

Na-MMT/PDADMAC composite polyelectrolyte presented a lamellar structure. Fig. 1(d) showed the uneven surface of the composite polyelectrolyte containing Na-MMT particles. Further, Fig. 1(e, f) was a cross-section of the composite polyelectrolyte at magnification. It could be observed that the cross section of the composite polyelectrolyte presents an obvious lamellar type fracture, and there are more dispersed Na-MMT particles at the fracture. According to the analysis of mechanism diagram (Fig. 4), under electrostatic interaction, cationic PDADMAC molecular chain could enter anion type Na-MMT layer, conduct cation exchanged between layers and expanded layer spacing. This further enhanced the ion migration rate and improved the cycle stability and thermal stability of the supercapacitor. Meanwhile, the sample contains Al, O, C, Na and Si (Fig. 1(g)), and the XRD, FTIR, TGA are shown in Fig. S1. Fig. 2(a, c, e) were CV curves of supercapacitors with three different electrodes. It can be seen from the Fig. 2(a, c, e), CV curve shapes with different content of Na-MMT all had closed shape and high symmetry, showing good capacitive behavior [9,10]. (Fig. 2(a, b) showed a typical double-layer capacitance and Fig. 2

Fig. 1. Illustration of the fabrication of Na-MMT/PDADMAC composite polyelectrolyte film (a).SEM images of Na-MMT/PDADMAC composite polyelectrolyte(b-f).EDAX images of Na-MMT/PDADMAC composite polyelectrolyte(g).

B. Huang, X. Wu / Materials Letters 269 (2020) 127657

Fig. 2. CV curves of carbon (NiCo(OH)2 and PPy) electrode supercapacitor (scan rate = 20 mV s electrode (current density = 1.0 A g 1)(b, d , f).

(c) showed a significant redox peak with a typical pseudocapacitance). Fig. 2(b, d, f) were the respective charge–discharge curves of supercapacitors with three different electrodes. It can be seen from Fig. 2(b, d, f) that the all GCD curves are highly symmetric and show excellent charge–discharge performance [11–12]. Furthermore, changes of CV curves and GCD curves of three different electrodes were all related to the content of Na-MMT. Interestingly, when the content of Na-MMT was 0.6 g, the CV curve area of different electrodes was the largest, and the specific capacitance was 230F g 1, 1520F g 1 and 778.75F g 1, respectively (relevant calculation process can be found in Tables S1-S3). This indicated that the high compatibility of Na-MMT/PDADMAC composite polyelectrolyte with three different electrodes made supercapacitors owned excellent electrochemical properties. Owing to thermal stability was an important indicator in the practical application of supercapacitors, the CV curves (from 15℃ to 50℃) of supercapacitors with three different electrodes and

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) (a, c, e).GCD curves of supercapacitor based on carbon, NiCo(OH)2 and PPy

the capacitance retention after 1000 cycles were tested. Fig. 3(a, c, e) showed CV curves of Na-MMT/PDADMAC polyelectrolyte with carbon, (NiCo(OH)2 and PPy electrode at 15℃, 35℃ and 50℃, respectively. As can be seen from Fig. 3(a, c, e), when the scanning rates of CV curves were successively 40 mV s 1 and 100 mV s 1, the CV curves still has fine symmetry and closed shape, showing good capacitive behavior. Fig. 3(b, d, f) showed the capacitance retention of three different supercapacitors after 1000 cycles at 15℃, 35℃, and 50℃, respectively. It could be seen from Fig. 3(b, d, f) that even when the current density was 10 A g 1, the capacitance remained above 90% after 1000 cycles. Such excellent cycling performance is mainly due to that the Na-MMT/PDADMAC polyelectrolyte owned fine temperature resistance performance (TGA, Fig. S1). Fig. 4 showed the combustion of solid composite electrolyte film. As shown in Figure.(a-c), PDADMAC polyelectrolyte film had a short combustion time (about 8 s) . Figure. (d-i) showed the

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Fig. 3. CV curves of carbon electrode supercapacitor at different temperature (scan rate = 40 mV s 1)(a).CV curves of NiCo(OH)2 electrode supercapacitor and PPy electrode supercapacitor at different temperature (scan rate = 100 mV s 1)(c,e).The cyclic properties of carbon (NiCo(OH)2 and PPy) electrode supercapacitor at different temperature (current density = 10 A g 1)(b,d,f).

combustion of Na-MMT/PDADMAC polyelectrolyte films with different content of Na-MMT. It could be seen that with the increase of the content of Na-MMT, the burning time of composite films gradually extended, reaching a maximum of 50 s. Compared with pure PDADMAC film, the combustion time of Na-MMT/PDADMAC composite polyelectrolyte film was significantly improved (Picture of other films with different Na-MMT contents of combustion can be found in Fig. S3). Combined with the mechanism diagram (Fig. 4(j–l)), this was due to the high content of Na-MMT in the electrolyte film made of composite polymer, and part of the NaMMT entered the PDADMAC molecular chain or accumulated on the outer side of the molecular chain. Because Na-MMT was a relatively stable two-dimensional layered structure, the existence of layer spacing reduced the heat transfer rate and prolonged the burning time of films.

4. Conclusion In summary, this work showed that added Na-MMT to the PDADMAC polyelectrolyte can effectively improve the thermal stability of supercapacitors and the ability to adapt to three different electrodes. After 1000 cycles at 15℃, 35℃ and 50℃, the capacitance retention of carbon, NiCo(OH)2 and Polypyrrole electrode based on this composite electrolyte basically maintain above 90%. Moreover, with the increase of Na-MMT, the combustion resistance time of Na-MMT/PDADMAC solid polyelectrolyte film gradually improved and the maximum flame resistance time reach 50 s super to pure PDADMAC polyelectrolyte of 8 s, indicating that the solid electrolyte film has good heat resistance. Therefore, the combination of Na-MMT and PDADMAC provided a new method for further study of composite polyelectrolyte.

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Fig. 4. (a–c) is the combustion photo of PDADMAC polyelectrolyte film, (d-f) is the combustion photo of Na-MMT(0.6 g)/PDADMAC composite polyelectrolyte film, (g-i) is the combustion photo of Na-MMT(1.2 g)/PDADMAC composite polyelectrolyte film, (j-l) is the mechanism diagram of Na-MMT/PDADMAC composite polyelectrolyte.

CRediT authorship contribution statement

Appendix A. Supplementary data

Bin Huang: Conceptualization, Methodology, Software, Investigation, Writing - original draft, Validation, Formal analysis, Visualization. Xinming Wu: Validation, Formal analysis, Visualization, Software, Resources, Writing - review & editing, Supervision, Data curation.

Supplementary data to this article can be found online at https://doi.org/10.1016/j.matlet.2020.127657.

Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgement This work was supported by Natural Science Foundation of Shaanxi Province of China (2018JM5141) and the National Nature Science Foundation of China (21975169).

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