sulfur batteries

sulfur batteries

Solid State Sciences 95 (2019) 105924 Contents lists available at ScienceDirect Solid State Sciences journal homepage: www.elsevier.com/locate/sssci...

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Solid State Sciences 95 (2019) 105924

Contents lists available at ScienceDirect

Solid State Sciences journal homepage: www.elsevier.com/locate/ssscie

ZnO/carbon nanotube/reduced graphene oxide composite film as an effective interlayer for lithium/sulfur batteries

T

Zhenghao Suna, Yaping Guoa, Baoe Lia,∗∗, Taizhe Tanb, Yan Zhaoa,∗ a b

School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, China Synergy Innovation Institute of GDUT, Heyuan, Guangdong Province, China

A R T I C LE I N FO

A B S T R A C T

Keywords: Lithium/sulfur batteries ZnO/carbon nanotube/reduced graphene oxide (ZnO/CNT/RGO) composite Interlayer Electrochemical performance

The application of lithium/sulfur (Li/S) batteries is negatively affected by the insulation of sulfur and large volumetric change during the cycles as well as the polysulfides dissolution. To solve the above problems, we fabricated a composite interlayer for Li/S batteries using ZnO nanocrystals anchored on connected carbon nanotube and graphene. The preparation of ZnO/carbon nanotube/reduced graphene oxide (ZnO/CNT/RGO) composite film was inspired from the combination of a one-step sol-gel synthetic technique and vacuum-assisted filtration. The ZnO/CNT/RGO interlayer showed effective adsorption of polysulfides during diffusion experiments. This ZnO/CNT/RGO interlayer can efficiently increase sulfur utilization by immobilizing soluble intermediate polysulfides. When used as a composite interlayer in Li/S batteries, an impressive high capacity of 768 mAh g−1 at 0.2C was achieved after 150 cycles and improved rate performance of 597 mAh g−1 at 2C was obtained. This study offers a facile method to improve the electrochemical performance of the Li/S batteries.

1. Introduction With the rapid development of energy systems, high-capacity sustainable batteries are becoming in high demand. Lithium/sulfur (Li/S) batteries have become popular in the energy storage field because of their high theoretical energy density equal to ∼2600 Wh kg−1, environmental benignity of sulfur, low cost, and natural abundance [1]. However, several disadvantages limit their commercial applications. Low electronic conductivity of sulfur and the discharge products can cause low active material utilization [2,3]. A more serious issue is associated with spontaneous formation of polysulfides (Li2Sx, 4 ≤ x ≤ 8) as discharge by-products and their diffusion into the electrolytes [4]. These polysulfides could dissolve through the separator and finally deposit on the surface of the Li metal anode, causing the low sulfur utilization, rapid capacity fading and low coulombic efficiency [5,6]. To overcome this problem, researchers typically use various cathode materials such as conductive polymers, carbon-based materials and metal oxides [7]. However, a complicated process and strict control of reaction conditions are usually necessary to synthesize the above sulfur based composite cathodes [8]. Another increasingly popular strategy is applying an interlayer to place between the separator and the sulfur cathode [9]. Such functional interlayer barrier restrains polysulfides migration to the Li anode as well as works as the upper-current ∗

collector, improving overall utilization of sulfur [10]. Different kind of carbon materials have been widely applied in functional interlayers using vacuum filtration [11]. For example, reduced graphene oxide and carbon nanotubes can form a highly conductive, free-standing interlayer by vacuum filtration [12,13]. Such carbon-based interlayers can inhibit polysulfides diffusion and improved electrochemical performances of Li/S batteries [14]. Although a substantial progress has been made, the physical barrier made from carbon materials with weak adsorption ability to polysulfides cannot totally alleviate the shuttle effect of dissolved polysulfides [15]. With this concern, previous studies have also used metal oxides as sulfur hosts to chemically bind polysulfides, such as TiO2, MnO2 and V2O5 [16–19]. Among all possible candidates, ZnO has advantages of environmental friendliness, nature abundant, and polar nature, which have used as sulfur immobilizer for Li/S batteries [20]. One example of ZnO application in the interlayer for Li/S batteries is done by Yu et al. [21]. They designed an interlayer composed of reduced graphene oxide (RGO) with ALD-deposited ZnO acting as a barrier inhibiting polysulfides diffusion. Inspired by this strategy, we propose the fabrication of free-standing ZnO/carbon nanotube/reduced graphene oxide (ZnO/CNT/RGO) composite film acting as a conductive interlayer for Li/S batteries. The ZnO nanocrystals were homogeneously anchored on the CNT/RGO

