Impact of the Mechanical Properties of a Functionalized Cross-Linked

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Cite This: ACS Appl. Mater. Interfaces 2019, 11, 22481−22491

Impact of the Mechanical Properties of a Functionalized CrossLinked Binder on the Longevity of Li−S Batteries C. Y. Kwok,† Q. Pang,† A. Worku,‡ X. Liang,† M. Gauthier,*,‡ and L. F. Nazar*,† †

Waterloo Institute of Nanotechnology and Department of Chemistry and ‡Department of Chemistry, University of Waterloo, 200 University Ave. W., Waterloo, Ontario N2L 3G1, Canada

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S Supporting Information *

ABSTRACT: One of the very challenging aspects of Li−S battery development is the fabrication of a sulfur electrode with high areal loading using conventional Li-ion binders. Herein, we report a new multifunctional polymeric binder, synthesized by the free-radical cross-linking polymerization of [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETMAC) and ethylene glycol diacrylate (EGDA) to form poly(AETMAC-co-EGDA), that not only helps to confine the soluble polysulfide species but also has the desired mechanical properties to allow stable cycling of high-sulfur loading cathodes. Through a combination of spectroscopic and electrochemical studies, we elucidate the chemical interactions that inhibit polysulfide shuttling. We also show that extensive cross-linkage enables this polymeric binder to exhibit a low degree of swelling as well as high tensile modulus and toughness. These attributes are essential to maintain the architectural integrity of the sulfur cathode during extended cycling. Using this material, Li−S cells with a high-sulfur loading (6.0 mg cm−2) and a lowintermediate electrolyte/sulfur ratio (7 μL:1 mg) achieve an areal capacity of 5.4 mA h cm−2 and can be (dis)charged for 300 cycles with stable reversible redox behavior after the initial cycles. KEYWORDS: Li−S batteries, high areal sulfur loading, functionalized cross-linked binder, polysulfide chemisorption, mechanical properties

1. INTRODUCTION The rising demands in advanced energy storage devices for electric vehicles, unmanned aerial vehicles, and robots call for forward-looking battery technologies that can exceed the specific energy afforded by intercalation chemistry.1 An approach based on lithium−sulfur (Li−S) conversion chemistry is promising for next-generation electrochemical batteries, due to sulfur’s high theoretical specific capacity of 1675 mA h g−1 and energy density of 2800 W h L−1.2 The high natural abundance and innocuity of sulfur further contributes to the low cost and appeal of such a system.3,4 The commercialization of Li−S batteries, however, has been plagued by low areal sulfur loading, poor sulfur utilization, and capacity degradation. These drawbacks originate from the dissolution and shuttling of lithium polysulfides, a large volume change in the cathode during cycling, and a lengthened electronic/ionic pathway in thick electrodes.5−8 Considerable effort has been devoted toward the optimization of cell components, including the development of new host materials,9−11 separators,12,13 and electrolytes.14,15 Despite these recent advances,16,17 fabricating a high areal capacity stable-cycling Li−S battery still remains a major challenge. Low-sulfur loading (150 cycles) of the poly(DADMAC-co-EGDA)-based sulfur cathode is ascribed to its high degree of swelling as well as to the low tensile strength and toughness of the polymer. At such a high degree of swelling, the ammonium cations may interact with the solvent molecules as much as with the polysulfides. The poly(AETMAC-co-EGDA)-based electrode reached a higher capacity of 5 mA h cm−2 (after the first few conditioning cycles needed to fully wet the electrode)37,67−69 and ultimately stabilized at ∼3 mA h cm−2 on the 50th cycle. Most importantly, capacity retention was excellent over the latter cycling period.

