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Polymer Chemistry Polymer Chemistry View Article Online PAPER View Journal | View Issue Solution processible hyperbranched inverse- vulcanized polymers as new cathode materials Cite this: Polym. Chem., 2015, 6, 973 in Li–S batteries† Yangyang Wei,a Xiang Li,b Zhen Xu,a Haiyan Sun,a Yaochen Zheng,a,c Li Peng,a Zheng Liu,a Chao Gao*a and Mingxia Gao*b Soluble inverse-vulcanized hyperbranched polymers (SIVHPs) were synthesized via thiol–ene addition of polymeric sulfur (S8) radicals to 1,3-diisopropenylbenzene (DIB). Benefiting from their branched molecular architecture, SIVHPs presented excellent solubility in polar organic solvents with an ultrahigh concen- tration of 400 mg mL−1. After end-capping by sequential click chemistry of thiol–ene and Menschutkin quaternization reactions, we obtained water soluble SIVHPs for the first time. The sulfur-rich SIVHPs were employed as solution processible cathode-active materials for Li–S batteries, by facile fluid infiltration into conductive frameworks of graphene-based ultralight aerogels (GUAs). The SIVHPs-based cells showed high initial specific capacities of 1247.6 mA h g−1 with 400 charge–discharge cycles. The cells also demonstrated an excellent rate capability and a considerable depression of shuttle effect with stable cou- Received 24th September 2014, lombic efficiency of around 100%. The electrochemical performance of SIVHP in Li–S batteries over- Accepted 14th October 2014 whelmed the case of neat sulfur, due to the chemical fixation of sulfur. The combination of high DOI: 10.1039/c4py01055h solubility, structure flexibility, and superior electrochemical performance opens a door for the promising www.rsc.org/polymers application of SIVHPs. Introduction On the other hand, the Li–S battery is emerging as a new kind of lithium ion battery. Organosulfur compounds and sul- Hyperbranched polymers (HPs) have attracted wide attention furized carbons are being explored to be used as cathode Published on 22 October 2014. Downloaded by Zhejiang University 25/10/2016 08:19:29. due to their distinctive chemical and physical properties, materials in lithium ion batteries, aimed at exceeding the per- 3 which are derived from their unique three-dimensional dendri- formance of marketable products like LiCoO2 and LiMnO2. tic molecular architecture with high content of functional However, the energy density of Li–S batteries of this kind was groups, low viscosity and high solubility.1 HPs have been hard to improve since it was fairly difficult to obtain organo- applied in some fields including coatings, processing additives sulfur compounds and sulfurized carbons with sulfur content and electrolytes in lithium ion batteries.2 However, HPs have over 50 wt%.4 Additionally, sulfurized carbons usually need never been used as electrode materials, probably due to the tedious thermal treatments above 250 °C, due to their poor difficulty in the design of the desired molecular structures. solubility.5 Recently, Pyun and co-workers addressed such a challenge via bulk inverse vulcanization, which was the copoly- merization of a large percentage of sulfur (50–99 wt%) and a – aMOE Key Laboratory of Macromolecular Synthesis and Functionalization, modest amount of DIB (1 50 wt%). It exhibited high specific Department of Polymer Science and Engineering, Zhejiang University, 38 Zheda capacity and stability when using these copolymers as Road, Hangzhou, P. R. China. E-mail: [email protected] cathode-active materials in Li–S batteries.6 However, partial b State Key Laboratory of Silicon Materials, Key Laboratory of Advanced Materials solubility led to hard processability below the thermal and Applications for Batteries of Zhejiang Province & Department of Materials decomposition temperature of these polymers. Therefore, poly- Science and Engineering, Zhejiang University, Hangzhou 310027, PR China. E-mail: [email protected]; Tel: +86-571-87952615 mers with high sulfur content and high solubility are eagerly cCollege of Chemistry and Chemical Engineering, Yantai University, expected. 