Corresponding author. Corresponding author. E-mail addresses: [email protected] (B. Li), [email protected] (Y. Zhao).

∗∗

https://doi.org/10.1016/j.solidstatesciences.2019.06.013 Received 2 March 2019; Received in revised form 27 May 2019; Accepted 28 June 2019 Available online 29 June 2019 1293-2558/ © 2019 Elsevier Masson SAS. All rights reserved.

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Fig. 1. Schematic of the ZnO/CNT/RGO interlayer preparation.

2.3. Cell assembly and electrochemical characterization

matrix via sol-gel method, and the resulting composite was vacuumfiltered to form a free-standing thin film as an efficient interlayer for Li/ S batteries. As expected, this interlayer could enable improving the electrical conductivity and alleviating the shuttle effect, leading to the much-improved electrochemical performance.

The sulfur cathode composite S/RGO was prepared by previous reports [22]. Mixture containing 80 wt% of S/RGO composite, 10 wt% of ketjen black (purchased from Shanghai Huzheng Nano Technology Co.) and 10 wt% of polyvinylidene fluoride (PVDF) binder (99.9%, purchased from Aladdin Co., China) was added to N-methylpyrrolidinone. Formed slurry was coated on Al foils and dried at 60 °C in vacuum for 12 h. The sulfur cathode was punched into circular disks with a diameter of 12 mm and the sulfur loading at 1.7 mg cm−2. The high sulfur loading S/RGO electrode was controlled at 4.3 mg cm−2 by adjusting the coating thickness. We used 1 mol/L of lithium bis(tri-fluoromethanesulfonyl)imide (LiTFSI, purchased from Sigma Aldrich) dissolved in dimethoxy ethane and 1,3-dioxolane with 1:1 vol ratio as electrolyte. For each electrode, around 45 and 40 μL electrolyte (the ES ratio was 20:1) was added in the Li/S batteries with and without ZnO/CNT/RGO interlayer, respectively. Coin cells (CR2025) were assembled in Ar-filled glove box (Mbraun, Unilab, Germany) with S/RGO composite cathode, the ZnO/ CNT/RGO films, Celgard 2400 separator and metallic Li foil as an anode. Properties of the prepared S/RGO composites were consistent with Galvanostatic charge/discharge measurements were performed at room temperature using multichannel battery tester (BTS-5V5mA, Neware) in the 1.5–3.0 V range (vs Li+/Li electrode).

2. Experimental 2.1. ZnO/CNT/RGO composite interlayer fabrication Fabrication procedure of the ZnO/CNT/RGO composite interlayer was shown in Fig. 1. First, 2 g of zinc acetate (Zn(CH3COO)2, ≥99%, Sigma-Aldrich) was dissolved in 130 mL of ethanol. Then 0.7 g of 7 wt% CNT dispersion (from Nanjing Xianfeng) and 10 g of 0.5 wt% of RGO aqueous suspension (purchased from Chengdu Organic Chemicals) were added under constant stirring. Subsequently, 60 mL of ethanol solution containing 1.5 g of KOH (≥95%, Sigma-Aldrich) was injected. The mixture was stirred for 24 h at 40 °C. ZnO/CNT/RGO films were fabricated using vacuum filtration of the hybrid dispersion using a 100 nm filter (in diameter). The flexible films became detached after vacuum drying for 12 h at 60 °C. The mass loading of ZnO/CNT/RGO composite interlayer with a typical density of 0.85 mg cm−2 with a diameter of 19 mm. Consequently, the weight of the ZnO/CNT/RGO composite interlayer was 2.4 mg.

