具有高离子电导率且综合性能优异的凝胶电解质是储能材料领域的研究热点。以简单的冻融法制备了一种基于聚乙烯醇(PVA)和壳聚糖(CS)的水凝胶聚合物电解质,并获得高离子电导率。系统地探索了水凝胶冷冻时间、浸泡电解液的时间以及电解液种类对水凝胶离子电导率的影响,得出了适合该物理交联PVA/CS凝胶电解质的制备条件。结果表明:PVA与CS质量比为1∶2,经过5h冷冻12h解冻获得的凝胶具有较均匀的三维孔洞结构和较低的结晶度,没有发生水凝胶无限溶胀以及溶解的现象。该水凝胶浸泡饱和NaCl电解液6h后其离子电导率达到最大值1.68S/cm,浸泡1mol/L H2SO4电解液的离子电导率在4h时最大为0.83S/cm。此外,5mm厚的水凝胶在12h后达到溶胀平衡,体积和质量溶胀率分别约为170%和145%;凝胶断裂伸长率在室温下可以达到200％左右。
Gel electrolyte with high ionic conductivity and excellent comprehensive performance is a research hotspot in the field of energy storage materials.A hydrogel polymer electrolyte based on polyvinyl alcohol (PVA) and chitosan (CS) was prepared by a simple freeze-thaw method,and high ionic conductivity was obtained.The effects of hydrogel freezing time,soaking time in the electrolyte,and the types of electrolytes on the ionic conductivity of the hydrogel were systematically explored.The suitable preparation conditions for the physical crosslinking PVA/CS gel electrolyte were obtained.The results showed that the PVA/CS gel had a relatively uniform three-dimensional-hole structure and low crystallinity when the mass ratio of PVA to CS was 1∶2,and the hydrogel was frozen for 5h and thawed for 12h.No infinite swelling and dissolution of the hydrogel occurred.The ionic conductivity of the hydrogel soaked in saturated sodium chloride electrolyte for 6h and 1mol/L H2SO4 electrolyte for 4h reached the maximum value of 1.68S/cm and 0.83S/cm,respectively.Additionally,the 5mm-thick hydrogel reached swelling equilibrium after 12h,the volume and mass swelling rates of hydrogel were about 170% and 145%,respectively,and the elongation at break could reach about 200% at room temperature.
[1] Bruce P G,Scrosati B,Tarascon J M.Nanomaterials for rechargeable lithium batteries[J].Angewandte Chemie International Edition,2008,47(16):2930-2946.
[2] Cong L N,Xie H M,Li j H.Hierarchical structures based on two-dimensional nanomaterials for rechargeable lithium batteries[J].Advanced Energy Materials,2017,7(12):1601916-1601941.
[3] Goodenough J B,Park K S.The li-ion rechargeable battery:a perspective[J].Journal of the American Chemical Society,2013,135(4):1167-1176.
[4] Liu Y L,Liu J,Wang J J,et al.Formation of size-dependent and conductive phase on lithium iron phosphate during carbon coating[J].Nature Communications,2018,9:929-936.
[5] Zhong C,Deng Y D,Hu W B,et al.A review of electrolyte materials and compositions for electrochemical supercapacitors[J].Royal Society of Chemistry,2015,44(21):7484-7539.
[6] Zhang B H,Zhang Y H,Zhang N,et al.Synthesis and interface stability of polystyrene-poly(ethylene glycol)-polystyrene triblock copolymer as solid-state electrolyte for lithium-metal batteries[J].Journal of Power Sources,2019,428:93-104.
[7] Huang Y F,Wu P F,Zhang M Q,et al.Boron cross-linked graphene oxide/polyvinyl alcohol nanocomposite gel electrolyte for flexible solid-state electric double layer capacitor with high performance[J].Electrochimica Acta,2014,132:103-111.
[8] 裴英伟,张红,王星辉.可充电锌离子电池电解质的研究进展[J].储能科学与技术,2022,11(7):2075-2082.
[9] 刘云鹏,李雪,韩颖慧,等.锂离子超级电容器电极材料研究进展[J].高电压技术,2018,44(4):1140-1148.
[10] Raza W,Ali F,Raza N,et al.Recent advancements in supercapacitor technology[J].Nano Energy,2018,52:441-473.
[11] Gown H,Hong J Y,Kim H,et al.Recent progress on flexible lithium rechargeable batteries[J].Energy & Environmental Science,2014,7(2):538-551.
[12] Choi J,Chaffari R,Baker L B,et al.Skin-interfaced systems for sweat collection and analytics[J].Science Advances,2018,4:3921-3931.
