Synergetic effect of block and catalysis on polysulfides by functionalized bilayer modification on the separator for lithium-sulfur batteries
Abstract
One crucial problem hindering the commercial application of lithium-sulfur batteries with high theoretical specific energy is the ceaseless shuttle of soluble lithium polysulfides (LiPSs) between cathodes and anodes, which usually leads to rapid capacity fade and serious self-discharge issues. Herein, a unique bilayer coating strategy designed to modify the polypropylene separator was developed in this study, which consisted of a bottom zeolite (SSZ-13) layer serving as a LiPS movement barrier and a top ZnS layer used for accelerating redox processes of LiPSs. Benefiting from the synergetic effect, the bilayer-modified separator offers absolute block capability to LiPS diffusion, moreover, significant catalysis effect on sulfur species conversion, as well as outstanding lithium-ion (Li+) conductivity, excellent electrolyte wettability, and desirable mechanical properties. Consequently, the assembled lithium-sulfur cell with the SSZ-13/ZnS@polypropylene separator demonstrates excellent cycle stability and rate capability, showcasing a capacity decay rate of only 0.052% per cycle at 1 C over 500 cycles.
Keywords
INTRODUCTION
Lithium-ion batteries (LIBs) have significantly boosted rapid growth of high-performing mobile devices and electric vehicles[1]. However, further increase in energy density remains necessary for the industry requirements. In this case, lithium-sulfur (Li-S) batteries are considered as one of the most attractive energy storage devices on account of a high specific capacity (1,675 mAh g-1) and mass energy density
Massive strategies for settling obstinate problems mentioned above have been proposed such as electrolyte optimization[9], sulfur host design[10] and separator coating[11]. Among them, separators are advantageous platforms to address critical issues such as dendrite proliferation, “shuttle effect”, and interfacial instability. At the same time, modifying commercial separators is one of the preferred routes due to its simplicity and effectiveness. Currently, research of the surface coating on the separators concentrates on various functional polymers[12,13] or polar compounds[14,15]. For instance, Chen et al. developed a Fe,N co-doped mesoporous carbon sphere (Fe-N-MCS) as a coating material of polypropylene (PP) separators, which not only created a physical block to restrain LiPSs but also contributed to abundant adsorption sites for LiPS conversion[16].
Zeolite molecular sieve is a kind of aluminosilicate with very regular nanoscale pore sizes between 0.3 and
Herein, we propose a novel bilayer modification on the separator via a facile coating method, which mainly consists of a bottom zeolite layer and a top ZnS layer. Benefiting from the synergetic effect of block and catalysis provided by the bilayer modifier mentioned above [Figure 1A], the Li-S cell reaches a distinguished initial specific capacity of 1,364.22 mAh g-1 at 0.2 C, and an average capacity attenuation of only 0.052% per cycle at 1 C upon 500 cycles, which is much superior to other cells with monolayer-modified and pristine separators. Even at a high sulfur loading and lean electrolyte condition, the cell with the bilayer coating separator maintains brilliant cycle stability. This work provides a fresh idea to design a synergistically modified separator used for constructing shuttle-free and highly stable Li-S batteries.
EXPERIMENTAL
Modified separator fabrications
The ZnS powder was synthesized using a simple hydrothermal method[27], where CH4N2S (99%, Innochem) and Zn(Ac)2∙2H2O (99%, Innochem) were mixed uniformly in ethylene glycol with the molar ratio equal to 1:1 under continuous stirring. Then, the solution was transferred and sealed in a Teflon-lined stainless autoclave and heated at 180 °C for 24 h. Finally, the product was cleaned with distilled water and dried at
The zeolite molecular sieve (SSZ-13, Si/Al molar ratio of 25~30, Zhizhen), conductive carbon (Super P), and polyvinylidene fluoride (PVDF) were mixed in the N-Methyl-2-pyrrolidone (NMP) at a mass ratio of 8:1:1. The obtained SSZ-13 slurry was loaded on a piece of a commercialized PP separator (Celgard 2400) and then dried at 50 °C overnight to produce the SSZ-13@PP separator. The same method was used to prepare the ZnS slurry. The obtained ZnS slurry was coated on the pristine separator and SSZ-13@PP separator to further fabricate ZnS@PP- and SSZ-13/ZnS@PP-modified separators, respectively. The thickness of the coating layer can be regulated by the doctor blade gap and slurry viscosity. The final mass loading of the SSZ-13/ZnS coating on the separator was controlled at ~2.6 mg cm-2.