3. Results and discussion 2.2. Material characterization Crystal structures of pure ZnO and ZnO/CNT/RGO composites were investigated by XRD analysis and their corresponding XRD peaks are shown in Fig. 2a. Peaks corresponding to the (100), (002), (101), (102), (110), (103), (200), (112), (201) and (202) planes of hexagonal ZnO dominate in both XRD spectra. Lattice parameters determined from these peaks are a = 0.3257 nm and c = 0.52156 nm (using JCPDS card No. 36-1451) [23]. The broad peak observed at 2θ∼25° corresponds to the carbon from the ZnO/CNT/RGO composite [24]. Thus, the composite consisted of carbon and well crystallized ZnO. Peaks corresponding to the (200), (112) and (201) planes of ZnO in the XRD pattern of the ZnO/CNT/RGO composite were obscured by the overlapping

Crystal structures were analyzed by X-ray powder diffraction (XRD) performed using Rigaku Ultima IV diffractometer with Cu-Ka radiation. Thermal gravimetric analysis (TGA, Henven HTG-1) was performed in flowing air at 10° min−1 heating rate. The N2 adsorption/desorption tests were analyzed by Brunauer-Emmett-Teller (BET, Gold APP V-Sorb 2800P). Sample morphologies were examined using scanning electron microscopy (SEM, Hitachi S–3400 N) and a transmission electron microscopy (TEM, JEOL JEM-2010). Surface compositions were analyzed by X-ray photoelectron spectroscopy (XPS) using Thermo Scientific KAlpha XPS spectrometer. 2

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Fig. 2. (a) XRD analysis of pure ZnO and ZnO/CNT/RGO composites. (b) TGA curve of the ZnO/CNT/RGO composite in air.

peaks of CNT and RGO. To determine ZnO content in the ZnO/CNT/ RGO composite, we performed TGA analysis (see Fig. 2b). Weight loss in the 25–100 °C range is attributed to the water loss. Carbon started decomposing at ∼150 °C completely disappearing at ∼755 °C. When the temperature is further increased to 755 °C, the loss of weight is negligible due to the total loss of carbon material in the ZnO/CNT/RGO composite. The remaining weight was attributed to ZnO in the ZnO/ CNT/RGO and it accounted for 68.4% of the total initial weight. A large amount of ZnO can improve the ion transport efficiency and adsorb polysulfides, and the carbon material improves the conductivity of the film [25]. The specific surface area and pore size distribution of ZnO/CNT/ RGO composite were evaluated based on nitrogen absorption-desorption experiment and using the BET isotherm method. The specific surface area of ZnO/CNT/RGO composite is about 94.8 m2 g−1, the corresponding adsorption-desorption curve is shown in Fig. 3a. The Barret-Joyner-Halenda (BJH) desorption pore size distribution was given in Fig. 3b. ZnO/CNT/RGO composite exhibited a micropores and macropores structures which facilitate the adsorption of sulfur and polysulfides in the electrolyte [26]. Morphology and crystalline structure of the ZnO/CNT/RGO composite were analyzed by SEM and TEM. Fig. 4a shows SEM image of the ZnO/CNT/RGO composite. Numerous CNTs attached to the graphene surface can be clearly seen. These CNTs formed a three-dimensional network. ZnO nanoparticles were closely anchored on the surfaces of both graphene and CNTs. ZnO/CNT/RGO as interlayer in Li/S batteries can maintain good cycling stability of a battery because of its good mechanical strength and flexibility (see insert in Fig. 4a). Fig. 4b shows TEM image of the ZnO/CNT/RGO composite. ZnO nanoparticles 50–100 nm in size look homogeneously anchored to the RGO and CNT. Using high resolution transmission electron microscope (HRTEM), the lattice fringe scan be clearly seen, and the corresponding distances