30 Qingquan Road, Yantai 264005, P. R. China Herein, we synthesized a kind of SIVHPs via thiol–ene †Electronic supplementary information (ESI) available: Data of molar masses addition of S8 radicals to DIB in solution. These SIVHPs before and after modification of SIVHPs, solubility of SIVHPs in electrolyte, GPC possess relatively high molecular weights and excellent solubi- curves of SIVHPs, differential scanning calorimetry for preparation of SIVHPs, −1 FTIR spectra, TGA curves and EIS spectra for SIVHPs. See DOI: 10.1039/ lity in organic solvents (up to 400 mg mL ). When modified c4py01055h via sequential thiol–ene and Menschutkin click reactions, This journal is © The Royal Society of Chemistry 2015 Polym. Chem.,2015,6,973–982 | 973 View Article Online Paper Polymer Chemistry SIVHPs were endowed with water solubility for the first time. where W is the solubility of SIVHPs, m0 is the mass of SIVHPs 7 8 The solution of SIVHPs in CHCl3 was absorbed into GUAs (g) and m1 is the mass of the insoluble part of SIVHPs (g). and used as a cathode-active material in Li–S batteries. The Li–S batteries showed high coulombic efficiency (∼100%), Synthesis of soluble inverse-vulcanized hyperbranched superior cycling performance and good rate capability. polymers via thiol–ene addition of S8 radicals to DIB in solution Experimental S8 and DIB were mixed in CHCl3 (or toluene, etc.) with feed molar ratios of S8 to DIB from 2 to 8 (8, 4, 8/3, 2 and 8/5). The Materials volume of solvent was calculated to get a mass fraction of reac- DIB and 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) were tants of 35%. The reaction took place in an autoclave under N2 – purchased from TCI Shanghai. 3-(Dimethylamino)-1-propane- atmosphere followed by heating to 150 °C 180 °C (150, 160, – thiol was acquired from Atomax Chem Co. Ltd Sublimed 170, 180, 190 and 200 °C) for 0.5 7 hours (0.25, 0.5, 0.75, 1, 2, 3, 5, 7 hours). After cooling down to room temperature, the sulfur, chloroform (CHCl3), dimethylformamide (DMF), tetra- hydrofuran (THF), toluene, 1,4-dioxane, anisole, N-methyl-2- solution was precipitated with n-hexane. After being dried at – pyrrolidone (NMP) and other organic solvents were purchased 80 °C, the orange-red product was achieved (yield: 35% 80%). 1 δ – from Sinopharm Chemical Reagent Co. Ltd DIB was passed H NMR (400 MHz, CDCl3), (ppm): 7.32 (C6H4), 5.63 4.94 v – – – – – 13 through a column of basic alumina before using and all the (C CH2), 4.26 2.48 (Sn CH2 C), 2.37 0.44 (C CH3). C NMR δ – – other materials were used as received. (500 MHz, CDCl3), (ppm): 146.5 137.1, 129.9 120.5, 117.6, 112.8, 59.4–41.5, 33.7–11.6. FTIR: 2967.24 (C–H), 1598.24 Instrumentation (CvC), 1537.32–1340.99 (C–H), 1213.91 (C–C), 855.08–650.48 – – −1 Gel permeation chromatography (GPC) was recorded on a Per- (C H), 486.50 (C S) cm . kinElmer HP 1100, using THF as the eluent at a flow rate of − Synthesis of quaternary ammonium SIVHPs 1 mL min 1, RI-WAT 150 CVt+ as the detector and linear poly- styrene for calibration at 40 °C for characterization of apparent SIVHPs (0.04 g, 1 mmol), 3-(dimethylamino)-1-propanethiol molecular weights. 1H NMR (400 MHz) spectroscopy measure- (DPT) (0.60 g, 5 mmol) and DMPA (21 mg, 0.08 mmol) were ments were carried out on a Varian Mercury Plus 400 NMR added into dried toluene (2 mL) in a 25 mL round-bottom 13 spectrometer. C NMR (500 MHz) measurements were carried flask. After being sealed, the mixture was bubbled with N2 for out on an Avance III 500 NMR spectrometer. Fourier transform 15 min to eliminate oxygen. Then, the reaction was triggered infrared (FTIR) spectra were recorded on a PE Paragon 1000 by UV-irradiation at 365 nm for 4 hours under stirring at room spectrometer (film or KBr disk). UV-visible spectra were temperature. The solution was subsequently diluted with 8 mL obtained using a Varian Cary 300 Bio UV-visible spectro- of dried DMF and cooled down to 0 °C. Another DMF (3 mL) photometer. Thermogravimetric analysis (TGA) was carried out solution of 3-bromo-1-propyne (14 mg, 1.2 mmol) was added on a PerkinElmer Pyris 6 TGA instrument under nitrogen with into the DMF solution above dropwise under vigorous stirring. − a heating rate of 10 °C min 1. SEM images were obtained by a The mixture was further stirred overnight and added into Published on 22 October 2014. Downloaded by Zhejiang University 25/10/2016 08:19:29. Hitachi S4800 field-emission SEM system. The cells were dis- diethyl ether solution dropwise for precipitation at 0 °C to charged and charged on a LAND electrochemical station attain orange precipitates. After being dried in vacuum at − (Wuhan) from 1.0 to 3.0 V at a current density of 100 mA g 1 room temperature, quaternary ammonium SIVHPs were sulfur to test the cycle life. Cyclic voltammograms (CV) were achieved (yield: 50%–80%). 1H NMR (400 MHz, DMSO), δ – – – u recorded on a CHI604c electrochemical workstation (Shanghai (ppm): 7.94 7.24 (C6H4), 4.00 3.73 (2H, CH2 C CH), + Chenhua) between 1.0 and 3.0 V to characterize the redox be- 3.60–3.39 (2H, C6H4–CH2–CH2–CH2–N ), 3.24–3.00 (7H, u + – – – – – havior and the kinetic reversibility of the cell. Electrochemical C CH,N(CH3)2), 3.00 2.92 (2H, C6H4 CH CH2 S), 2.85 2.73 – – – – + – – – – impedance spectrum (EIS) measurements were performed (2H, S CH2 CH2 CH2 N ), 2.25 1.96 (4H, C6H4 CH2 CH2 S, + 13 using a frequency response analyzer (Solartron 1255B, Solar- S–CH2–CH2–CH2–N ).
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