Characterizations
The microcosmic morphologies of the materials and separators were observed by a Tescan Mira4 scanning electron microscope (SEM) equipped with an energy disperse spectrum (EDS) microanalyzer. The powder X-ray diffraction (XRD) measurement was performed on a Rigaku Ultima IV X-ray diffractometer with
Electrochemical measurements
The sulfur cathode consisted of sulfur/mesoporous carbon (CMK-3, XF Nano) composite (prepared via melt-infiltration strategy at 155 °C for 12 h), Super P, and PVDF at a mass ratio of 8:1:1. The Li-S coin cell was assembled in an Ar-filled glove box, which was composed of a sulfur cathode and a lithium metal anode separated by a piece of pristine or modified separator. The coating layer in the modified separator was in contact with the sulfur cathode. The employed electrolyte was 1 M Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 2 wt% LiNO3 dissolved in the mixed dimethyl ether/1,3-Dioxolane (DME/DOL) solvent (v/v = 1:1). The Li-S cell was cycled on a Neware tester in the voltage range of 1.7~2.8 V. The electrochemical workstation (PARSTAT MC) was used to measure cyclic voltammetry (CV) at different scan rates and electrochemical impedance spectra (EIS).
To investigate sulfur redox kinetics, a symmetrical cell with two identical electrodes was assembled in
DFT computations
All theoretical calculations were conducted in a DMol3 module according to density functional theory (DFT). The exchange-correction function was described by the Perdew-Burke-Ernzerhof (PBE) within the generalized gradient approximation (GGA). The double numerical polarization (DNP) was selected as the basis setting. The all-electron relativistic method was adopted to manage the core and valence electrons. Grimme dispersion correction (DFT-D3) analyzed the van der Waals interaction. Linear/quadratic synchronous transit (LST/QST) methods identified the transition state and then determined the energy barrier of LiPS migration.
RESULTS AND DISCUSSION
The XRD pattern of as-prepared ZnS was provided in Figure 1B. Three characteristic peaks located at 28.9°, 48.1°, and 57.1° correspond to (111), (220), and (311) lattice planes of ZnS (JCPDS No. 80-0020), respectively, indicating successful preparation of the material. The inserted SEM image reveals a clear sphere morphology with the diameter distribution concentrated in the range of 50~100 nm
The above raw materials were coated on the pristine PP separator to create functionalized surface modification. Figure 2A shows the SEM image of the pristine PP separator, in which the micron-sized pores can be observed. These pores provide convenient channels for the electrolyte penetration and Li+ movement. Nevertheless, they also allow LiPSs to pass through freely, leading to metal corrosion once they get in touch with the lithium anode. In contrast, Figure 2B and C provides the top and cross-sectional images of SSZ-13/ZnS@PP separators, respectively. It is observed that the pristine separator is uniformly covered by the SSZ-13 and ZnS particles with tiny pores, fabricating a continuous and flat coating layer with a total thickness of approximately 9 μm. Moreover, the EDS elemental mappings in Figure 2D distinctly exhibit that the elements of SSZ-13 (Al, Si) and ZnS (Zn, S) are separated into two layers, revealing a compact bilayer architecture on the pristine separator (The strong Al signal at the bottom is mainly attributed to the aluminum object platform). It needs to be emphasized that the monolayer-modified
Figure 2. SEM images of (A) PP separator and (B) SSZ-13/ZnS@PP separator. (C) Cross-sectional image and (D) EDS elemental mappings of the SSZ-13/ZnS@PP separator. (E) Flexibility and (F) contact angle measurements of the SSZ-13/ZnS@PP separator.
The excellent mechanical property of the SSZ-13/ZnS@PP separator can be confirmed in Figure 2E since it remains intact after being folded several times, indicating ideal integration of the bilayer coating with the pristine separator substrate. In addition, the contact angle test evaluated the wettability of liquid electrolyte toward the modified separator. As depicted in Figure 2F, the SSZ-13/ZnS@PP separator offers a lower contact angle of 12° in contrast to the pristine separator (26°). It is considered that the polar ZnS particles on the top layer facilitate the rapid electrolyte penetration and, hence, Li+ transport.
To explore the barrier capability of the SSZ-13/ZnS@PP separator, an H-shaped glass device was applied to compare the permeability of LiPSs across the separator. As shown in Figure 3A, 5 mL Li2S6 (25 mM) solution (left side) and 5 mL DOL/DME mixed solvent (right side) were separated by different separators. For the device composed of PP separators, the right solution color becomes yellow after 12 h and turns brown at last, indicating a free Li2S6 permeation. For the ZnS@PP case, the permeation did not stop, but the diffusion concentration decreases owing to the chemisorption of LiPSs on the surface of ZnS. When
Figure 3. (A) LiPS diffusion tests in the H-shaped cells with different separators. (B) Molecular structures and calculated sizes of various LiPSs monomer units. (C) The calculated ionic conductivity for different separators. (D) UV-Vis spectra of Li2S6 solution before and after being adsorbed by the ZnS. (E) Zn 2p, (F) S 2p XPS spectra of ZnS before and after Li2S6 adsorption.
