Multifunctional Ion-Sieve Constructed by 2D Materials as an Interlayer

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A Multi-Functional Ion-Sieve Constructed by 2D Materials as Interlayer for Li-S Batteries Ding-Rong Deng, Chengdong Bai, Fei Xue, Jie Lei, Pan Xu, MingSen Zheng, and Quanfeng Dong ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b22660 • Publication Date (Web): 06 Mar 2019 Downloaded from http://pubs.acs.org on March 6, 2019

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ACS Applied Materials & Interfaces

A Multi-Functional Ion-Sieve Constructed by 2D Materials as Interlayer for Li-S Batteries Ding-Rong Deng§,†, Cheng-Dong Bai§,‡, Fei Xue‡, Jie Lei‡, Pan Xu‡, Ming-Sen Zheng*,‡ and Quan-Feng Dong‡

†College

of Mechanical and Energy Engineering, Jimei University, Xiamen, Fujian, 361005,

China ‡State

Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry,

College of Chemistry and Chemical Engineering, iChem (Collaborative Innovation Center of Chemistry for Energy Materials) Xiamen, Fujian, 361005, China

KEYWORDS : 2D materials, multi-functional ion-sieve, Li-S battery, high performance, interlayer

ACS Paragon Plus Environment

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ABSTRACT For Li-S batteries, interlayer between the separator and sulfur cathode to prevent lithium polysulfides travel across the membrane is a research hotspot. The good blocking ability for LiPSs lead these interlayers can promote the electrochemistry performance with high S loading. However, most of these interlayers are just used as a simple blocking wall. Such a blocking wall, e.g. the lower Li+ ion conductivity, would often reduce the electrochemical performance especially under large current density. Here, we report a multi-functional ion-sieve made by three 2D sheets, g-C3N4, BN and graphene. A g-C3N4 which possesses orderly channels with a size of 3 Å in the crystalline structure can effectively prevent polysulfides from passing through, but allow lithium ions to pass freely; while the BN sheets acts with exellent catalysis for sulfur redox and graphene plays as an extended collector which can promote the conductivity of the sulfur electrode region. Benefiting from the synergistic effect among these 2D materials, the ionsieve interlayer makes the Li-S battery an excellence performance at a large rate with both high sulfur-loadings and high sulfur content. And the host materials is not necessary in these cells. It liberated a discharge capacity about 600 mAh g-1 after 500 cycles at 1 C, and the capacity attenuation was less than 0.01% per cycle with a 6 mg cm-2 areal S-loading (pure S as the active material). The reversible capacity could keep more than 400 mAh g-1 at 2 C which is amount to an area current density of 26.88 mA cm-2.


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1. INTRODUCTION In batteries, interlayer or membrane has always been regarded as a component of seperating anode and cathode without any other functions. Actually, it is of great significance to develop membranes with complexity and versatile functions in battreies. Two-dimensional (2D) materials, attribute to their tunable optical, electronic and chemical properties, have attracted increasing research interest. These materials can offer a wide range of basic building blocks for complex composites with designed functional.1-5 For the last few years, many researches have been embarking on two-dimensional graphitic material such as graphene, graphitic carbon nitride (gC3N4) and hexagonal boron nitride (h-BN). The unique hexatomic ring molecular structure and 2D nano structure enable them to possess many advantages such as appealing electronic structure and good physicochemical stability which make a promising candidate for the field of electrochemical energy storage.6-13 Lithium-sulfur batteries are the most promising future energy storage system attribute to its extremely high theoretical capacity (1675 mAh g-1), environmental friendliness and low cost. However, because of the “shuttle effect” in the electrochemistry process and the poor conductivity of S which lead to a poor rate capability, terrible cycling stability and low utilization of S; lithium-sulfur batteries have not yet been applied after years of research.14-18 To solve the above-mentioned problems, many researches have been embarking on using other materials to composite with sulfur. The variety of matrix can improve the electroconductibility, reduced the volume expansion or adsorb the soluble lithium polysulfides during the dischrage and charge process of Li-S battery.19-32 Another way to deal with shuttle is to use an interlayer between the sulfur cathode and separator. The basic idea of this approach is to prevent from passing of polysulfides by steric hindrance.33-47 A variety of materials have been tried to use as


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the interlayer for lithium-sulfur battery including 2D graphitic material like graphene or boron nitride.39,40,42,43 Because of the good blocking ability for LiPSs, some of these interlayers could be used in the lithium-sulfur battery with high S loading.41-44 However, most of these interlayers is just acted as a simple blocking wall. Such a blocking wall, e.g. the lower Li+ ion conductivity, would often reduce the electrochemical performance especially under large current density. And the single barrier function actually increases the amounts of inactive material. It is ideal situation to design and build an interlayer with multi-functional where can not only polysulfide be blocked but also Li+ ion can travel freely and, the S redox reaction will be promoted simultaneously.

