Batteries. and Zhaoyin Wen a,* a. CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics,

Transcription

1 Supporting Information High-strength Internal Crosslinking Bacterial Cellulose Network Based Gel Polymer Electrolyte for Dendrite-suppressing and High-rate Lithium Batteries Dong Xu a,b, Bangrun Wang a,b, Qing Wang a,b, Sui Gu a,b, Wenwen Li a,b, Jun Jin a, Chunhua Chen c, and Zhaoyin Wen a,* a. CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai , P. R. China. b. University of Chinese Academy of Sciences, Beijing , P. R. China c. CAS Key Laboratory of Materials for Energy Conversion, University of Science and Technology of China, Hefei, Anhui, , P. R. China. *. Corresponding author Tel: , Fax: S-1

2 Figure S1 SEM images of (a) freeze-dried and (b) oven-dried BC films. Figure S2 TGA curves of BC-GPES and commercial separator obtained in air atmosphere in the temperature range of 50 C to 500 C at a rate of 10 C min-1. S-2

3 Figure S3 Optical images of BC-GPE for the bending measurement. The obtained BC-GPE shows good bending property. As shown in Figure S3a, the gel polymer electrolyte was rolled on a glass rod without any rupture. When further unfolded (Figure S3b), the BC-GPE could recovered to be a flat film without damage. The excellent bending property of BC-GPE was predicted by the tensile strength test in Figure 3d. The outstanding blending property of BC-GPE makes it possible to be used in flexible energy storage systems. Figure S4 Galvanostatic cycling test of LiLE-SLi at 0.5 ma cm -2. S-3

4 Figure S5 Initial chargedischarge cycles of LiFePO 4 BC-GPELi and LiFePO 4 LE-SLi batteries Figure S6 EIS plots of the LiFePO 4 BC-GPELi and LiFePO 4 LE-SLi batteries before and after 150 cycles at 5C. S-4

5 Figure S7 SEM images of (a) the lithium anode of the LiFePO 4 LE-SLi battery, and (b) the lithium anode of the LiFePO 4 BC-GPELi battery after 150 cycles at 0.5C S-5

6 Figure S8 Galvanostatic cycling tests of (a) LiBC-GPELi cells and (b) LiLE-SLi cells at 0.5 S-6

7 ma cm -2. Figure S9 Cycling performances of LiFePO 4 LE-SLi batteries at (a) 0.5C and (b) 5C; cycling performances of LiFePO 4 BC-GPELi batteries at (c) 0.5C and (d) 5C. S-7

8 Figure S10 Schematics of the morphological changes of lithium anode with (a) commercial separator and liquid electrolyte and (b) BC-GPE during chargedischarge cycles. S-8

9 Table S1 Mechanical properties comparison of various gel polymer electrolytes Reference Gel polymer electrolytes Tensile strength (MPa) Our work BC-GPE NonwovenP(VDF-HFP) Electrospun PVDFHydroxyethyl cellulosepvdf PEOPEGLATP TPUPVDF Cellulose acetate-liclo DEBAPEGDEDPPO 3D-GPE Silk fibroinionic liquid LiPBPABPEO PPCCellulose Poly (vinylene carbonate) 41.4 S-9

10 Table S2 Electrolyte conservation rates of both BC-GPE and LE-S GPE conservation Ionic conductivity BC-GPE 93.32% S cm -1 LE-S 21.29% S cm -1 S-10

11 Table S3 Ionic conductivity and rate comparison of various gel polymer electrolytes Reference Gel polymer electrolytes Ionic conductivity 25 C (S cm -1 ) at Discharge capacity (ma h g -1 ) Our work BC-GPE C PVDF-HFPPEOPS C 12 PVDF-HFPIonic liquid C Electrospun PVDF-HFPIonic liquid C PEO C Electrospun PVDFHydroxyethyl cellulosepvdf C 3C PMMAPolyurethane acrylateionic liquid S-11

12 3C 16 poly(ε-caprolactone) Ethylene carbonate C 0.5C POSSIonic liquid C 18 Poly (methyl methacrylate-maleic anhydride) C 19 Lignocellulose Polyethylene Glycol C Electrospun PANTEOSPSZ C PVDF-HFPOligomeric ionic liquid C Poly(styrene-co-methyl acrylate) C S-12