S7f). This further confirms that the individual S/C composite particles were strongly bound to the current collector. In summary, the low swelling capability of poly(AETMAC-coEGDA) ensures sufficient interactions between its ammonium cations and the polysulfide anions. This cross-linked polymer also conveys a higher tensile strength, stiffness, and toughness to the electrode, for increased tolerance to delamination, and favors electrode durability. To further correlate the electrochemical performance with the mechanical properties of the sulfur electrodes fabricated with these binders, electrochemical impedance spectroscopy (EIS) studies were performed during cycling (Figure S8). The interfacial resistance of both the PVDF- and poly(DADMACco-EGDA)-based electrodes increased during the first 50 cycles. This is in strong agreement with the SEM analysis (see surface topology in Figure 4 and cross-section in Figure S7), which suggests that the architecture of these electrodes slowly deteriorates as a result of their inferior physical properties (Figure 4b,c). In contrast, the EIS of the poly(AETMAC-co-EGDA)-based electrode (Figure S8c) remained largely unchanged. This indicates that although both poly(DADMAC-co-EGDA) and poly(AETMAC-co-EGDA) contain ammonium cation subunits that engage in chargetransfer interactions with the polysulfide anions,8,51 the latter polymer provides superior mechanical binding strength between the cathode components as well as with the current collector, preserving the electrode integrity during cycling. High-sulfur loading (∼6.0 mg cm−2) electrodes were fabricated using these binders as a further proof-of-concept. All of the cathodes were maintained at open circuit voltage for 4 h prior to cycling, to allow equilibrium swelling of the binder. Due to the electrode thickness, these cathodes were conditioned at a low current density of C/50 for one cycle (where all cathodes exhibit a similar initial discharge capacity between 800 and 1000 mA h g−1 or areal capacity between 4.5 22487

DOI: 10.1021/acsami.9b06456 ACS Appl. Mater. Interfaces 2019, 11, 22481−22491

Research Article

ACS Applied Materials & Interfaces

sulfur content of 75 wt %, as determined by thermogravimetric analysis (TGA). 4.4. Preparation of Li2Sn. In an Ar-filled glovebox, Li2S4 and Li2S6 were synthesized by allowing elemental sulfur (99.5%, SigmaAldrich) to react with lithium triethylborohydride (1 M, SigmaAldrich) in anhydrous tetrahydrofuran in the appropriate stoichiometric ratio. The resultant solution was vacuum-dried, followed by a final wash with toluene to isolate the powders. The lithium polysulfide powder was collected by vacuum drying in a Büchi vacuum oven at 60 °C for 6 h. 4.5. Preparation of the Li2S4−Homopolymer Mixture. All of the solid materials were vacuum-dried in a Büchi vacuum oven at 60 °C for 24 h prior to use. In an Ar-filled glovebox, 20 mg of homopolymer and 20 mg of Li2S4 were stirred in 2 mL of DME for 6 h. The material for FTIR analysis was collected by centrifugation (10k rpm, 10 min) followed by vacuum drying overnight at room temperature for 12 h. 4.6. Lithium Polysulfide Adsorptivity Measurement. The adsorptivity of lithium polysulfides onto the polymeric binders was determined by an electrochemical sulfur titration technique.54 In an Ar-filled glovebox, the binders and lithium polysulfide (Li2S4 or Li2S6) powders were stirred in DME at an concentration of 10 mg mL−1 for 18 h to allow saturation of the materials with Sn2−. The suspension was then centrifuged (10k rpm, 10 min) to remove the solid powders. The supernatant was collected and further diluted with 2 M LiTFSI in DME, utilizing a stainless steel current collector (type 316, 100 mesh, Alfa Aesar). The counter electrode compartment was filled with 1 M LiTFSI in DME and 2 wt % LiNO3. A porous glass frit was used to separate the two solutions in a two-electrode Swagelok cell. The oxidation potential of the sample solution was held at 3.0 V vs Li/Li+ to oxidize the excess lithium polysulfide to elemental sulfur, and the capacity was determined by integrating the time needed for the current to reach essentially zero. Lithium polysulfide solutions were also prepared in the absence of binders to establish a standard curve. 4.7. Tensile Tests. The P50 carbon paper samples with the composite material coated in the same manner as for electrode preparation were cut into 3″ × 1″ rectangular shapes and mounted via grip heads. Mechanical tests were carried out on a universal macrotribometer (UNMT-2MT, Centre for Tribology, Inc.) with a 10 kg load cell. The force and displacement were controlled by a step-motor at a pull rate of 0.01 mm s−1. 4.8. Physical Characterization. FTIR spectra were obtained on a Bruker Tensor 37 spectrometer. For polysulfide-contact experiments, the samples were mixed with KBr in an Ar-filled glovebox before transfer to a N2-filled chamber where the analysis was conducted. Lithium polysulfide adsorptivity was measured on a VMP3 multichannel potentiostat (Bio-logic) by chronoamperometry. SEM and EDAX elemental analysis studies were carried out on a Zeiss Ultra field emission SEM instrument equipped with an EDX attachment (Zeiss). TEM was performed on a ZEISS Libra 200 MC TEM instrument operating at 200 kV. The specific surface area and pore volume were measured using a Quantachrome Autosorb-1 system at 77 K. The specific surface area and pore size distribution were calculated by the Brunauer−Emmett−Teller method and the quenched solid density functional theory method, respectively. TGA, used to determine the sulfur content of the materials, was carried out on a TA Instruments SDT Q600 at a heating rate of 10 °C min−1 from room temperature to 800 °C under air flow. 4.9. Electrode Preparation. The electrodes were prepared from a water/dimethylformamide (6:4) slurry containing 80 wt % S-PHCS, 5 wt % Super P, 5 wt % 8 nm multiwall carbon nanotubes, and 10 wt % polymeric binder onto P50 carbon paper. Only dimethylformamide was used when PVDF is served as a binder. The sulfur loading on these electrodes was either 3.5 or 6.0 mg cm−2. The electrodes were dried in a 60 °C oven for 24 h before they were transferred to an Arfilled glovebox. Li−S coin cells (2325) were assembled with a lithium foil anode and an e lectrol yt e o f 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 2 wt % LiNO3 in a 1:1 v/v mixture of 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL) (BASF). The electrolyte/sulfur ratio was 7:1 (μL:mg) for the