Fig. 4. (a) SEM image of the ZnO/CNT/RGO composite. Insert shows a photograph of the ZnO/CNT/RGO composite film. (b) TEM and (c) HRTEM images as well as (d) SAED patterns of the ZnO/CNT/RGO composite.

are ∼ 0.262 and 0.512 nm (see Fig. 4c). These spacings agree well with the interplanar distances for (102) and (105) planes of ZnO [27]. The lattice fringes (shown in Fig. 4d) with 0.178, 0.192, 0.202, 0.262, 0.308,0.339 and 0.355 nm spacings correspond to (100), (002), (101), (102), (110), (103) and (200) planes of ZnO, respectively. The SAED pattern in Fig. 4d demonstrates polycrystalline ZnO with homogeneous diffraction rings, confirming presence of ZnO nanocrystals in the ZnO/ CNT/RGO composite. The XPS spectra of the ZnO/CNT/RGO composite interlayer after

Fig. 3. (a) N2 adsorption-desorption isotherm loops of ZnO/CNT/RGO composites. (b) Pore size distributions of ZnO/CNT/RGO composites. 3

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Fig. 5. XPS analysis of the ZnO/CNT/RGO composite interlayer after cycling.

Fig. 7a shows first three charge/discharge 0.2C cycles of Li/S battery with ZnO/CNT/RGO composite interlayer. Two typical potential platforms ascribed to the two stages of sulfur electrochemical redox reaction can be observed. The first discharge plateau at ∼2.3 V is related to the formation of soluble lithium polysulfides (Li2Sx, x ≥ 4) [31]. The second plateau at ∼2.1 V is associated with the further reduction of high-order polysulfides to Li2S2 and Li2S [32]. Such stable discharge platform indicated that Li/S batteries equipped with ZnO/CNT/RGO composite interlayer had a smooth discharge process with higher initial discharge capacity. The advantage of the ZnO/CNT/RGO composite interlayer for Li/S batteries was further demonstrated during the cycling performance of the cells at 0.2C (see Fig. 7b). Li/S batteries with ZnO/CNT/RGO composite interlayer delivered initial discharge capacity equal to 1061 mAh g−1. After 150 cycles, discharge capacity of this battery dropped to 768 mAh g−1. However, Li/S batteries without interlayer only delivered 981 mAh g−1 of the initial discharge capacity, and after 150 cycles capacity dropped to 608 mAh g−1. Thus, our ZnO/CNT/RGO composite interlayer absorbed polysulfides and inhibited reactions between polysulfides and lithium metal. Reversible capacities of Li/S batteries with ZnO/CNT/RGO composite interlayer equal to 938, 840, 723 and 597 mAh g−1 were achieved at 0.2, 0.5, 1 and 2C, respectively (Fig. 7c). The cells were able to recover to the 903 mAh g−1 after returning to 0.2C cycling demonstrating excellent reversibility. However, at 2C current density, conventional Li/S battery could only provide a discharge capacity equal to 403 mAh g−1. These results demonstrate that the ZnO/CNT/RGO composite interlayer was immobilizing polysulfides during the cycling, deactivating dissolved polysulfides [33]. We