DFT calculation was implemented to investigate the three-dimensional structures of various LiPSs. As provided in Figure 3B, the sizes of several LiPS molecules are all well in excess of the pore size of SSZ-13
The chemical affinity of ZnS to LiPSs can be confirmed in the UV-Vis spectrum in Figure 3D, where the intensity of S62- peak decreases prominently and the solution color becomes lighter after the ZnS powder was added into the LiPS solution. The latent interaction between LiPSs and ZnS was further investigated via XPS analyses. As shown in the Zn 2p spectra in Figure 3E, both Zn 2p3/2 and Zn 2p1/2 peaks shift towards lower binding energies after the ZnS was soaked in Li2S6 solution, suggesting the increased electron density at the metal center due to the polarization of electrons away from the terminal sulfur atoms (ST-1) in the Li2S6 to the electropositive Zn[32]. In the S 2p spectra [Figure 3F], two characteristic peaks located at 162.2 and
The redox kinetic behaviors of the restrained LiPSs by the functionalized modification on the separator were investigated via various CV measurements. The CV curves of the symmetrical cell in Figure 4A show that the cell employing a ZnS electrode has higher current response than the SP electrode, revealing the latent catalytic activity of ZnS for accelerating the redox kinetics of those adsorbed LiPSs. The CV curves of the Li-S cells with modified and pristine separators at various scan rates are provided in Figure 4B and C, respectively. The observed shifts of cathodic and anodic peaks (Oa, Ra and Rb)[34] stand for the increased polarization at high scan rates. The lithium-ion diffusion coefficient (
Figure 4. (A) CV curves of the symmetrical cells using different electrodes. CV curves of Li-S cells with (B) SSZ-13/ZnS@PP and (C) PP separator at various scan rates. Linear relationship of Ip-v0.5 for (D) peak Oa, (E) peak Ra and (F) peak Rb. (G) CV curves of Li-S cells with various separators. Tafel slopes derived from the (H) oxidation peak and (I) reduction peak.
Where Ip, n, A,
The CV curves of Li-S cells using different separators at a scan rate of 0.1 mV s-1 are displayed in Figure 4G. Remarkably, the reduction peaks for SSZ-13/ZnS@PP separators exhibit a positive shift with significantly higher peak currents relative to other counterparts, verifying that the bilayer modification is conducive to the reversible conversion and then adequately utilizing sulfur species. The Tafel slope is calculated from the oxidation peak at ~2.39 V and reduction peak at ~2.03 V. The cell with the SSZ-13/ZnS@PP separator shows a lower Tafel slope value of 56 mV dec-1 for the oxidation from Li2S to Li2Sx [Figure 4H] and
To further confirm the catalytic effect of the SSZ-13/ZnS coating, the discharge products of sulfur cathodes matched with different separators were examined by XPS (the cells were discharged designedly to the low-potential plateau). As observed in Figure 5A, the characteristic peaks of S 2p3/2 at ~162.1 eV in the S 2p spectra are assigned to the generated Li2S2 during discharging[38]. The stronger Li2S2 signal on the cathode surface matched with the modified separator compared to the pristine one illustrates the accelerated sulfur reduction process. Besides, the Li2S deposition experiment results are provided in Figure 5B and C for monitoring the formation of the discharge products. It can be seen that the accumulative capacity of deposited Li2S in the modified separator far exceeds that of the PP separator (165.93 vs. 105.14 mAh g-1), accompanied by higher current density and earlier precipitation time. This reveals that the SSZ-13/ZnS coating reduces the initial overpotential for the Li2S nucleation and realizes faster growth of Li2S[39].
Figure 5. (A) S 2p XPS spectra of sulfur cathodes matched with different separators after discharging to 2.11 V. Potentiostatic discharge profiles of Li2S deposition with (B) SSZ-13/ZnS@PP separator and (C) PP separator. (D) Energy profile for Li2S4 migration along the different adsorption sites on the ZnS (220) facet. (E) Li2S4 migration path on the ZnS (220) facet.
The LiPS migration usually depends on the exposed facets of the catalyst due to high surface affinity and reactivity. It was reported that the lowest energy shape of zinc blende nanoparticles is a rhombic dodecahedron, enclosed entirely by stoichiometric (220) facets[40]. Therefore, the geometrical configurations of the minimum energy path for LiPS migration on the (220) facet of ZnS were investigated by DFT calculation (Li2S4 as the prototype for modeling). As provided in Figure 5D and E, the migration barrier for Li2S4 on the ZnS surface was only 1.42 eV. This benefits the rapid diffusion of Li2S4 to the nearby conductive area (e.g., SP particles in the coating)[41] and then electrochemical conversion.
