Improving the Performance of LithiumâSulfur Batteries by Employing

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Improving the Performance of Lithium-Sulfur Batteries by Employing Polyimide particles as Hosting Matrixes Pei-Yang Gu, Yi Zhao, Jian Xie, Nursimaa Binte Ali, Lina Nie, Zhichuan J. Xu, and Qichun Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b01118 • Publication Date (Web): 29 Feb 2016 Downloaded from http://pubs.acs.org on March 2, 2016

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ACS Applied Materials & Interfaces

Improving the Performance of Lithium-Sulfur Batteries by Employing Polyimide Particles as Hosting Matrixes Pei-Yang Gu,1 Yi Zhao,1 Jian Xie,1 Nursimaa Binte Ali,1 Lina Nie,1 Zhichuan J. Xu,1* Qichun Zhang1,2* 1

School of Materials Science and Engineering, Nanyang Technological University, Singapore

639798, Singapore 2

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences,

Nanyang Technological University, Singapore 637371, Singapore *Correspondence to Q. Zhang/Z. Xu, e-mail: [email protected]; [email protected]

Abstract Sulfur cathodes with four polyimide (PI) compounds as hosting matrixes have been prepared through a simple one-step approach. These four PIs-S composites exhibited higher sulfur utilization and better cycling stability than pure sulfur. At a current rate of 300 mA g-1, the initial discharge capacities of PI-1S, PI-2S, PI-3S, and BBLS reached 1120, 1100, 1150, and 1040 mAh g-1, respectively. After the 30th cycle, PI-1S, PI-2S, PI-3S, BBLS and pristine sulfur powder still remained discharge capacities of 715, 673, 729, 643 and 550 mAh g-1. Especially, PI-1S and PI-3S cathodes exhibit excellent cycling stability with the discharge capacities of 522 and 574 mAh g-1 at the 450th cycle, respectively.

Keywords: Polyimide, lithium-sulfur batteries, long lifetime, poly(ethylene glycol), high specific capacity

Introduction Traditional rechargeable lithium-ion batteries based on lithium metal oxide cathodes and carbon anodes cannot meet the increasing demand of 21st century society due to the limit of theoretical specific energy.1-7 To achieve a higher specific energy, new electrode materials for both cathode and anode with high charge storage capacity are highly desirable.8-18 Among various kinds of

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cathodes, sulfur cathode is an exciting one due to its high theoretical capacity (~1673 mAh g-1), high energy density (~ 2600 Wh kg-1), element abundance, low cost, and low toxicity.19-27 However, lithium-sulfur batteries have not been commercialized yet due to their instable performance and short lifetime. These shortcomings are originated from the poor electrical conductivity of sulfur, the dissolution of intermediate lithium polysufides, as well as large volume expansion of sulfur (~80%) during discharge/charge process. Technically, low active-sulfur material utilization, low coulombic efficiency, poor rate capability, and rapid capacity decay are often observed in lithium-sulfur batteries. To overcome above problems, tremendous efforts have been devoted to designing new sulfur-based composites as cathodes in recent years.28-34 One of the most useful strategies is to use carbon nanostructures as the conductive matrix to encapsulate sulfur and trap polysulfides.35-40 Although some carbon-sulfur cathodes have already shown significant improvements on specific capacity and/or excellent cyclability up to hundreds of times, the fabrication of carbon nanostructures usually requires complicated and elaborate procedures including high-temperature process and corrosive acids for template removal. These harsh conditions have significantly limited the manufacturability of the sulfur cathode materials. Therefore, it is very urgent to develop novel alternatives, which are simple and scalable for the preparation of sulfur cathodes with high specific capacity and longer lifetime. Polyimides (PIs) can undergo charge and discharge processes by redox reactions and have excellent electrochemical performance as electrode materials in energy storage devices such as sodium-ion batteries and lithium-ion batteries.41-42 Moreover, PIs also have several other charming advantages including high thermal stability, excellent mechanical properties, and low cost.43-45 When PIs are employed for rechargeable lithium-sulfur batteries, they are expected to show better electrochemical properties due to the strong interaction between oxygens in the carboxylic groups of PIs and element sulfur during the heating treatment process, which can increase the utilization of element sulfur and may be beneficial for suppressing the shuttle effect.40 Furthermore, poly(ethylene glycol) (PEG) can be introduced into PIs for further performance enhancement of lithium-sulfur batteries because previous reports has already proven that the introduction of PEG could lead to better performance.46-49 As a result, PEG could minimize the dissolution and diffusion of polysulfides and accommodate volume expansion during discharge, therefore improving the cycling life of sulfur cathodes.