3. CONCLUSIONS Our work demonstrates the importance of cross-linked polymeric binders that exhibit both strong chemisorption and robust mechanical properties, utilizing poly(AETMAC-coEGDA) as a model system, for the fabrication of stable and high loading sulfur cathodes. The combination of a 3D network in the cross-linked polymer and strong charge-transfer interactions between the quaternary ammonium group and polysulfide lead to a very significant improvement in the electrochemical performance compared with a simple linear polymer binder such as PVDF. The tighter polymer network, compared to poly(DADMAC-co-EGDA), which contains similar chemical functionality, reduces electrolyte swelling and increases the tensile strength, Young’s modulus, and toughness. These factors are all critical for delamination tolerance. Excellent capacity retention over 300 cycles for compact thick electrodes (6.0 mg cm−2) was exhibited in Li−S cells with a moderate electrolyte−sulfur ratio. Moreover, traditional slurry processes can be used to cast the cathode material onto the current collector, which fits industrial protocols. We believe that these findings will inspire the battery community to place more focus on utilizing highly functional binders to achieve high areal capacity Li−S cathodes, including solid-state Li−S batteries that equally suffer from volume expansion during cycling. 4. EXPERIMENTAL METHODS 4.1. Preparation of Poly(AETMAC-co-EGDA) Cross-Linked Polymer. Free-radical polymerization was employed to cross-link AETMAC and EGDA at 80 °C in dry ethanol. The molar ratio between the monomer and the cross-linker was maintained at 4:1. AETMAC (80 wt % in H2O, Sigma-Aldrich) containing 600 ppm monomethyl ether hydroquinone inhibitor was first passed through an inhibitor-remover column (Sigma-Aldrich) twice prior to use. Next, 804 mg of the purified AETMAC aqueous solution, 157 mg of EGDA (90% technical, Sigma-Aldrich), 39 mg of AIBN (99%, recrystallized, Sigma-Aldrich) and 4 g of dry ethanol (Fisher Scientific) were introduced into a 50 mL round-bottom flask. The flask was sealed with a rubber septum, and the mixture was stirred rapidly for 15 min. After a clear solution was obtained, the mixture was purged gently with dry nitrogen for an additional 10 min before placing the flask in an oil bath (80 °C) on a stir plate. The stirred reaction was terminated after 12 h, and the cross-linked polymer was recovered by precipitation in acetone (ACS, Sigma-Aldrich). Finally, the polymer was filtered and rinsed with cold isopropanol (anhydrous, SigmaAldrich) to remove any unreacted precursors. 4.2. Preparation of Poly(DADMAC-co-EGDA) Cross-Linked Polymer. The free-radical cross-linking polymerization between DADMAC and EGDA was achieved in a similar manner to the experimental procedure described above. However, the co-polymerization temperature for poly(DADMAC-co-EGDA) was set to 60 °C, and the molar ratio of monomer to cross-linker was 2:1. In a typical procedure, a mixture of 604 mg of DADMAC (97% AT, SigmaAldrich), 353 mg of EGDA, 44 mg of AIBN, and 4 g of anhydrous ethanol in a 50 mL round-bottom flask was used for the reaction. The flask was sealed with a rubber septum, and the mixture was stirred for at least 15 min to allow dissolution of the reactants; the solution was then purged gently with dry nitrogen for 10 min. The flask was placed in an oil bath (60 °C), and the mixture was stirred for 12 h, although the contents turned cloudy 10 min after the start of polymerization. Finally, the cross-linked polymer was filtered and rinsed with cold isopropanol to remove any unreacted precursors. 4.3. Preparation of the Porous Hollow Carbon Sphere (PHCS) Sulfur Host. The host material was synthesized, as previously reported.10 Elemental sulfur was melt-diffused into the PHCSs at 160 °C for 12 h to afford the S-PHCS composite, with a 22488