Scheme 1. The scheme of the multi-functional ion-sieve constructed by three 2D materials (gC3N4, BN and graphene).

Herein, we have thus proposed a conception first, a multi-functional ion-sieve, concieved in effectively polysulfides bloked, fast Li+ migrating, and catalysis for S conversion. The multifunctional ion-sieve has been synthesized by three 2D graphitic material (g-C3N4, BN and graphene), where the g-C3N4 sheet and graphene sheet overlap into a sandwich structure and the


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BN flake are embedded vertically between them (Scheme 1). The g-C3N4 with a graphene-like structure, and at the molecular structure there are many highly ordered micropores with a small diameter about 3 Å, which is significantly smaller than the size of the soluble LiPSs but much larger than the diameters of Li-ion. It provided a space steric effect to prevent polysulfide travel across the membrane, but allow lithium ions to pass freely. The BN sheets acts an exellent catalysis for sulfur redox and graphene plays as an extended collector which can promote the conductivity of the sulfur electrode region. Benefiting from the synergistic effect among these 2D materials, the multi-functional ion-sieve shows a high conductivity for lithium-ions, excellent blocking ability for polysulfides and outstanding catalysis for S conversion reactions which lead to a preeminent performance for Li-S battery at a large current density with high S-loading. The cell could deliver a discharge capacity about 410 mAh g-1 under a rate of 2 C with an S-loading of 6 mg cm-2 (pure S as the active material without host materials). And the cell also showed a outstanding cycling stability at layer rate, after 500 cycles the specific capacity is about 600 mAh g-1 at 1 C, and the capacity attenuation was less than 0.01% per cycle. 2. RESULTS AND DISCUSSION g-C3N4 is a polymer consisted of many C3N4 monomers. Figure 1a is schematic diagram of the molecular structure of g-C3N4. The trilateral (C3N4)2 monomers constructed a 2D structure which has highly ordered channels with a diameter about 3 Å. The channel at this diameter is much smaller than the size of the soluble LiPSs, but is big enough for the shuttle of Li-ion. This illustrates that the g-C3N4 has a selectively penetrate for lithium ions, it can used as a so-called “ion-sieve” for Li-S batteries which lead to an excellent blocking ability for polysulfides and it does not affect the normal operation of the battery.


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Figure 1. (a) An illustration of microporous crystalline structures of g-C3N4. (b) XRD patterns of g-C3N4. (c) Pore-size distribution and BET specific surface area of g-C3N4. (d, e) SEM and TEM images of g-C3N4. (f, g) SEM images of g-C3N4 layer.

X-Ray Diffraction (XRD) was used to analyze the pattern of the as-prepared g-C3N4 sample as shown in Figure 1b. The diffraction peaks were all correspondence with the standard g-C3N4 crystal (JCPDS No. 87-1526) which illustrated a high purity of the sample. The N2 adsorptiondesorption isotherms (Figure 1c) shows the specific surface area of the g-C3N4 was 167.52 m2 g-1, and the pore volume was 0.403 cm3 g-1. And most pore of g-C3N4 sample is around 1.5 nm which is a small channel to limit the “shuttle effect” of LiPSs. So this g-C3N4 layer could sieve Li ions by the molecular structure and morphology structure. Figure 1d/e are the SEM/TEM images to characterizing the morphology and structure characteristics of the g-C3N4 sample. The g-C3N4 shows a morphology similar to graphene. It can be observed that the g-C3N4 presents a thin film which is highly crumpled and form a honeycomb-like structure. This graphene-like structure make the sample more compact and easier to cover the pp membranes with a thin thickness. Figure 1f and g show the g-C3N4 interlayer covered on the surface of the pp membrane. The


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layer was evenly coated on the pp separator whose big stretched holes have been modified very well (Figure S1). And the layer shows a thickness about 3 um with a weight only about 0.1 mg cm−2.

