Citation: Xue-yu TAO, Wen-bin MA, Xiao-dong HAN, Ke-hu ZHU, Shi-fang YE, Heng SHA, Lin GUO, Xian-yong WEI, Chong XU, Shen-gang ZHU. Preparation and application of self-healing polyvinyl alcohol/bacterial cellulose hydrogel electrolyte[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(3): 304-313. doi: 10.1016/S1872-5813(21)60179-2 shu

Preparation and application of self-healing polyvinyl alcohol/bacterial cellulose hydrogel electrolyte

Xue-yu TAO ^1,, ,
Wen-bin MA ¹ ,
Xiao-dong HAN ¹ ,
Ke-hu ZHU ¹ ,
Shi-fang YE ¹ ,
Heng SHA ¹ ,
Lin GUO ¹ ,
Xian-yong WEI ^{2, 3,,} ,
Chong XU ⁴ ,
Shen-gang ZHU ⁴

1.
School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, China
2.
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, China
3.
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining and Technology, Xuzhou 221116, China
4.
Technology Center of Huaibei Mining Group, Huaibei 235000, China

Corresponding author: Xue-yu TAO, taoxueyu@cumt.edu.cn Xian-yong WEI, wei_xianyong@163.com
Received Date: 24 September 2021
Revised Date: 1 November 2021
Accepted Date: 2 November 2021

Figures(8)

