Polyaniline-corn husk fiber composite based flexible self-standing electrode: Preparation and electrochemical properties
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摘要: 为满足可穿戴电子设备日益提升的要求，低成本、高性能柔性超级电容器成为研究的热点。在玉米苞叶纤维(CHF)基材表面原位生长聚苯胺(PANI)，继而以聚乙烯醇/硫酸(PVA/H2SO4)作为凝胶，通过简单的冻融法制备聚苯胺-玉米苞叶纤维柔性自支撑电极(PANI-CHF-GEL)。PANI-CHF-GEL显示出优异的力学性能(断裂强度为259 kPa，断裂伸长率为121%)和较好的韧性(断裂能为0.167 MJ·cm−3)。采用PVA/H2SO4 凝胶作为电解质组装得到的PANI-CHF-GEL//PANI-CHF-GEL对称固态超级电容器具有优越的电化学储能性能：在3.00 mA·cm−2的电流密度下，面积比电容高达1789.74 mF·cm−2，功率密度为0.34 mW·cm−2，能量密度为3.51 mW·h·cm−2。此外，该器件还显示出良好的柔性，弯曲90° 时仍能保持其初始性能，表明了其在可穿戴电子设备潜在的应用前景。Abstract: In order to meet the increasing requirements of wearable electronic devices, low-cost, high-performance flexible supercapacitors have become a research hotspot. In this work, flexible, self-standing PANI-CHF-GEL electrode was obtained by growing polyaniline (PANI) on the surface of corn husk fiber (CHF) and mixed with polyvinyl alcohol/sulfuric acid (PVA/H2SO4) gel, followed by a facile frozen-thawing method. PANI-CHF-GEL exhibits excellent mechanical properties (a fracture strength of 259 kPa at a fracture strain of 121%) and good toughness (a fracture energy of 0.167 MJ·cm−3). Employing PVA/H2SO4 as the gel electrolyte, the symmetric PANI-CHF-GEL//PANI-CHF-GEL solid supercapacitor delivers an areal capacitance of 1789.74 mF·cm−2, a power density of 0.34 mW·cm−2, and a corresponding energy density of 3.51 mW·h·cm−2 (@3.00 mA·cm−2). Moreover, the device retains its original properties even bent 90°, indicating its promise potentials for wearable electronics.
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Key words:
- corn husk fiber /
- polyaniline /
- composites /
- flexibility /
- self-standing /
- solid supercapacitor /
- electrochemical
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图 1 聚苯胺-玉米苞叶纤维柔性自支撑电极(PANI-CHF-GEL)制备示意图
Figure 1. Schematic preparation of polyaniline-corn husk fiber-gel (PANI-CHF-GEL) electrode
PANI—Polyaniline; PVDF—Polyvinylidene fluoride; ACET—Acetylene black; PVA—Polyvinyl alcohol
图 2 CH、CHF、PANI-CHF及PANI-CHF-GEL电极的SEM图像：CH (×100) (a)；CHF (×100) (b)；CHF (×500) (c)；PANI-CHF (×1000) (d)；PANI-CHF (×5000) (e)；PANI-CHF-GEL (×1000) (f) (黄色方框显示其特征结构)
Figure 2. SEM images of CH (×100) (a), CHF (×100) (b), CHF (×500) (c), PANI-CHF (×1000) (d), PANI-CHF (×5000) (e), PANI-CHF-GEL (×1000) (f) (Yellow squares indicate the characteristic structure)
图 3 (a) PANI、CHF、PANI-CHF的拉曼图谱；(b) CHF、PANI-CHF的XRD图谱；(c) CHF、PANI-CHF的XPS图谱； (d) C1s图谱；(e) N1s图谱；(f) O1s图谱
Figure 3. (a) Raman spectras of PANI，CHF and PANI-CHF; (b) XRD patterns of CHF and PANI-CHF; (c) XPS spectras of CHF and PANI-CHF; (d) Spectra of C1s; (e) Spectra of N1s; (f) Spectra of O1s
图 4 (a) PVA/H2SO4、PANI-GEL、PANI-CHF-GEL的应力-应变曲线；(b)通过应力-应变曲线计算不同样品的韧性和弹性模量
Figure 4. (a) Stress-strain curves of PVA/H2SO4, PANI-GEL, PANI-CHF-GEL; (b) Corresponding toughness and elasticity modulus calculated from the stress-strain curves
图 5 N/PANI-CHF-GEL、PANI-GEL、PANI-CHF-GEL的CV曲线(@20 mV·s−1) (a)、GCD曲线(@20 mA·cm−2) (b)；PANI-CHF-GEL的CV曲线(c)、GCD曲线(d)、EIS谱图(e)及循环稳定性(@20 mA·cm−2， 内嵌图为不同循环圈数的GCD曲线) (f)
Figure 5. CV curves (@20 mV·s−1) (a) and GCD curves (@20 mA·cm−2) (b) of N/PANI-CHF-GEL, PANI-GEL, PANI-CHF-GEL; CV curves (c), GCD curves (d), EIS curve (e), and cycling stability (@ 20 mA·cm−2, the inset is the GCD curve at different number of cycles) (f) of the PANI-CHF-GEL electrode
N/PANI-CHF-GEL—PANI-CHF-GEL electrode without PVDF and ACET added
图 6 PANI-CHF-GEL//PANI-CHF-GEL对称固态超级电容器的CV图(a)、GCD图(b)、EIS谱图(c)及循环稳定性(@20 mA·cm−2，内嵌图为不同循环圈数的实际GCD曲线) (d)，器件在不同弯曲角度下的CV图(e)及实物展示(f)
Figure 6. CV curves (a), GCD curves (b), EIS curve (c), and cycling stability (@ 20 mA·cm−2, the embedded graph is the actual GCD curve with different number of cycles) (d) of the symmetric PANI-CHF-GEL//PANI-CHF-GEL solid supercapacitor. The CV curves (e) and photos (f) of the supercapacitor under different bending angles
表 1 PANI-CHF-GEL基底电容器同其他文献报道的柔性超级电容器的电化学性能对比
Table 1. Comparison of PANI-CHF-GEL based supercapacitor with previously reported flexible supercapacitors
Electrode Substrate Areal capacitance/
(mF·cm−2)Energy density/
(mW·h·cm−2)Power density/
(mW·cm−2)Ref. PANI-CHF-GEL NA 1789.74 3.51 0.34 This work CNC@MoS2 Carbon cloths 120.70 0.016 9.30 [19] rGO/TA Filter paper 40.37 3.60×10−3 107.60×10−3 [20] MnO2/graphite Tape 577.50 16.80×10−3 16.00 [21] PPy-rGO-PPy Cu:Ni-PET 684.00 95.00×10−3 — [22] PPy/rGO PET 230.00 11.00×10−3 0.03 [23] Notes: PANI-CHF-GEL—Polyaniline-corn husk fiber-PVA/H2SO4; CNC@MoS2—Carbon nanocones on carbon cloths@MoS2; rGO/TA—Reduced graphene oxide/Tannin; PPy-rGO-PPy—Polypyrrole-reduced graphite oxide-polypyrrole; Cu:Ni-PET—Cu:Ni-polyethylene terephthalate; PPy/rGO—Polypyrrole/Reduced graphite oxide. 
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