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Herein, four PI compounds with different conjugated degrees (named as BBL, PI-1 to PI-3 (Chart 1)) have been synthesized and used as the matrixes for sulfur. The detailed synthetic process can be found in the Supplementary Information (SI). Note that the sulfur cathode was fabricated through one-step simple approach. The electrochemical behaviors of four PI-S composites as well as pristine sulfur powder have been conducted via CR2025 coin-type test cells, which are assembled in an Ar-filled glove box.

Chart 1The Structures of PI-1, PI-2, PI-3 and BBL

Experimental Section Materials.

Naphthalene-1,4,5,8-tetracarboxylic

acid,

1,2,4,5-tetraaminobenzene

tetrahydrobromide, 1,2-bis(2-aminoethoxy)ethane, m-cresol, hydrazine monohydrate, isoquinoline, fuming nitric acid and 1-bromo-2-ethylhexaneare are commercially available. All chemicals and solvents were used directly without further purification. Instrumentation and Characterization. The electrochemical behaviors were investigated via CR2025 coin-type test cells, which are assembled in an Ar-filled golve box. The working electrode was consisted of 70 wt% active materials, 20 wt% conductivity agent (ketjen black, KB), and 10 wt% polymer binder (Clevios P solution, PEDOT: PSS). The electrolyte was 1 M LiTFSI in 1,2-dimethoxymethane/1,3-dioxolane (1:1 v/v) with 0.25 M LiNO3. A Celgard 2300 membrane was used as the separator. Lithium sheet was employed as both counter and reference electrode. The galvanostatic discharge-charge cycles were performed on a Neware Battery tester over a



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range of 1.9 V to 2.7 V at room temperature. The specific capacities mentioned in lithium sulfur batteries were calculated based on the mass of sulfur. The solid-state UV-Vis diffuse-reflectance spectrum was recorded at room temperature on powder samples with a Model UV-2501 PC. A BaSO4 plate was used as a standard (100% reflectance). The absorption data were calculated from the reflectance spectrum using the Kubelka–Munk function α/S = (1 − R)2/2R, where α is the absorption coefficient, S is the scattering coefficient and R is the reflectance.

Sulfur impregnation in these composites. In a typical fabrication, the as-prepared compounds (PI-1, PI-2, PI-3, and BBL) and commercial sulfur (a weight ratio of 1:2) were grounded into power and subsequently heated at 155 oC for 24 h under Ar atmosphere, the as-obtained composites were denoted as PI-1S, PI-2S, PI-3S, and BBLS.

Synthesis. Taking PI-1 as one example: naphthalene-1,4,5,8-tetracarboxylic acid (NTCDA, 268 mg, 1 mmol) and 1,2-bis(2-aminoethoxy)ethane (148 mg, 1 mmol) were added into a mixed solvent containing 20 mL m-cresol and 0.5 mL isoquinoline at room temperature. After stirring for 6 h, the mixture was heated to reflux under nitrogen for 12 h. After cooling to room temperature, the resulted mixture was poured into 1 M NaOH solution. The as-obtained participate was filtrated, washed repeatedly with water, NaOH solution (1M) and acetone, then, dried under vacuum at 150 o

C for 12 hours. PI-2 and PI-3 were prepared according to the similar procedure described for

PI-1.

Results and Discussion In order to meet the need of large-scale synthesis, PIs were prepared through a one-step polymerization route. Different diamines were chosen as the starting materials to understand the difference between rigid and flexible backbone and the effect from hydrophilic and hydrophobic backbones.