13 23 Electrospun Poly fluoride) (vinylidene C Polyoxyethylene-b polyacrylonitrile network C 100 Table S4 Fitting results of the EIS plots of the LiFePO4BC-GPELi and LiFePO4LE-SLi batteries before and after 150 cycles at 0.5C Battery Before cycling After cycling Rb (Ω) Rƒ (Ω) Rb (Ω) Rƒ (Ω) Rct (Ω) LiFePO4BC-GPELi LiFePO4LE-SLi S-13

14 Reference: (1) Zhu, Y.; Yang, Y.; Fu, L.; Wu, Y. A Porous Gel-type Composite Membrane Reinforced by Nonwoven: Promising Polymer Electrolyte with High Performance for Sodium Ion Batteries. Electrochimica Acta 2017, 224, (2) Zhang, M. Y.; Li, M. X.; Chang, Z.; Wang, Y. F.; Gao, J.; Zhu, Y. S.; Wu, Y. P.; Huang, W. A Sandwich PVDFHECPVDF Gel Polymer Electrolyte for Lithium Ion Battery. Electrochimica Acta 2017, 245, (3) Zhai, H.; Xu, P.; Ning, M.; Cheng, Q.; Mandal, J.; Yang, Y. A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries. Nano Letters 2017, 17, (4) Wu, N.; Wang, W.; Wei, Y.; Li, T. Studies on the Effect of Nano-Sized MgO in Magnesium-Ion Conducting Gel Polymer Electrolyte for Rechargeable Magnesium Batteries. Energies 2017, 10. (5) Sudiarti, T.; Wahyuningrum, D.; Bundjali, B.; Arcana, I. M. Mechanical Strength and Ionic Conductivity of Polymer Electrolyte Membranes Prepared from Cellulose Acetate-Lithium Perchlorate. In Innovation in Polymer Science and Technology 2016; Yudianti, R.; Azuma, J., Eds.; (6) Lu, Q.; He, Y.-B.; Yu, Q.; Li, B.; Kaneti, Y. V.; Yao, Y.; Kang, F.; Yang, Q.-H. Dendrite- Free, High-Rate, Long-Life Lithium Metal Batteries with a 3D Cross-Linked Network Polymer Electrolyte. Advanced Materials 2017, 29. S-14

15 (7) Karimi, F.; Peppley, B. A. Comparison of Conventional Versus Microwave Heating for Polyol Synthesis of Supported Iridium Based Electrocatalyst for Polymer Electrolyte Membrane Water Electrolysis. Int. J. Hydrog. Energy 2017, 42, (8) Zhang, Y.; Cai, W.; Rohan, R.; Pan, M.; Liu, Y.; Liu, X.; Li, C.; Sun, Y.; Cheng, H. Toward Ambient Temperature Operation with All-Solid-State Lithium Metal Batteries with A sp(3) Boron-based Solid Single Ion Conducting Polymer Electrolyte. Journal of Power Sources 2016, 306, (9) Zhao, J. H.; Zhang, J. J.; Hu, P.; Ma, J.; Wang, X. G.; Yue, L. P.; Xu, G. J.; Qin, B. S.; Liu, Z. H.; Zhou, X. H.; Cui, G. L. A Sustainable and Rigid-Flexible Coupling Cellulose-supported Poly (Propylene Carbonate) Polymer Electrolyte Towards 5 V High Voltage Lithium Batteries. Electrochimica Acta 2016, 188, (10) Chai, J.; Liu, Z.; Zhang, J.; Sun, J.; Tian, Z.; Ji, Y.; Tang, K.; Zhou, X.; Cui, G. A Superior Polymer Electrolyte with Rigid Cyclic Carbonate Backbone for Rechargeable Lithium Ion Batteries. Acs Applied Materials & Interfaces 2017, 9, (11) Prabakaran, P.; Manimuthu, R. P.; Gurusamy, S.; Sebasthiyan, E. Plasticized Polymer Electrolyte Membranes Based on PEOPVdF-HFP for Use as an Effective Electrolyte in Lithium-ion Batteries. Chin. J. Polym. Sci. 2017, 35, (12) Muthupradeepa, R.; Sivakumar, M.; Subadevi, R.; Suryanarayanan, V. Sulfonium Cation Based Ionic Liquid Incorporated Polymer Electrolyte for Lithium Ion Battery. Polym. Bull. 2017, 74, S-15