100 cycles were shown in Fig. 5. C1s spectrum of ZnO/CNT/RGO composite (shown in Fig. 5a) displays different peaks. C–S peak at the 285.9 eV demonstrates that sulfur and polysulfides are blocked in the ZnO/CNT/RGO composite interlayer [28]. Deconvoluted XPS spectrum of the S2p peak (shown in Fig. 5b) shows distinguishable peaks and corresponding to the different chemical environment of sulfur atoms bonded to ZnO/CNT/RGO composite interlayer. Thus, certain chemical bonds formed between S and ZnO/CNT/RGO composite interlayer after cycling. XPS results demonstrated S–C bonds and Zn–S bonds; thus, we believe that the ZnO/CNT/RGO composite interlayer can effectively immobilize polysulfides by chemically binding with them [29]. To demonstrate that ZnO/CNT/RGO composite interlayer can effectively inhibit polysulfides diffusion, we photographed the polysulfides diffusion evolution in H-shaped test tubes during diffusion experiment (see Fig. 6). Commercial separator and ZnO/CNT/RGO composite interlayer were placed into H-shaped glass tubes. Right and left sides of the H-shaped glass tubes were filled with Li2S6 solution in tetrahydrofuran (THF) and pure THF, respectively [30]. Because of the concentration gradient, Li2S6 diffused through the separator from the left side to the right side, causing a color change (see Fig. 6a). In comparison, the H-shaped glass tubes were equipped with ZnO/CNT/ RGO composite interlayer, in Fig. 6b. After 8 h, the color change of the THF solution on the right side was slight, indicating that almost no Li2S6 passed through the ZnO/CNT/RGO composite interlayer. Benefiting from the adsorption of polysulfides by ZnO/CNT/RGO composite interlayer, Li/S batteries can exhibit excellent cycle performance. To further clarify effect of ZnO/CNT/RGO composite interlayer on the battery performance, various electrochemical tests were conducted.

Fig. 6. Photographs of the polysulfides diffusion process conducted in H-shaped test tubes (a) with and (b) without ZnO/CNT/RGO composite interlayer. 4

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Fig. 7. (a) Charge and discharge curves of the Li/S batteries with the ZnO/CNT/RGO composite interlayer at 0.2C. (b) Cycling performance of the Li/S batteries at 0.2C rate with and without the ZnO/ CNT/RGO composite interlayer. (c) Rate capability of the Li/S batteries with and without the ZnO/CNT/ RGO composite interlayer at different current densities. (d) Cycling performance of the Li/S batteries at 0.2C rate with a high sulfur loading.

advantages of the ZnO/CNT/RGO composite interlayer under high sulfur loading, the cycling performance with a high sulfur loading of 4.3 mg cm−2 were measured at 0.2C. As shown in Fig. 7d, the Li/S batteries with ZnO/CNT/RGO composite interlayer exhibited a high initial discharge capacity of 901 mAh g−1 and remained at 719 mAh g−1 after 50 cycles, with a high initial areal capacity 3.9 mAh cm−2. The Li/S batteries with the ZnO/CNT/RGO composite interlayer with such high areal capacity improve the practical application of Li/S batteries. In order to further prove that the ZnO/CNT/RGO composite interlayer can effectively capture polysulfides, SEM and elemental mapping images of the ZnO/CNT/RGO composite interlayer after cycling were shown in Fig. 8. Compared to the microstructure image of the ZnO/ CNT/RGO composite interlayer before cycling (Fig. 8a), the ZnO/CNT/ RGO composite interlayer after cycling (Fig. 8c) covered with redistributed sulfur or polysulfides. The effective inhibition of the polysulfides is further confirmed by the elemental mapping. As shown in Fig. 8b, the interlayer before cycling exhibits a few sulfur element distributions due to the signal noise. However, a significant elemental distribution of sulfur was shown in the ZnO/CNT/RGO composite interlayer after cycling (Fig. 8d), which suggests that the interlayer can effective block the migration of polysulfides. In order to verify the function of ZnO/CNT/RGO composite interlayer on suppress the growth of Li dendrites, Li–Li symmetrical batteries were assembly and measured at an ultrahigh current density of

Fig. 8. SEM image of ZnO/CNT/RGO composite interlayer (a) before and (c) after cycling. EDX mapping of Zn, O, C and S elemental distributions in the ZnO/CNT/RGO composite interlayer (b) before and (d) after cycling.

