Preparation and application of self-healing polyvinyl alcohol/bacterial cellulose hydrogel electrolyte
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摘要: 以聚乙烯醇（PVA）、细菌纤维素(BC)和硫酸为原料，采用物理交联的冻融循环法制备了聚乙烯醇/细菌纤维素复合水凝胶电解质；经过冻融循环后，聚乙烯醇和细菌纤维素形成了大量的分子间氢键，赋予复合水凝胶良好的自修复性能和力学性能。探讨了纤维素含量对水凝胶电解质力学性能和离子电导率的影响，结果表明，BC含量为0.6%时复合水凝胶自修复性能最好，力学性能最强，断裂强度高达0.41 MPa，离子电导率最高达到138.9 mS/cm，一次修复后离子电导率仍然可达84.1 mS/cm ，修复率高达74%。在该自修复聚乙烯醇/细菌纤维素水凝胶电解质表面原位聚合聚苯胺电极，设计组装柔性一体化超级电容器，研究了苯胺浓度对超级电容器性能的影响。结果表明，苯胺浓度为0.2 mol/L时，超级电容器器件在0.2 mA/cm2的电流密度下达到580.8 mF/cm2的高比电容、出色的能量密度（20.17 μW·h/cm2）和功率密度（50 μW/cm2），且一次修复后的电容保持率达到66%，显示出良好的自修复性能，以及保持结构完整性和电化学稳定性的巨大潜力。这些发现表明了自修复聚乙烯醇/细菌纤维素复合水凝胶电解质在柔性可穿戴储能装置中巨大的应用前景。Abstract: Polyvinyl alcohol (PVA), bacterial cellulose (BC) and sulfuric acid were used as raw materials to prepare PVA/BC composite hydrogel electrolyte (CHEPVA/BC) by physical cross-linking freezing-thawing cycle method. After freeze-thaw cycles, PVA and BC form a large number of intermolecular hydrogen bonds, which endow the composite hydrogel with good self-healing property (SHP) and mechanical properties (MPs). The effect of BC content (BCC) on MPs and ionic conductivity (IC) of CHEPVA/BC were discussed. The results show that the composite hydrogel with BCC of 0.6% has the best SHPs and MPs, with breaking strength and IC as high as 0.41 MPa and 138.9 mS/cm, respectively. After the first healing cycle (FHC), IC and healing rate still reach 84.1 mS/cm and 74%, respectively. Polyaniline electrode was polymerized in-situ on the surface of the self-healing CHEPVA/BC, and a flexible all-in-one supercapacitor was designed and assembled. The results show that when aniline concentration is 0.2 mol/L, the supercapacitor device achieves high specific capacitance (580.8 mF/cm2), excellent energy density (20.17 μW·h/cm2) and power density (50 μW/cm2) at current density of 0.2 mA/cm2, and the capacitance retention rate after the FHC reaches 66%, showing good self-healing performance and great potential to maintain mechanical integrity and electrochemical stability. These findings indicate that the self-healing CHEPVA/BC has great application prospects in flexible wearable energy storage devices.
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Key words:
- polyvinyl alcohol /
- bacterial cellulose /
- composite hydrogel electrolyte /
- self-healing /
- supercapacitor
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图 2 PVA/BC复合水凝胶(a)柔韧性和可加工性，(b)应力-应变曲线，(c)离子电导率和含水率
Figure 2 Flexibility and machinability (a), stress-strain curves (b), ionic conductivity and moisture content (c) of PVA/BC composite hydrogel electrolyte
图 3 （a） PVA，（b） BC和（c） 6-PBHE的扫描图; （d） 6-PBHE、PVA和BC的红外光谱谱图；（e）6-PBHE，PVA和BC的X射线衍射谱图
Figure 3 SEM images of (a) PVA, (b) BC and (c) 6-PBHE. (d) FTIR spectra of 6-PBHE, PVA and BC. (e) XRD of 6-PBHE, PVA and BC
图 4 PVA/BC复合水凝胶电解质自修复性能：（a） PVA/BC复合水凝胶电解质自修复过程，（b） 自修复机制示意图，水凝胶电解质修复前后的（c）阻抗图和（d）离子电导率
Figure 4 Self-healing performance of PVA/BC composite hydrogel electrolyte (a) Schematic diagram of PVA/BC composite hydrogel electrolyte self-healing process and (b) self-healing mechanism. (c) Nyquist diagram and (d) ionic conductivity before and after hydrogel electrolyte self-healing.
图 5 PANI-PBHE柔性一体化超级电容器的组装
Figure 5 Preparation of PANI-PBHE flexible all-in-one supercapacitors
图 6 不同苯胺浓度的x-PANI-6-PBHE超级电容器的 （a） CV曲线，（b） GCD曲线，（c） 比电容，（d） Nyquist图，（e） 倍率性能和（f） 拉贡图；（g） 2-PANI-6-PBHE超级电容器的循环稳定性
Figure 6 (a) CV curves, (b) GCD curves, (c) areal specific capacitance, (d) Nyquist plots, (e) rate capability and (f) Ragone plots of x-PANI-6-PBHE SCs with different aniline concentrations; (g) cyclic stability of 2-PANI-6-PBHE SC
图 7 2- PANI-6-PBHE超级电容器的自修复性能 (a) 2-PANI-6-PBHE超级电容器的自修复过程2-PANI-6-PBHE超级电容器的 (b) CV (c) GCD (d) 阻抗图以及 (e) 基于不同测试的修复率
Figure 7 Self-healing Performance of 2-PANI-6-PBHE SC (a) : Schematic diagram of 2-PANI-6-PBHE SC device self-heal process; (b) : CV curves; (c): GCD curves; (d): Nyquist plots and (e) healing efficiency based on different tests of original and healed 2-PANI-6-PBHE SC
表 1 本工作与其他超级电容器电化学性能比较
Table 1 Comparison of area specific capacitance between our SC device and other supercapacitors
Electrode Electrolyte Specific capacitance/
(mF·cm−2)Energy density/
(μW·h·cm−2)Power density/
(μW·cm−2)Reference PANI PVA/BC/H2SO4 581 20.17 50 this work SWCNT-PANI PVA/H2SO4 15.8 NA NA [23] Carbon sponge PANa/Fe3 /LiCl 212.5 0.21/(mW·h·cm−2) 25.4/(mW·cm−2) [28] PPy PVA/H2SO4 58.8 6.94 500 [29] PANI PVA/PA 85.3 NA NA [30] PANI/PVA PVA/PA 260.1 14.3 97.5 [31] PANI/ H2SO4/ HClO4 PVA/H2SO4 149.3 13.0 0.40/(mW·cm−2) [32] 
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