Figure 2. Diffusion process of polysulfides with the g-C3N4 layer (a) and pp separator (b) in a shaped device after different time.

The permeation experiments of the g-C3N4 interlayer and pp separator were conducted using an H-shaped device (Figure 2). A 20 mM L2S6 solution was injected into the left-chamber and the blank was added into the aother one. When the g-C3N4 layer put between the two chamber, the color of thr right side has nearly no change even after 48h. In contrast, only after 0.5h, the colour of the lucid electrolyte with pp separator starts changing to yellow, and then turn to much deeper after 6 h. This phenomenon suggests the g-C3N4 layer has an effectively blocking effect


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for LiPSs which means that the g-C3N4 layer may improve the cycling stability for the Li-S batteries.

Figure 3. EIS of pp separators and g-C3N4 interlayer sandwiched between SS plates.

After saturated in the electrolyte, the ionic conductivity of g-C3N4 layer was tested placed between two stainless steel (SS) electrodes. The common electrolyte for Li-S bettery is used for both the pp separator and g-C3N4 layer. Figrue 3 was the electrochemical impedance spectroscopy (EIS) of these two layers with a frequency range from 1 Hz to 100k Hz. The resistance offered by the separator (Rs) and electrolyte (Re) is measured. In this case, Rs is generally ignored, the resistance tested by EIS is attributed to Re. And the Re for separator and g-C3N4 layer is 2.61Ω and 2.84 Ω, respectively. The ionic conductivity of layer or separator can acquire by an equation: σ= d/(S × Rs) in which d is the thickness of the separator (20 um) or gC3N4 layer (23 um) and S is the area of the electrode. Hence, the ionic conductivity of g-C3N4


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layer and pp separator is 0.621 mS cm-1 and 0.589 mS cm-1, respectively. It illustrates that the gC3N4 ion-sieve has a good permeability for lithium-ions which doesn't lower the ionic conductivity of the cell.

Figure 4. (a) Discharge capacity and coulombic efficiency of the cell with g-C3N4, without interlayer and the cell used g-C3N4 as host materials at 1 C. (b) Digital picture and XPS of S 2p of the metal lithium after 100 cycles with and without g-C3N4 layer, respectively.


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Figure S2 and Figure 4 is the electrochemical performance of the g-C3N4 ion-sieve as an interlayer for lithium-sulfur batteries, pure S was used as the active material and there was no any host material in the cathode. The discharge specific capacity of the 1st cycle is about 1250 mAh g-1 at 0.1 C, and the discharge capacity was approximately maintained at 1100 mAh g-1 after 30 cycles. Due to the high conductivity of Li+ and the blocking effect for LiPSs, the cell with gC3N4 layer shows much higher capacity than that without interlayer at a series of current density (Figure S2). And what most importantly is that the cell with g-C3N4 layer can present much higher cycling stability. At a rate of 1 C, even after 500 cycles, the reversible capacity could still be delivered at about 600 mAh g-1, and the capacity attenuation was less than 0.02% per cycle (Figure 4a). As a contrast, the cell without interlayer could only remain a capacity about 200 mAh g-1. And the cell with the g-C3N4 as host material was tested under the same condition, the cycling stability of this cell is far less than the g-C3N4 use as interlayer. It shows that the suppressions of “shuttle effect” of the polysulfides is main attributed to the “ionic sieve” instead of the normal adsorption. After 100 cycles, the metal lithium anode was taken out for characterizing. There was no obvious color changes in the lithium anode from the cell with gC3N4 layer, manifesting effective restriction for LiPSs with the g-C3N4 layer (Figure 4b). But yellow scope in the lithium metal without interlayer is conspicuous, illustrating the ability of common separator to block the shuttle of polysulfide is insufficient. XPS of S 2p in the abovementioned anodes shown in Figure 4b. The signals around 160-164 eV and 167-172 eV are attributed to Li2Sx (1≤x≤8) species and the S-O in electrolyte, respectively. For both the cell without and with the interlayer, there were obvious peaks of S-O discovered. While the signal of Li2Sx in the lithium metal for the cell without layer is much higher than that in the cell with gC3N4 layer.