DOI: 10.1021/acsami.9b06456 ACS Appl. Mater. Interfaces 2019, 11, 22481−22491

Research Article

ACS Applied Materials & Interfaces

Temperature Sodium-Air and Sodium-Sulfur Batteries. Beilstein J. Nanotechnol. 2015, 6, 1016−1055. (3) Manthiram, A.; Fu, Y.; Chung, S.-H.; Zu, C.; Su, Y.-S. Rechargeable Lithium-Sulfur Batteries. Chem. Rev. 2014, 114, 11751−11797. (4) Evers, S.; Nazar, L. F. New Approaches for High Energy Density Lithium-Sulfur Battery Cathodes. Acc. Chem. Res. 2013, 46, 1135− 1143. (5) Lv, D.; Zheng, J.; Li, Q.; Xie, X.; Ferrara, S.; Nie, Z.; Mehdi, L. B.; Browning, N. D.; Zhang, J.-G.; Graff, G. L.; Liu, J.; Xiao, J. High Energy Density Lithium-Sulfur Batteries: Challenges of Thick Sulfur Cathodes. Adv. Energy Mater. 2015, 5, No. 1402290. (6) Pope, M. A.; Aksay, I. A. Structural Design of Cathodes for Li-S Batteries. Adv. Energy Mater. 2015, 5, No. 1500124. (7) Zhou, W.; Guo, B.; Gao, H.; Goodenough, J. B. Low-Cost Higher Loading of a Sulfur Cathode. Adv. Energy Mater. 2016, 6, No. 1502059. (8) Chen, H.; Ling, M.; Hencz, L.; Ling, H. Y.; Li, G.; Lin, Z.; Liu, G.; Zhang, S. Exploring Chemical, Mechanical, and Electrical Functionalities of Binders for Advanced Energy-Storage Devices. Chem. Rev. 2018, 118, 8936−8982. (9) Lee, J. T.; Zhao, Y.; Thieme, S.; Kim, H.; Oschatz, M.; Borchardt, L.; Magasinski, A.; Cho, W. I.; Kaskel, S.; Yushin, G. Sulfur-Infiltrated Micro- and Mesoporous Silicon Carbide-Derived Carbon Cathode for High-Performance Lithium Sulfur Batteries. Adv. Mater. 2013, 25, 4573−4579. (10) He, G.; Evers, S.; Liang, X.; Cuisinier, M.; Garsuch, A.; Nazar, L. F. Tailoring Porous in Carbon Nanospheres for Lithium-Sulfur Battery Cathode. ACS Nano 2013, 7, 10920−10930. (11) Zheng, J.; Tian, J.; Wu, D.; Gu, M.; Xu, W.; Wang, C.; Gao, F.; Engethard, M. H.; Zhang, J.-G.; Liu, J.; Xiao, J. Lewis Acid-Base Interactions between Polysulfides and Metal Organic Framework in Lithium Sulfur Batteries. Nano Lett. 2014, 14, 2345−2352. (12) Ahn, W.; Lim, S. N.; Lee, D. U.; Kim, K.-B.; Chen, Z.; Yeon, S.H. Interaction Mechanism between a Functionalized Protector Layer and Dissolved Polysulfide for Extended Cycle Life of Lithium Sulfur Batteries. J. Mater. Chem. A 2015, 3, 9461−9467. (13) Do, V.; Deepika; Kim, M. S.; Kim, M. S.; Lee, K. R.; Cho, W. I. Carbon Nitride Phosphorus as an Effective Lithium Polysulfide Adsorbent for Lithium-Sulfur Batteries. ACS Appl. Mater. Interfaces 2019, 11, 11431−11441. (14) Shyamsunder, A.; Beichel, W.; Klose, P.; Pang, Q.; Scherer, H.; Hoffmann, A.; Murphy, G. K.; Krossing, I.; Nazar, L. F. Inhibiting Polysulfide Shuttle in Lithium-Sulfur Batteries trough Low-IonPairing Salts and a Triflamide Solvent. Angew. Chem., Int. Ed. 2017, 56, 6192−6197. (15) Gordin, M. L.; Dai, F.; Chen, S.; Xu, T.; Song, J.; Tang, D.; Azimi, N.; Zang, Z.; Wang, D. Bis(2,2,2-trifluoroethyl) Ether as an Electrolyte Co-solvent for Mitigating Self-Discharge in Lithium-Sulfur Batteries. ACS Appl. Mater. Interfaces 2014, 6, 8006−8010. (16) Li, S.-Y.; Wang, W.-P.; Duan, H.; Guo, Y.-G. Recent Progress on Confinement of Polysulfides through Physical and Chemical Methods. J. Energy Chem. 2018, 27, 1555−1565. (17) Pang, Q.; Liang, X.; Kwok, C. Y.; Nazar, L. F. Advances in Lithium-Sulfur Batteries Based on Multifunctional Cathodes and Electrolytes. Nat. Energy 2016, 1, No. 16132. (18) Eroglu, D.; Zavadil, K. R.; Gallagher, K. G. Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery. J. Electrochem. Soc. 2015, 162, A982−A990. (19) Chung, S.-H.; Chang, C.-H.; Manthiram, A. A Carbon-Cotton Cathode with Ultrahigh-Loading Capability for Statically and Dynamically Stable Lithium-Sulfur Batteries. ACS Nano 2016, 10, 10462−10470. (20) Du, W.-C.; Yin, Y.-X.; Zeng, X.-X.; Shi, J.-L.; Zang, S.-F.; Wan, L.-J.; Guo, Y.-G. Wet Chemistry Synthesis of Multidimensional Nanocarbon-Sulfur Hybrid Materials with Ultrahigh Sulfur Loading for Lithium-Sulfur Batteries. ACS Appl. Mater. Interfaces 2016, 8, 3584−3590.

