Weavable, Conductive Yarn-Based NiCo//Zn Textile Battery with High Energy Density and Rate Capability Yan Huang, Wing Shan Ip, Yuen Ying Lau, Jinfeng Sun, Jie Zeng, Nga Sze Sea Yeung, Wing Sum Ng, Hongfei Li, Zengxia Pei, Qi Xue, Yukun Wang, Jie Yu, Hong Hu and Chunyi Zhi * Corresponding E-mail: cy.zhi@cityu.edu.hk (C. Zhi) List of Contents Supplementary Methods: Method S1. Physicochemical Characterization of the Yarn Electrodes. Supplementary Tables: Table S1. Comparison of electrochemical performance of various batteries and supercapacitors. Supplementary Figures: Figure S1. Photograph of patterns hand-knitted by the conductive yarns. Figure S2. Surface contact angle results of yarns without (a) vs. with (b) hydrothermal treatment in NaOH. Figure S3. EDX quantitative elemental analysis of the as-electrodeposited NCHO. Figure S4. CV (a) and GCD curves of NCHO-electrodeposited yarns under various deposition times. Figure S5. GCD curves of (a) Zn-, and (b) Bi-based batteries with different composition of cathode.
Figure S6. CV curves of the NiCo//Zn yarn battery with various deposition times of Zn. Figure S7. CV curves of the NiCo//Zn yarn battery measured in various concentrations of KOH. Figure S8. GCD curves of the NCHO-electrodeposited yarns with various lengths. Figure S9. CV curves of the bare stainless steel yarn and the Zn-electroplated yarn. Figure S10. Optical image of the solid-state yarn battery. Figure S11. Ragone plot comparing areal energy and power densities of aqueous batteries and supercapacitors. Data of our work are normalized to the whole battery including two yarn electrodes and solid electrolyte. Figure S12. A SEM image of the NCHO electrodes during deformation. Scale bar: 100 nm.
Method S1. Physicochemical Characterization of the Yarn Electrodes. The wettability of a single yarn was determined by the KRÜSS Drop Shape Analyzer DSA100. The microstructure and morphology of yarns were characterized by scanning electron microscope (SEM) (JEOL JSM-6335F) with an acceleration voltage of 5 kv. X-ray diffraction (XRD) was performed on a Philips X'Pert High Resolution Materials Research Diffractometer using Cu Kα radiation (λ = 1.54 Å). X-ray photoelectron spectroscopy (XPS) analyses were conducted on an ESCALAB 250 photoelectron spectroscopy (Thermo Fisher Scienctific) at 1.2 10 9 mbar using Al K α X-ray beam (1486.6 ev). The XPS spectra were charge corrected to the adventitious C 1s peak at 284.5 ev.
Table S1. Comparison of electrochemical performance of various batteries and supercapacitors. C L P L E L Ref. Electrode Electrolyte (mah cm -1 ) (mw cm -1 ) (mwh cm -1 ) (mah cm -2 ) (mw cm -2 ) (mwh cm -2 ) (mah cm -3 ) (W cm -3 ) (Wh cm -3 ) Our work Zn//NiCoO 3H x aqueous 0.037 17.13 0.06 0.17 75.72 0.27 16.56 7.57 0.027 (2 electrodes) (2 electrodes) (2 electrodes) (2 electrodes) (2 electrodes) (2 electrodes) solid 0.019 8.19 0.03 0.076 32.77 0.12 5.04 2.18 0.008 (device) (device) Ref. 10 PPy@MnO 2@rGO// 0.023 1.33 0.009 2.76 0.16 0.0011 PVA/H PPy@MnO 3PO 4 2@rGO (device) (device) Ref. 16 ZnO//NiO KOH 0.5 0.01 PVA/KOH 0.2 0.008 Ref. 17 Co9S8//Co3O4@RuO2 PVA/KOH 1.91 0.9 0.001 Ref. 18 C//C/MnO 2 2.75 Ref. 24 CF@NiO//CF@Fe 3O 4 KOH 0.8 0.006 PVA/KOH 0.6 0.005 Ref. 25 4 V/500 uah Li thin film battery 0.006 0.007 Ref. 26 CNTs//Fe3O4-C 0.029 0.0012 Ref. 27 CoO@PPy//AC 0.1 0.0013 Ref. 28 TiO 2@MnO 2//TiO 2@C 0.21 0.0005 Ref. 29 MnO 2//Fe 2O 3 0.12 0.00031 Ref. 30 TiN//Fe 2N 0.2 0.0003 Ref. 31 MnO 2//WON 0.6 0.0011 Ref. 32 MnO 2//Ti-Fe 2O 3@PEDOT 0.52 0.0006 Ref. 33 VO x//vn 0.83 0.0004 Ref. 34 Graphene//Co 3O 4 1.2 0.0004 Ref. 35 MnO 2/ZnO//MnO 2/ZnO PVA/H 3PO 4 0.014 0.00003 Ref. 36 CNT/TiO 2//CNT/TiO 2 0.00015 Ref. 37 NiSn//LiMnO 2 100 0.21 Ref. 38 Li//MWCNT/Mno 2 2.43 0.0357 Ref. 39 Co xfe 3-xO 4//Co 3O 4@Ni-Co-O KOH 40 2 Ref. 40 Li 4Ti 5O 12//LiFePO 4 0.037 22 2.2 Ref. 41 FeO x//ni(oh) 2 KOH 40 0.4 Ref. 42 Li 4Ti 5O 12//LiCoO 2 10.2 0.8 Ref. 43 Zn//MnO 2 PAA/KOH 5.6 0.9 8 Ref. 44 SWCNT/rGo// SWCNT/rGo 1 (device) Ref. 45 rgo/cnt// rgo/cnt PVA/H 3PO 4 140 0.19 0.0038 0.19 0.0035 Ref. S1 PPy//PPy PVA/H 3PO 4 3.6 0.033 Ref. S2 CNT//CNT PVA/H 3PO 4 7 0.01 Ref. S3 C//C H 2SO 4 9 0.0027 Ref. S4 CNT//CNT PVA/H 3PO 4 32 0.0018 Ref. S5 PANI/SWCNT//PANI/SWCNT PVA/H 2SO 4 0.145 0.00057 Ref. S6 MnO 2/ZnO//MnO 2/ZnO PVA/H 3PO 4 0.014 0.00003 Ref. S7 graphene//graphene Na 2SO 4 0.0075 0.000027 C A P A E A C V P V E V 0.003 (device)
Figure S1. Photograph of patterns hand-knitted by the conductive yarns. These mechanically tough conductive yarns can suffer hand knitting to form arbitrary patterns without any breakage.