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Due to the effective blocking effect for LiPSs of the g-C3N4 layer, here the frequently-used electrolyte additive, LiNO3, is no longer need. The cell with g-C3N4 ionic sieve liberated a discharge capacity of 1281 mAh g-1 at 0.1 C and the charge capacity was 1314 mAh g-1, with a over-charge only of 102%, manifesting that a unconspicuous polysulfide shuttling (Figure S3). As a contrast, cells with pp membrane showed a high over-charge > 330%, indicating the serious polysulfide shuttling in the process of lithium-sulfur batteries. And at a rate of 0.5 C, the same situation happened. In the LiNO3-free electrolytes, the cell with g-C3N4 ionic sieve exhibited a higher efficiency and better capacity retention than the cell pp membrane as shown in Figure S3c. These phenomena is in accord with the previous test which illustrates the g-C3N4 layer acted as an ionic sieve could effective prevent polysulfide travel across the membrane. However, the gC3N4 interlayer just exerts the action as a blocking wall here, which is far from reaching high comprehensive battery performance. In Figure S2a, at a rate of 5 C, the discharge capacity with only g-C3N4 is less than 200 mAh g-1.


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Figure 5. (a) XPS characterization of cathode by the cell without and with BN/graphene layer after 1st discharge to 1.7 eV. (b) Discharge/charge voltage profiles for the first cycle at different rate. (c)Rate capability of the cell with BN/graphene. (d) Coulombic efficiency and discharge capacity of the cell with BN/graphene interlayer under a rate of 1 C and 2 C.


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An adsorption test for polysulfides were shown in Figure S4. It can been found that the 2D graphitic material, BN sheets, has capacity of adsorption for polysulfides. And when the BN sheets composite with graphene, a strong synergistic effect between the these two 2D graphitic material (graphene and BN) could greatly improve the adsorption for polysulfides which may improve greatly sulfur redox kinetics. These had been reported used as a host materials for lithium-sulfur batteries in our previous work.32 In order to demonstrate this, a layer made by BN/graphene composite was used in Li-S battery (the characterization of the layer was shown in Figure S5). After the 1st discharge to 1.7 V, the XPS of S element in the cathode electrode of the cell with and without the layer were measurand (Figure 5a). The signals between 167-171 eV are attributed to the S-O in the electrolyte. The signal at about 164-163 eV being corresponded to the soluble LiPSs (Li2Sn, n≥4). The binding energy around 161.7 eV/160.3 eV assigned to the discharging product Li2S2/Li2S. The signals of Li2Sn in the electrode without layer is obvious, while the peaks around 160.3 eV are distinctly weaker, manifesting the reaction is not complete. In contrast, peaks of Li2Sn in the electrode with BN/graphene layer are more weaker, on the contrary, the Li2S peaks were distinctly stronger, these will due to the more exhaustive reduction reaction from LiPSs to Li2S. These results illustrate the BN/graphene layer has excellent catalysis for Li-S battery which could lead to high utilization of S. Figure 5b is the charge/discharge curve of the 1st cycle under different current densities. At 0.1 C, the cell with BN/graphene layer can liberate a high discharge capacity of 1463mAh g−1 even without any host materials in the electrode. Meanwhile, capacity could be charged to 1453 mAh g−1, these manifesting at the process of charge and discharge, there both have a high utilization of S. And even under a higher rate 2 C, the capacity could be keep at approximately 850 mAh g−1. As shown in Figure 5c, when the rate increase from 0.1 C, 0.2 C, 0.5 C, 1 C to 2 C,


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the capacities are 1484 mAh g-1, 1211 mAh g-1, 1042 mAh g-1, 847 mAh g-1 and 664 mAh g-1, respectively. And the discharge capacity could keep at 520 mAh g-1 even at a rate as high as 5 C. And due to the strong adsorption capacity for LiPSs, the cell with BN/graphene shows a excellent cyclic stability at the large rate when the area loading of S is not so high (1.5 mg cm-2) . And after 300 cycles, the capacity can still keep at about 735 mAh g−1 and 550 mAh g−1 under 1 C and 2 C with the pure S as the active material. In the BN/graphene, Figure S5 shows that the BN sheets is tend to array vertically on the surface of graphene, and the pore size of most BN/graphene is about 4 nm which is too big to limit the “shuttle effect” of polysulfides. It illustrates that the “shuttle effect” could be partially reduced by BN/graphene layer due to adsorption, which can not completely block the polysulfide travel across the membrane especially at a high S loading. As shown in Figure S6, when the S area loading was 6 mg cm-2, cell with the BN/graphene layer has a large dischrge capacity at first, but only goes though 100 cycles, the capacity quickly drop to less than 400 mAh g−1 and keep at less than 300 mAh g−1 after 500 cycles.