electrochemical studies. Cycling performance and rate capability studies were performed on a multi-channel Arbin instrument. Cyclic voltammetry and electrochemical impedance spectroscopy studies were recorded on a Bio-logic VMP3 electrochemical station with a scan rate of 0.1 mV s−1 and amplitude of 10 mV in the frequency range of 200 mHz to 500 kHz, respectively.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b06456. FTIR transmission spectra for the cross-linked polymers and the mechanical blends of their homopolymer; calibration plots for the polysulfide adsorptivity measurements; SEM and TEM images, TGA curves, N2 isotherm analysis results for the PHCSs and S-PHCSs; SEM images of the P50 current collector; elemental mapping of a cast sulfur cathode, cyclic voltammetry and Nyquist plots and cross-sectional SEM images for the three sulfur cathodes with the different binders (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (M.G.). *E-mail: [email protected] (L.F.N.). ORCID

C. Y. Kwok: 0000-0003-1007-8699 M. Gauthier: 0000-0001-9486-1810 Author Contributions

C.Y.K., L.F.N., and M.G. conceived the concept and designed experimental work. C.Y.K. and A.W. prepared and characterized the cross-linked polymers, and optimized the crosslinking density of the polyelectrolytes. C.Y.K. prepared the cathode materials, performed the physical characterization of the materials and electrodes as well all of the electrochemical studies, with assistance from Q.P., A.W., and X.L. All author thoroughly discussed the analysis of the data. C.Y.K., A.W., and L.F.N. wrote the manuscript with contributions from all of the authors. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy (DOE), Office of Science, Basic Energy Science. The authors thank Kelvin Liew and Prof. Boxin Zhao at the University of Waterloo for their generous help in performing the mechanical measurements on the electrodes. We thank Dr Shahrzad Hosseini Vajargah for the collection of the TEM images. This research was also partially supported by the Natural Sciences and Engineering Council of Canada (NSERC) through their Discovery and Canada Research Chair programs to L.F.N. and a doctoral scholarship (PGS-D) to C.Y.K.

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REFERENCES

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DOI: 10.1021/acsami.9b06456 ACS Appl. Mater. Interfaces 2019, 11, 22481−22491

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DOI: 10.1021/acsami.9b06456 ACS Appl. Mater. Interfaces 2019, 11, 22481−22491