[13] Choudhury N A,Sampath S,Shukla A K.Hydrogel-polymer electrolytes for electrochemical capacitors:an overview[J].Energy & Environmental Science,2009,2:55-67.
[14] Yang C H,Suo Z G.Hydrogel ionotronics[J].Nature Reviews Materials,2018,3:125-142.
[15] Zhou G B,Yang L Y,Li W J,et al.A regenerable hydrogel electrolyte for flexible supercapacitors[J].iScience,2020,23(9):101502-101513.
[16] Ko J M,Nam J H,Won J H,et al.Supercapacitive properties of electrodeposited polyaniline electrode in acrylic gel polymer electrolytes[J].Synthetic Metals,2014,189:152-156.
[17] Liu L,Wang X D,Yang C H,et al.PVdF-HFP-based gel polymer electrolyte with semi-interpenetrating networks for dendrite-free lithium metal battery[J].Acta Metallurgica Sinica,2021,34:417-424.
[18] Hwang T,Frank Z,Neubauer J,et al.High-performance polyvinyl chloride gel artificial muscle actuator with graphene oxide and plasticizer[J].Scientific Reports,2019,9(1):9658-9666.
[19] Pyarasani R D,Jayaramudu T,John A.Polyaniline-based conducting hydrogels[J].Journal of Materials Science,2019,54:974-996.
[20] Fei H J,Yang C Y,Bao H,et al.Flexible all-solid-state supercapacitors based on graphene/carbon black nanoparticle film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes[J].Journal of Power Sources,2014,266:488-495.
[21] Zahid A A,Ahmed R,Rehman S R U,et al.Nitric oxide eleasing chitosan-poly(vinyl alcohol) hydrogel promotes angiogenesis in chick embryo model[J].International Journal of Biological Macromolecules,2019,136:901-910.
[22] Shital N B,Sangawar V S.Synthesis and study of PVA based gel electrolyte[J].Chemical Science Transactions,2012,3:653-657.
[23] Alipoori S,Torkzadeh M M,Mazinani S,et al.Performance-tuning of PVA-based gel electrolytes by acid/PVA molecular weight[J].Nature,2021,3(310),DOI:10.1007/s42452-021-04182-7.
[24] Zhang X H,Yin Z,Guo Y,et al.Facial and large-scale synthesis of PVA/chitosan/collagen hydrogel for wound healing[J].New Journal of Chemistry,2020,44:20776-20784.
[25] Katayoon K,Ebrahim M,Bahram S,et al.Chitosan/PVA hydrogels incorporated with green synthesized cerium oxide nanoparticles for wound healing applications[J].European Polymer Journal,2020,134,109853-109862.
[26] 雒春辉,赵宇斐.高强度耐溶胀仿软骨PVA/CS水凝胶的合成及性能[J].精细化工,2020,37(9):1812-1818.
[27] Jiang X C,Xiang N P,Zhang H X,et al.Preparation and characterization of poly(vinyl alcohol)/sodium alginate hydrogel with high toughness and electric conductivity[J].Carbohydrate Polymers,2018,186:377-383.
[28] Zha X J,Zhang S T,Pu J H,et al.Nanofibrillar poly(vinyl alcohol) ionic organohydrogels for smart contact lens and human-interactive sensing[J].ACS Applied Materials Interfaces,2020,12:23514-23522.
[29] Hu O D,Chen G Q,Gu J F,et al.A facile preparation method for anti-freezing,tough,transparent,conductive and thermoplastic poly(vinyl alcohol)/sodium alginate/ glycerol organohydrogel electrolyte[J].International Journal of Biological Macromolecules,2020,164:2512-2523.
[30] Hu O D,Lu J,Chen G Q,et al.An antifreezing,tough,rehydratable,and thermoplastic poly(vinyl alcohol)/sodium alginate/poly(ethylene glycol) organohydrogel electrolyte for flexible supercapacitors[J].ACS Sustainable Chemistry & Engineering,2021,9(29):9833-9845.
[31] Guo Y,Zheng K Q,Wan P B.A flexible stretchable hydrogel electrolyte for healable all-in-one configured supercapacitors[J].Small,2018,14(14):1704497-1704505.
[32] Peng S J,Jiang X Z,Xiang X T,et al.High-performance and flexible solid-state supercapacitors based on high toughness and thermoplastic poly(vinyl alcohol)/NaCl/glycerol supramolecular gel polymer electrolyte[J].Electrochimica Acta,2019,324:134874-134884.
基金资助
国家自然科学基金面上项目(51472166)
PDF