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Figure 6. (a) Rate capability of the cell with BN/graphene-C3N4 double layer, BN/graphene layer and without interlyer at different current densities. (b) Discharge/charge curve of the cell with BN/graphene-C3N4 double layer at corresponding rate. (c) Discharge capacity of the cell with BN/graphene-C3N4 double layer, BN/graphene layer, g-C3N4 layer and without interlyer at 1 C. All the sulfur-loading of these cell is 6 mg cm-2.

Due to the ionic sieve effect of g-C3N4 and the strong catalysis of BN/graphene, the multifunctional ion-sieve constructed by these three 2D sheets as the interlayer possesses high conductivity for lithium-ions, excellent blocking ability for polysulfides and outstanding catalysis for S conversion reactions which make the cell shows a high sulfur utilization and cycling stability at a large current density with high S-loading. g-C3N4 sheet and graphene sheet


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overlap into a sandwich structure and the BN flake are embedded vertically between them (the characterization of the interlayer was shown in Figure S7). Under the circumstances, host material is not even necessary in the cathode. Figure 6 shows the electrochemical testing of the cell with this multi-functional ion-sieve at a S-loading of 6 mg cm-2 (pure S as the active material without host materials). At a rate of 0.1 C, the cell could liberate a discharge capacity above 1100 mAh g-1 which corresponded to an areal capacity of 6.6 mAh cm-2. Because of the synergy of graphene, BN and g-C3N4, the cell with the multi-functional ion-sieve can liberate much higher capacity than the cell with only BN/graphene layer at different current density. Even the rate is increased to 2 C which corresponded to a high area current density of 26.88 mA cm-2, the cell still liberate a capacity more than 400 mAh g-1. And most important is that cell with the multi-functional ion-sieve showed a high cycling stability at a large rate of 1 C. After 500 cycles, the cell shows a reversible capacity of 603 mAh g−1 with a only 0.01% per cycle capacity decay rates which is a pretty high level in such a large S-loading. Under the same test conditions, the cell with g-C3N4 layer and BN/graphene presented low sulfur utilization and poor cycle stability, respectively.

3. CONCLUSION In conclusion, a multi-functional ion-sieve constructed by three 2D graphitic materials (gC3N4, BN and graphene) were synthesized whose architecture is a double layer sandwich structure. The g-C3N4 act as an ionic sieve for preventing polysulfide travel across the membrane and allow lithium ions to pass freely; the BN sheets can catalyze conversion reaction of S and graphene played as an extended collector to improve the conductivity of the cathode region. Due to the synergistic effect between these 2D materials, the ion-sieve demonstrate an excellence performance at a large rate with high S-loading. When the areal loading of S is 6 mg cm-2 (the


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pure S as the active material ), it showed an excellent cycling stability at a large rate. And after 500 cycles, the specific capacity is about 600 mAh g-1 at 1 C with a capacity attenuation less than 0.01% per cycle. Even the current density increase to 2 C (26.88 mA cm-2), the reversible capacity could still keep at above 400 mAh g-1. We believe that the ion-seive concept could provide a new avenue for researching on interlayers to be used in various of batteries.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publication website. Additional experimental methods, SEM and electrochemical performance (PDF) AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] §D.D.R.

and B.C.D. contributed equally to this work.

The authors declare no competing financial interest.

ACKNOWLEDGMENT


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We gratefully acknowledge the financial support from the National 973 Program (2015CB251102), the Key Project of NSFC (21673196, 21621091, 21703186), the Fundamental Research Funds for the Central Universities (20720150042, 20720170101)

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ToC figure


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Multifunctional Ion-Sieve Constructed by 2D Materials as an Interlayer

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