Application of porous conductive gel PAM/CNTs-PEG in zinc-air batteries
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摘要: 为实现锌-空气电池工业化生产，优化其空气扩散电极性能，使其有利于气体的扩散，并形成更多的三相界面。导电水凝胶是由导电材料和交联聚合物网络组成，聚合物网络提供支架，而导电材料赋予水凝胶良好的导电性。多孔的结构可以给气体更多的扩散通路，也有利于催化层的负载，形成更多的三相界面。本文采用聚丙烯酰胺基水凝胶，以聚乙二醇-2000 (PEG2000)为制孔剂，合成多孔聚丙烯酰胺/碳纳米管-聚乙二醇(PAM/CNTs-PEG)导电水凝胶。将制备的PAM/CNTs-PEG导电水凝胶浸泡于乙醇溶液中，可形成不同数量的介孔。本文研究了不同浸泡时间对于多孔PAM/CNTs-PEG导电水凝胶在柔性锌空电池中的性能影响。实验结果表明：乙醇浸泡5 h的导电凝胶电化学性能最好。当电压从1 mA/cm2 时的1.23 V到5 mA/cm2时的1.11 V，仅衰减了0.12 V。8.5 mA/cm2时产生最大功率密度为77.35 mW/cm2，且放电时具有1104.85 mA·h/g的高克容量，远高于其他导电凝胶。且有较好的导电性和应变灵敏度，可应用于传感等领域。Abstract: In order to realize the industrial production of zinc-air battery, the performance of its air diffusion electrode is optimized to make it conducive to the diffusion of gas and to form more three-phase interfaces. The conductive hydrogel is composed of a conductive material and a cross-linked polymer network, the polymer network provides the scaffold, and the conductive material gives the hydrogel good electrical conductivity. The porous structure can give more diffusion paths to the gas, and is also conducive to the load of the catalytic layer, forming more three-phase interfaces. In this paper, polyacrylamide hydrogel was used to synthesize porous polyacrylamide/carbon nanotubes-polyethylene glycol (PAM/CNTs-PEG) conductive hydrogel with polyethylene glycol 2000 (PEG2000) as pore-making agent. The prepared PAM/CNTs-PEG conductive hydrogels were immersed in ethanol solution to form different numbers of mesopores. The effect of different immersion time on the properties of porous PAM/CNTs-PEG conductive hydrogels in flexible zinc-air cells was studied. The experimental results show that the electrochemistry performance of the conductive gel soaked in ethanol for 5 h is the best. When the voltage changes from 1.23 V at 1 mA/cm2 to 1.11 V at 5 mA/cm2, the attenuation is only 0.12 V. The maximum power density is 77.35 mW/cm2 at 8.5 mA/cm2, and the high gram capacity of 1104.85 mA·h/g at discharge is much higher than that of other conductive gels. It has good electrical conductivity and strain sensitivity and can be used in sensing and other fields.