also believe that ZnO/CNT/RGO composite interlayer could work as an upper current collector and reduce the charge-transfer resistance improving rate capability of the Li/S batteries. In order to verify the

Fig. 9. Voltage-time curves of Li–Li symmetric batteries with and without ZnO/CNT/RGO composite interlayer at a current density of 5 mA cm−2. 5

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Table 1 Comparison of the electrochemical performance of previous reports with our work. Sample

Sulfur loading (content or areal loading)

Initial capacity (mAh g−1, at n C)

Final capacity (mAh g−1) (after cycles)

High Rate performance (mAh g−1, at n C)

Ref.

RGO/AC interlayer PP/GO/Nafion ternary separator PrNPs Carbon layer-coated separator GO/CNT films ZnO/CNT/RGO interlayer

58.2% 1.2 mg cm−2

1078 mAh g−1 (0.1C) 1090 mAh g−1 (0.1C)

655 mAh g−1 (100 th) Not mentioned

348 mAh g−1 (1.5C) 667 mAh g−1 (2C)

[36] [37]

70%, 1.1 mg cm−2 60%, 1.6 mg cm−2 1.0 mg cm−2 68.3%, 1.7 mg cm−2

986 mAh g−1 (0.2C) 1090 mAh g−1 (0.5C) 1370 mAh g−1 (0.2C) 1061 mAh g−1 (0.2C)

695 mAh 778 mAh 787 mAh 768 mAh

5 mA cm−2. As shown in Fig. 9, in the Li–Li symmetrical batteries with the ZnO/CNT/RGO composite interlayer, Li stripping and plating exhibits a low and stable over potential of less than 0.2 V for over 200 h, indicating a uniform Li deposition and a stable SEI layer. In comparison, the Li–Li symmetrical batteries without ZnO/CNT/RGO composite interlayer exhibits an over potential increases from 0.35 V to 0.6 V which suggests the uncontrollable Li dendrite growth and the damage of SEI layer [34,35]. To compare the electrochemical performance of these interlayers or modified separators, further comparison among these Li/S batteries are carried out as shown in Table .1 [36–40]. It is significant note that the cycling performance of the Li/S batteries with ZnO/CNT/RGO composite interlayer exhibits a good cycle performance and rate capability.

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[8]

4. Conclusions We report a ZnO/CNT/RGO film prepared by sol-gel technique and vacuum filtration to realize the physical blocking and chemical trapping dual function of polysulfides in Li/S batteries. The ZnO nanocrystals uniformly anchored on the RGO achieve effective adsorption of polysulfides, and the interwoven CNT network improves the mechanical strength and the conductivity of ZnO/CNT/RGO film. Furthermore, the embedded ZnO/CNT/RGO film acts as a conductive upper current collector, which reduces the polarization of the Li/S batteries, increases the discharge specific capacity and achieve a stable and reversible electrochemical process. Li/S batteries with ZnO/CNT/RGO interlayer had high initial discharge capacity of 1061 mAh g−1 and a reversible capacity of 768 mAh g−1, which retained after 150 cycles at a rate of 0.2C. Meanwhile, Li/S batteries with ZnO/CNT/RGO interlayer show a high specific capacity of 597 mAh g−1 at 2C rate. Thus, we combined benefits of both ZnO and carbon materials and prepared composite film to improve electrochemical performance of Li/S batteries. The Li/S batteries with ZnO/RGO/CNT interlayer deliver a high initial areal capacity of 3.9 mAh cm−2, improving the potential of practical applications. This simple method can help to further promote development of the Li/S batteries technology.

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Acknowledgements

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The authors gratefully acknowledge the support by the Natural Science Foundation of Hebei Province of China (Project No. E2017202032); Technology Foundation for returned overseas Chinese scholars (No.C2015003038); the Program for the Outstanding Young Talents of Hebei Province; Cultivation Project of National Engineering Technology Center [Grant No. 2017B090903008].

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