Figure S2. Surface contact angle results of yarns without (a) vs. with (b) hydrothermal treatment in NaOH. NaOH greatly improves the wettability of pristine conductive yarns by the hydrothermal treatment. The treated yarn is so hydrophilic that once the droplet contacts the yarn, it is quickly adsorbed into the yarn without leaving a visible liquid/solid interface.
Figure S3. EDX quantitative elemental analysis of the as-electrodeposited NCHO. The atomic ratio is ca. 1: 1: 3 (Ni:Co:O), which is consistent with that of Ni to Co in the precursor electrolyte.
Figure S4. CV (a) and GCD curves of NCHO-electrodeposited yarns under various deposition times. The capacity initially increases with the increase of electrodeposition time of NCHO, and then decreases. The optimum time is 20 min.
Figure S5. GCD curves of (a) Zn-, and (b) Bi-based batteries with different composition of cathode. Compared with the absence of Ni or Co, the bimetallic hydroxide of Ni and Co have higher capacities and discharge voltage plateau.
Figure S6. CV curves of the NiCo//Zn yarn battery with various deposition times of Zn. In the time of Zn electroplating we studied, Zn is always over amount compared to NCHO and therefore the capacity just slightly increases with the Zn electrodeposition time.
Figure S7. CV curves of the NiCo//Zn yarn battery measured in various concentrations of KOH. The liquid electrolyte is optimized to be 5 M KOH due to its good ionic conductivity and low viscosity.
Figure S8. GCD curves of the NCHO-electrodeposited yarns with various lengths. With the increase of length, the capacity increases. When the capacity is normalized to the length of conductive yarns, our highly conductive yarns show an almost constant capacity per length.
Figure S9. CV curves of the bare stainless steel yarn and the Zn-electroplated yarn. Compared with the Zn anode, the bare stainless steel yarn barely contributes capacity. Therefore, the impressive electrochemical performances are believed to fully arise from our NiCo//Zn battery.
Figure S10. Optical image of the solid-state yarn battery. The volume of the whole device including the two yarns and their surrounding electrolyte is determined as Width Height Length = 750 µm 500 µm 1 cm = 0.00375 cm 3. The device area is estimated to be 2 (Width + Height) Length = 2 (750 µm + 500 µm) 1 cm = 0.25 cm 2.
Figure S11. Ragone plot comparing areal energy and power densities of aqueous batteries and supercapacitors. Data of our work are normalized to the whole battery including two yarn electrodes and solid electrolyte. Our yarn batteries also show higher areal energy and power densities compared with aqueous batteries and supercapacitors. S1-S6
Figure S12. A SEM image of the NCHO electrodes during deformation. Scale bar: 100 nm. Being different from those intrinsically flexible polymers and carbon materials, metal oxides are vulnerable to break and produce cracks upon deformation. The cracks formed on the NCHO during mechanical deformation are likely responsible for the observed capacity loss.
Supplementary References S1. Yuan, L. Y.; Yao, B.; Hu, B.; Huo, K. F.; Chen, W.; Zhou, J. Polypyrrole-Coated Paper for Flexible Solid-State Energy Storage. Energy Environ. Sci. 2013, 6, 470-476. S2. Le, V. T.; Kim, H.; Ghosh, A.; Kim, J.; Chang, J.; Vu, Q. A.; Pham, D. T.; Lee, J.-H.; Kim, S.-W.; Lee, Y. H. Coaxial Fiber Supercapacitor Using All-Carbon Material Electrodes. ACS Nano 2013, 7, 5940-5947. S3. Fu, Y. P.; Fu, Y.; Cai, X.; Wu, H.; Lv, Z.; Hou, S.; Peng, M.; Yu, X.; Zou, D. Fiber Supercapacitors Utilizing Pen Ink for Flexible/Wearable Energy Storage. Adv. Mater. 2012, 24, 5713-5718. S4. Ren, J.; Bai, W. Y.; Guan, G. Z.; Zhang, Y; Peng, H. S. Flexible and Weaveable Capacitor Wire Based on a Carbon Nanocomposite Fiber. Adv. Mater. 2013, 25, 5965-5970. S5. Meng, Q. H.; Wang, K.; Guo, W.; Fang, J.; Wei, Z. X.; She, X. L. Thread-like Supercapacitors Based on One-Step Spun Nanocomposite Yarns. Small 2014, 10, 3187-3193. S6. Liu, W. W.; Feng, Y. Q.; Yan, X. B.; Chen, J. T.; Xue, Q. J. Superior Micro- Supercapacitors Based on Graphene Quantum Dots. Adv. Funct. Mater. 2013, 23, 4111-4122.