16 (13) Tong, Y.; Xu, Y.; Chen, D.; Xie, Y.; Chen, L.; Que, M.; Hou, Y. Deformable and Flexible Electrospun Nanofiber-Supported Cross-Linked Gel Polymer Electrolyte Membranes for High Safety Lithium-ion Batteries. Rsc Advances 2017, 7, (14) Li, W.; Pang, Y.; Liu, J.; Liu, G.; Wang, Y.; Xia, Y. A PEO-based Gel Polymer Electrolyte for Lithium Ion Batteries. Rsc Advances 2017, 7, (15) Li, L.; Wang, F.; Li, J.; Yang, X.; You, J. Electrochemical Performance of Gel Polymer Electrolyte with Ionic Liquid and PUAPMMA Prepared by Ultraviolet Curing Technology for Lithium-ion Battery. Int. J. Hydrog. Energy 2017, 42, (16) Muchakayala, R.; Song, S.; Gao, S.; Wang, X.; Fan, Y. Structure and Ion Transport in an Ethylene Carbonate-Modified Biodegradable Gel Polymer Electrolyte. Polym. Test 2017, 58, (17) Lee, J. H.; Lee, A. S.; Lee, J.-C.; Hong, S. M.; Hwang, S. S.; Koo, C. M. Hybrid Ionogel Electrolytes Derived from Polyhedral Oligomeric Silsesquioxane for Lithium Ion Batteries. J. Nanosci. Nanotechnol. 2017, 17, (18) Zhong, X.-P.; Huang, Y.; Cao, H.-J.; Lin, Y.-H.; Liu, B.; Song, A. M.; Chen, Z.-M.; Tang, S.-H.; Wang, M.-S.; Li, X. Polyhedral Oligomeric Silsesquioxane-modified Gel Polymer Electrolyte Based on Matrix of Poly(Methyl Methacrylate-Maleic Anhydride). Journal of Solid State Electrochemistry 2017, 21, (19) Song, A.; Huang, Y.; Liu, B.; Cao, H.; Zhong, X.; Lin, Y.; Wang, M.; Li, X.; Zhong, W. Gel Polymer Electrolyte Based on Polyethylene Glycol Composite Lignocellulose Matrix with Higher Comprehensive Performances. Electrochimica Acta 2017, 247, S-16

17 (20) Smith, S. A.; Williams, B. P.; Joo, Y. L. Effect of Polymer and Ceramic Morphology on the Material and Electrochemical Properties of Electrospun PANPolymer Derived Ceramic Composite Nanofiber Membranes for Lithium Ion Battery Separators. Journal of Membrane Science 2017, 526, (21) Kuo, P.-L.; Tsao, C.-H.; Hsu, C.-H.; Chen, S.-T.; Hsu, H.-M. A New Strategy for Preparing Oligomeric Ionic Liquid Gel Polymer Electrolytes for High-Performance and Nonflammable Lithium Ion Batteries. Journal of Membrane Science 2016, 499, (22) Zheng, Z.; Gao, X.; Luo, Y.; Zhu, S. Employing Gradient Copolymer To Achieve Gel Polymer Electrolytes with High Ionic Conductivity. Macromolecules 2016, 49, (23) Zhu, Y.; Xiao, S.; Shi, Y.; Yang, Y.; Hou, Y.; Wu, Y. A Composite Gel Polymer Electrolyte with High Performance Based on Poly(Vinylidene Fluoride) and Polyborate for Lithium Ion Batteries. Advanced Energy Materials 2014, 4. (24) Kuo, P.-L.; Wu, C.-A.; Lu, C.-Y.; Tsao, C.-H.; Hsu, C.-H.; Hou, S.-S. High Performance of Transferring Lithium Ion for Polyacrylonitrile-Interpenetrating Cross linked Polyoxyethylene Network as Gel Polymer Electrolyte. Acs Applied Materials & Interfaces 2014, 6, S-17