To

obtain

PI-2

and

PI-3,

2,7-diaminobenzo[lmn][3,8]phenanthroline-

1,3,6,8(2H,7H)-tetraone and 9,9-bis(2-ethylhexyl)-9H-fluorene-2,7-diamine dihydrochloride were prepared according to literatures.41,50-51 BBL was synthesized according to our previous report through one-pot polycondensation between naphthalene-1,4,5,8-tetracarboxylic acid and 1,2,4,5-tetraaminobenzene tetrahydrobromide.52 The synthetic route (Scheme S1) and the detailed


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synthetic process can be found in SI. PIs and BBL were characterized by Fourier transform infrared (FT-IR) spectroscope (Figure S2). Detailed characterization of BBL has been reported in our previous work.52 The FT-IR spectrum of PI-2 exhibits two absorption bands at 1704 and 1322 cm-1, which are associated with the vibrational modes of C=O and C-N in aromatic rings and in agreement with the previous report.42 The absorption spectra of PI-1 and PI-3 are different from that of PI-2, but they are similar to each other (1708 and 1662 cm-1 (C=O), 1337 cm-1 (C-N) for PI-1; 1721 and 1676 cm-1 (C=O), 1336 cm-1 (C-N) for PI-3), reflecting the similarity of their structures. As a result, almost all characteristic absorption bands of imide groups could be found in PIs, which confirms the completion of imidization and successful polymerization of the PIs. The SEM images in Figure S3 reveal that the morphologies are different between PIs and PIs-S as well as between PIs-S and pristine sulfur powder, indicating that PIs can be used as the host matrixes for sulfur because there is almost no bulky sulfur powder existing in matrixes (Figure S3b, 3d, 3e, 3h). The thermal properties of PI-1, PI-2, PI-3 and BBL were evaluated by thermogravimetric analysis (TGA) under nitrogen atmosphere. As shown in Figure 1, PI-1, PI-2, PI-3 and BBL exhibit very good thermal stability with onset decomposition temperatures at ~345, 340, 411 and 528 oC (considering the 5% weight loss temperature), respectively. The content of sulfur in the PIs-S and BBLS composites was determined by TGA. Seen from Figure 1, the weight loss before 310 oC can be considered from sulfur powder because it can completely sublimate at 310 oC. As a result, the contents of sulfur in the PIs-S and BBLS composite are 66 wt%, 63 wt%, 66 wt%, and 65 wt%.



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Figure 1 TGA curves of sulfur powder, (a) PI-1/PI-1S, (b) PI-2/PI-2S, (c) PI-3/PI-3S, and (d) BBL/BBLS with a heating rate of 10 oC min-1 under N2. The electrochemical behaviors of all samples were performed via CR2025 coin-type test cells assembled in an Ar-filled glove box. Figure 2a-2f show the discharge/charge profiles of the first, 5th, 10th, 20th and 30th cycles at 300 mA g-1. All voltage profiles exhibit two typical discharge plateaus, which correspond to the reduction from elemental sulfur to long-chain polysulfides (Li2Sx, 4 ≤ x ≤ 8) at 2.3 V and further reduction of long-chain polysulfides to short-chain Li2S2 and Li2S at 2.1 V. At a current rate of 300 mA g-1, the initial discharge capacities of PI-1S, PI-2S, PI-3S, and BBLS reached 1120, 1100, 1150, and 1040 mAh g-1, respectively, while pristine sulfur powder only displayed a low first discharge capacity of 914 mAh g-1. Note that the initial discharge capacity of PI-1 and PI-3 are 22% and 25%, which are higher than that of pristine sulfur powder. After the 30th cycle, PI-1S, PI-2S, PI-3S, BBLS and pristine sulfur powder remained discharge capacities of 715, 673, 729, 643 and 550 mAh g-1, respectively. The serious capacity fade in the initial 30 cycles is attributed to lose the active material with two reasons (the partial dissolution of the reaction products (Sx) into the liquid electrolytes and the irreversible reaction between sulfur and PIs). The 30th discharge capacities of PI-1 and PI-3 are still 30% and 32%,


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which are higher that of pristine sulfur powder. As shown in Figure 2f, the discharge capacities of PIs-S and BBLS still remained 654, 565, 651 and 572 mAh g-1 at a current rate of 300 mA g-1 after 150 cycles. In addition, PIs-S and BBLS show a coulombic efficiency close to 100%, which is attributed to the addition of LiNO3 to the electrolyte and satisfies the basic requirements for cathode materials.14,53-55 The discharge capacities of PIs-S and BBLS are always higher than that of pristine sulfur powder due to the strong interaction between oxygens in the carboxylic groups of PIs and element sulfur during the heating treatment process. The generated chemical bond could increase the utilization of element sulfur and is beneficial for suppressing the shuttle effect, resulting in the excellent performance of lithium-sulfur batteries.40 The solid-state UV-Vis spectra of PI-1 and PI-1S are shown in Figure 3a. PI-1 shows three absorption peaks (322, 542 and 707 nm). However, after heating with sulfur at 155oC for 24 h under Ar atmosphere, two longer peaks were blue-shifted to 493 and 609 nm, suggesting that there is a strong interaction between sulfur and

PI-1.