Polyvinyl alcohol (PVA), bacterial cellulose (BC) and sulfuric acid were used as raw materials to prepare PVA/BC composite hydrogel electrolyte (CHE_PVA_/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 CHE_PVA_/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 CHE_PVA_/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 CHE_PVA_/BC has great application prospects in flexible wearable energy storage devices.
- polyvinyl alcohol,
- bacterial cellulose,
- composite hydrogel electrolyte,
- self-healing,
- supercapacitor
1. [1]
  DUBEY R, GURUVIAH V. Review of carbon-based electrode materials for supercapacitor energy storage[J]. Ionics,2019,25(4):1419−1445. doi: 10.1007/s11581-019-02874-0
2. [2]
  SELVARAJ T, PERUMAL V, KHOR S F, ANTHONY L S, GOPINATH S C B, MOHAMED N M. The recent development of polysaccharides biomaterials and their performance for supercapacitor applications[J]. Mater Res Bull,2020,126:110839.
3. [3]
  HUANG Shan-shan, ZHAO Xiao-yan, XIE Feng-mei, CAO Jing-pei, WEI Xian-yong, TAKARADA Takayuki. Preparation of HyperCoal-based activated carbons for electric double layer capacitor[J]. J Fuel Chem Technol,2014,42(5):539−544.
4. [4]
  YE T T, LI L H, ZHANG Y. Recent progress in solid electrolytes for energy storage devices[J]. Adv Funct Mater,2020,30(29):2000077.
5. [5]
  DU Wei-shi, LV Yao-kang, CAI Zhi-wei, ZHANG Cheng. Flexible all-solid-state supercapacitor based on three-dimensional porous graphene/titanium-containing copolymer composite film[J]. Acta Phys-Chim Sin,2021,33(9):1828−1837.
6. [6]
  HUANG Y, ZHU M S, HUANG Y, PEI Z X, LI H F, WANG Z F, XUE Q, ZHI C Y. Multifunctional energy storage and conversion devices[J]. Adv Mater,2016,28(38):8344−8364. doi: 10.1002/adma.201601928
7. [7]
  GUO K, YU N, HOU Z Q, HU L T, MA Y, LI H Q, ZHAI T Y. Smart supercapacitors with deformable and healable functions[J]. J Mater Chem A,2017,5(1):16−30.
8. [8]
  CHEN X X, DAM M A, ONO K, MAL A, SHEN H B, NUTT S R, SHERAN K, WUDL F. A thermally re-mendable cross-linked polymeric material[J]. Science,2002,295(5560):1698−1702. doi: 10.1126/science.1065879
9. [9]
  JIN Y H, Yu C, DENMAN R J, ZHANG W. Recent advances in dynamic covalent chemistry[J]. Chem Soc Rev,2013,42(16):6634−6654. doi: 10.1039/c3cs60044k
10. [10]
  NAKAHATA M, TAKASHIMA Y, YAMAGUCHI H, HARADA A. Redox-responsive self-healing materials formed from host-guest polymers[J]. Nat Commun,2011,511.
11. [11]
  VOORHAAR L, HOOGENBOOM R. Supramolecular polymer networks: Hydrogels and bulk materials[J]. Chem Soc Rev,2016,45(14):4013−4031. doi: 10.1039/C6CS00130K
12. [12]
  YU K, TAYNTON P, ZHANG W, DUNN M L, QI H J. Influence of stoichiometry on the glass transition and bond exchange reactions in epoxy thermoset polymers[J]. RSC Adv,2014,4(89):48682−48690. doi: 10.1039/C4RA06543C
13. [13]
  CANADELL J, GOOSSENS H, KLUMPERMAN B. Self-healing materials based on disulfide links[J]. Macromolecules,2011,44(8):2536−2541. doi: 10.1021/ma2001492
14. [14]
  CHAO A, NEGULESCU J, ZHANG D H. Dynamic covalent polymer networks based on degenerative imine bond exchange: tuning the malleability and self-healing properties by solvent[J]. Macromolecules,2016,49(17):6277−6284. doi: 10.1021/acs.macromol.6b01443
15. [15]
  LEE D H, HEO G, PYO K H, KIM Y, KIM J W. Mechanically robust and healable transparent electrode fabricated via vapor-assisted solution process[J]. ACS Appl Mater Interfaces,2016,8(12):8129−8136. doi: 10.1021/acsami.6b01099
16. [16]
  PYO K H, LEE D H, KIM Y, KIM J W. Extremely rapid and simple healing of a transparent conductor based on Ag nanowires and polyurethane with a Diels–Alder network[J]. J Mater Chem C,2016,4(5):972−977. doi: 10.1039/C5TC04030B
17. [17]
  CHEN D D, WANG D R, YANG Y, HUANG Q Y, ZHU S J, ZHENG Z J. Self ‐ healing materials for next ‐ generation energy harvesting and storage devices[J]. Adv Energy Mater,2017,7(23):1700890. doi: 10.1002/aenm.201700890
18. [18]
  SUN X X, LUO C H, LUO F L. Preparation and properties of self-healable and conductive PVA-agar hydrogel with ultra-high mechanical strength[J]. Eur Polym J,2020,124:109465. doi: 10.1016/j.eurpolymj.2019.109465
19. [19]
  WU G F, JIN K Y, LIU L, ZHANG H X. A rapid self-healing hydrogel based on PVA and sodium alginate with conductive and cold-resistant properties[J]. Soft Matter,2020,16(13):3319−3324. doi: 10.1039/C9SM02455G
20. [20]
  HERNANDEZ R, SARAFIAN A, LOPEZ D, MIGANGOS C. Viscoelastic properties of poly(vinyl alcohol) hydrogels and ferrogels obtained through freezing-thawing cycles[J]. Polymer,2004,45(16):5543−5549. doi: 10.1016/j.polymer.2004.05.061
21. [21]
  WONG K K H, HUTTER J L, ZINKE-ALLMANG M, WAN W K. Physical properties of ion beam treated electrospun poly(vinyl alcohol) nanofibers[J]. Eur Polym J,2009,45(5):1349−1358. doi: 10.1016/j.eurpolymj.2009.02.002
22. [22]
  WU Z Y, LIANG H W, CHEN L F, HU B C, YU S H. Bacterial cellulose: A robust platform for design of three dimensional carbon-based functional nanomaterials[J]. Accounts Chem Res,2016,49(1):96−105. doi: 10.1021/acs.accounts.5b00380
23. [23]
  ZHAO N N, WU F, XING Y, QU W J, CHEN N, SHANG Y X, YAN M Y, LI Y J, LI L, CHEN R J. Flexible hydrogel electrolyte with superior mechanical properties based on poly (vinyl alcohol) and bacterial cellulose for the solid-state zinc-air batteries[J]. ACS Appl Mater Inter,2019,11(17):15537−15542. doi: 10.1021/acsami.9b00758
24. [24]
  ZHANG X F, MA X F, HOU T, GUO K C, YIN J Y, WANG Z G, SHU L, HE M, YAO J F. Inorganic salts induce thermally reversible and anti‐freezing Cellulose hydrogels[J]. Angew Chem Int Ed,2019,58(22):7366−7370. doi: 10.1002/anie.201902578
25. [25]
  CAMPANELLA A, DHLER D, BINDER W H. Self ‐ healing in supramolecular polymers[J]. Macromol Rapid Comm,2018,39(17):1700739. doi: 10.1002/marc.201700739
26. [26]
  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. doi: 10.1002/smll.201704497
27. [27]
  MA W B, ZHU K H, YE S F, WANG Y, GUO L, TAO X Y, GUO L T, FAN H L, LIU Z S, ZHU Y B, WEI X Y. A self-healing hydrogel electrolyte towards all-in-one flexible supercapacitors[J]. J Mater Sci: Mater Electron,2021,32:20445−20460. doi: 10.1007/s10854-021-06555-5
28. [28]
  XIA L Y, HUANG L, QING Y, ZHANG X Q, WU Y Q, JIANG W P, LU X Y. In situ filling of a robust carbon sponge with hydrogel electrolyte: A type of omni-healable electrode for flexible supercapacitors[J]. J Mater Chem A,2020,8(16):7746−7755. doi: 10.1039/D0TA01764G
29. [29]
  YIN B S, ZHANG S W, KE K, WANG Z B. Advanced deformable all-in-one hydrogel supercapacitor based on conducting polymer: Toward integrated mechanical and capacitive performance[J]. J Alloy Compd,2019,805:1044−1051. doi: 10.1016/j.jallcom.2019.07.144
30. [30]
  WANG Y H, LV C, JI G C, HU R F, ZHENG J P. An all-in-one supercapacitor with high stretchability via a facile strategy[J]. J Mater Chem A,2020,8(17):8255−8261. doi: 10.1039/D0TA00757A
31. [31]
  LAI F L, FANG Z M, CAO L, LI W, LIN Z D, ZHANG P. Self-healing flexible and strong hydrogel nanocomposites based on polyaniline for supercapacitors[J]. Solid State Ionics,2020,26(6):1−11.
32. [32]
  HOU L Y, ZHI X M, ZHANG W Y, ZHOU H H. Boosting the electrochemical properties of polyaniline by one-step co-doped electrodeposition for high performance flexible supercapacitor applications[J]. J Electroanal Chem,2020,863:114064. doi: 10.1016/j.jelechem.2020.114064
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