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图 1 聚丙烯酰胺/碳纳米管-聚乙二醇(PAM/CNTs-PEG)导电凝胶的制备示意图
AM—Acrylamide; CMC-Na—Sodium carboxymethyl cellulose
Figure 1. Schematic diagram of the preparation of polyacrylamide/carbon nanotubes-polyethylene glycol (PAM/CNTs-PEG) conductive gel
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图 2 未加制孔剂(a)、乙醇浸泡1 h (b)、乙醇浸泡2 h (c)、乙醇浸泡5 h (d)及乙醇浸泡10 h (e)后制得的PAM/CNTs-PEG导电凝胶的SEM图像
Figure 2. SEM images of PAM/CNT-PEG conductive gel prepared after no pore-making agent (a), 1 h ethanol immersion (b), 2 h ethanol immersion (c), 5 h ethanol immersion (d) and 10 h ethanol immersion (e)
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图 3 加入制孔剂后不同乙醇浸泡时间下的PAM/CNTs-PEG导电水凝胶的 FTIR图谱
Figure 3. FTIR spectra of PAM/CNT-PEG conductive hydrogels at different ethanol soaking time after adding pore-making agent
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图 4 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的溶胀曲线
Figure 4. Swelling curves of PAM/CNTs-PEG conductive hydrogels without PEG or with PEG for different ethanol immersion time
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图 5 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的应力-应变曲线
Figure 5. Stress-strain curves of PAM/CNTs-PEG conductive hydrogels without PEG or with PEG for different ethanol immersion time
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图 6 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的倍率性能
Figure 6. Rate performance of PAM/CNTs-PEG conductive hydrogels without PEG or with PEG for different ethanol immersion time
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图 7 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的极化曲线
Figure 7. Polarization curves of PAM/CNTs-PEG conductive hydrogels without PEG and with PEG in different ethanol soaking time
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图 8 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的最大功率密度曲线
Figure 8. Maximum power density curves of PAM/CNTs-PEG conductive hydrogels without PEG or with PEG for different ethanol immersion time
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图 9 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的放电曲线
Figure 9. Discharge curves of PAM/CNTs-PEG conductive hydrogels without PEG and with PEG added for different ethanol soaking time
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图 10 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的交流阻抗图谱
Figure 10. EIS impedance profiles of PAM/CNTs-PEG conductive hydrogels without PEG or with PEG for different ethanol immersion time
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图 11 加入PEG乙醇浸泡5 h的PAM/CNTs-PEG导电水凝胶的传感图
Figure 11. Sensing diagram of PAM/CNTs-PEG conductive hydrogel immersed in ethanol for 5 h with PEG
表 1 未加PEG及加入PEG不同乙醇浸泡时间的PAM/CNTs-PEG导电水凝胶的孔隙率
Table 1 Porosity of PAM/CNTs-PEG conducting hydrogels without PEG and with PEG in different ethanol soaking time
Sample Pore volume/
(mL·g−1)Density ρ/(g·cm−3) Porosity/% Unadded 0.0070 1.2129 3.96 1 h 0.0065 1.3217 6.50 2 h 0.0374 1.2364 27.35 5 h 0.2194 1.0754 65.71 10 h 4.7320 1.0206 95.89 
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其他类型引用(13)
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锌-空气电池要实行工业化生产，其核心部分是空气扩散电极，如果优化其性能，就有望使其有利于气体的扩散，并形成更多的三相界面，更有利于电极的电化学反应。导电水凝胶是由导电材料和交联聚合物网络组成，聚合物网络提供支架，而导电材料赋予水凝胶良好的导电性。多孔的结构可以给气体更多的扩散通路，也有利于催化层的负载，形成更多的三相界面。
采用聚丙烯酰胺基水凝胶，以聚乙二醇-2000(PEG2000)为制孔剂，采用原位聚合合成多孔PAM/CNTs-PEG导电水凝胶。羧甲基纤维素钠(CMC-Na)为黏结剂，将PAM和CNTs黏连。聚乙二醇可溶于乙醇，将制备的PAM/CNTs-PEG导电水凝胶浸泡于乙醇溶液中，可形成不同数量的介孔。本文研究了不同浸泡时间对于多孔PAM/CNTs-PEG导电水凝胶在柔性锌空电池中的性能影响。
实验结果表明：这种多孔结构提高了氧气的进入量，提供了更多的三相界面，大大改善了空气阴极的电化学性能。当电压从1 mA/cm2时的1.23 V到5 mA/cm2时的1.11 V，仅衰减了0.12 V，且有高度的可逆性及稳定的放电窗口。浸泡乙醇5 h的导电凝胶在128.50 mA/cm2时产生最大的峰值功率密度77.35 mW/cm2。且该导电水凝胶有较好的导电性和较高的应变灵敏度，可以满足监测人体日常运动的需要。
Schematic diagram of the preparation of PAM/CNTs-PEG conductive gel
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