The

structure

of

2,7-bis(2-octyldodecyl)benzo[lmn][3,8]

phenanthroline-1,3,6,8(2H,7H)-tetraone (NDI20) is similar to PIs. However, since it is a small molecule, it might be much easier to interact with sulfur than polymers. Figure 3b displays that there are much different absorption spectra between NDI20 and NDI20S (NDI20 was heating with sulfur at 155oC for 24 h under Ar atmosphere). In addition, ethylene oxide segment was introduced into PI-1 that could minimize the dissolution and diffusing of polysulfides during discharge, therefore improving the cycling life of sulfur cathode. Furthermore, the performances of PI-1 and PI-3 are better than PI-2 and BBL probably because the flexible backbones of PI-1 and PI-3 are easier to interact with element sulfur than the rigid backbones. More importantly, PI-1S and PI-3S cathodes exhibit a prolonged cycling stability, with the discharge capacities of 522 and 574 mAh g-1 at a current rate of 300 mA g-1 at the 450th cycle and coulombic efficiency does not decrease (Figure 4a). Figure 4b and Figure 4d display the rate capability performance of these two cathodes from 0.8 to 3.0 A g-1. Even at a high rate of 3 A g-1, the PI-1S and PI-3S cathodes still remained high capacities of 470 and 480 mAh g-1, respectively. The discharge capacities of PIs-S and BBLS decrease steeply with the increasing discharge rate, and the discharge capacities of PIs-S and BBLS can return to increase when the current density is back to 0.8 A g-1, suggesting the excellent electrical contact between PIs and element sulfur.



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Figure 2 Discharge-charge profiles from 1st to 30th cycle at 300 mA g-1 between 1.9 and 2.7 V for (a) pristine S cathode, (b) PI-1S cathode, (c) PI-2S cathode, (d) PI-3S cathode, (e) BBLS cathode; and (f) cycle performance and coulombic efficiency for PIs-S and BBLS at 300 mA g-1.

Figure 3 (a) Solid-state absorption spectra of PI-1 and PI-1S; (b) solid-state absorption spectra of NDI20 and NDI20S.


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Figure 4 (a) The Prolonged cycle performances and coulombic efficiencies of lithium/sulfur batteries for PI-1 and PI-3 at 300 mA g-1; (b-e) Rate performances of lithium/sulfur batteries for PIs-S and BBLS from 0.8 A g-1 to 3 A g-1. Conclusions In summary, four polyimide (PI) compounds have been synthesized and have been combined with sulfur for high performance lithium-sulfur batteries. Compared with pristine sulfur, these four PIs-S composites exhibited higher sulfur utilization and better cycling stability. Especially, PI-1 and PI-3 cathodes exhibit the excellent prolonged cycling stability, with the discharge capacities of 522 and 574 mAh g-1 at a current rate of 300 mA g-1 at the 450th cycle. The high-performance of organic lithium-sulfur batteries with polyimides as active elements could be ascribed to the formation of chemical bonds between polymers and sulfur during the heating treatment process,



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which plays a key role in enhancing the utilization of element sulfur and could be beneficial for suppressing the shuttle effect.

ASSOCIATED CONTENT Supporting Information. Synthesis,

1

HNMR spectrum, FT-IR spectra, SEM images, and Cycle performance and

coulombic efficiency of lithium-sulfur batteries

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected]. *E-mail: [email protected].

Author Contributions P.-Y Gu and Y. Zhao contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the ﬁnal version of the manuscript.

Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS Q.Z. acknowledges financial support from AcRF Tier 1 (RG133/14 and RG 13/15) and Tier 2 (ARC 2/13) from MOE, and the CREATE program (Nanomaterials for Energy and Water Management) from NRF, Singapore. Q.Z. also thanks the support from Open Project of State Key Laboratory of Supramolecular Structure and Materials (Grant number: sklssm20163), Jilin University, China.

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Improving the Performance of LithiumâSulfur Batteries by Employing

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