Thus far, the above results well support the conclusion that the favorable entrapping-diffusion-conversion process of LiPSs can be realized by the separator modification strategy. It needs to be emphasized that the original concept of the SSZ-13/ZnS bilayer coating is chemically anchoring LiPSs and accelerating their conversion earlier to the physical block. In other words, the zeolite layer was set as a final defense for resisting LiPS diffusion. Mixing the zeolite and ZnS together in a monolayer can simplify the coating procedure. However, the block and catalytic capability towards LiPSs could be simultaneously weakened due to the incomplete coating of the SSZ-13 and ZnS on the separator. Thus, the bilayer design is essential for better exerting their synergetic effects.
The GITT test explored the effect of the functional coating on the conversion reaction process of the Li-S system. As shown in Figure 6A and B, compared to the PP sample, the cell with the SSZ-13/ZnS@PP separator displays smaller IR drops of QOCV (quasi-open-circuit voltage, 25.9 mV) and CCV (close-circuit voltage, 32.9 mV), suggesting the enhanced redox kinetics[42,43]. At the same time, the S8 dissolution process of the SSZ-13/ZnS@PP and PP cells accounts for approximately 34% (8.93/25.9 h) and 37% (6.73/18.2 h) of the discharge phase, respectively. The relatively smaller proportion in the modified separator can be attributed to higher efficiency for Li2S nucleation[44,45].
Figure 6. GITT measurements of the Li-S cells with (A) PP separator and (B) SSZ-13/ZnS@PP separator. (C) Comparison of charge/discharge profiles for different separators at 0.2 C. (D) Cycle stability of the Li-S cells with various separators at 0.2 C. (E) Shuttle currents of the Li-S cells with different separators. (F) Rate capabilities of the Li-S cells. (G) Long-term cycling performance of the Li-S cells at 1 C. (H) Cycle performance of the Li-S cell with SSZ-13/ZnS@PP separator at high sulfur loading at 0.2 C.
The Li-S full cell was assembled to investigate the actual contribution of the various modified coatings on the electrochemical performance. The discharge curves of these cells all deliver two well-defined potential plateaus, as exhibited in Figure 6C. However, larger capacity at low-potential plateau (QL) and higher QL/QH value in the SSZ-13/ZnS@PP cell manifest favorable conversion of LiPSs to insoluble sulfides[46,47]. A smaller polarization can also be observed with the SSZ-13/ZnS@PP separator, indicating enhanced electrochemical reversibility. The SSZ-13/ZnS@PP cell produces a high initial specific capacity (1,364.22 mAh g-1) at
The rate tests of Li-S cells with different separators were conducted at current densities ranging from 0.1 C to 2 C. The initial specific capacity with the SSZ-13/ZnS@PP separator reaches 1,383.47 mAh g-1 at
Besides, the long-term cycle stabilities of the Li-S cells at 1 C are exhibited in Figure 6G. The SSZ-13/ZnS@PP cell delivers a discharge capacity of 885.4 mAh g-1 and maintains at 655 mAh g-1 after 500 cycles with an attenuation rate of only 0.052% per cycle. The acquired cell performances with the separator modification strategy in this work are competitive and even superior to some recent reports adopting other coating materials (as summarized in Supplementary Table 1). Subsequently, the acceptable cycling capability of the Li-S cell with an SSZ-13/ZnS@PP separator at a higher sulfur loading of ~5.2 mg cm-2 and a lower E/S ratio of 10 uL mg-1 is also indicated in Figure 6H, reflecting great potential of the SSZ-13/ZnS@PP separator for practical applications.
CONCLUSIONS
In summary, we have successfully engineered a bilayer modification on the separator for Li-S cells, establishing an excellent synergetic relationship between inhibiting the diffusion of LiPSs and catalyzing their conversion. The experimental studies and DFT calculations reveal that the appropriate pore size of SSZ-13 zeolite physically blocks the movement of the LiPSs towards the lithium anode but ensures free and rapid transport of Li+. Additionally, the introduced ZnS coating chemically interacts and then accelerates the redox kinetics of the confined sulfur species by providing a low surface migration barrier. Consequently, the SSZ-13/ZnS@PP separator endows the Li-S cell with a high discharge capacity of 1,364.22 mAh g-1 at 0.2 C, preferable capacity decay of 0.052% per cycle over 500 cycles at 1 C, and satisfactory rate capability. This work provides a simple but effective strategy of separator structure engineering to develop advanced Li-S batteries for commercial applications.
DECLARATIONS
Authors’ contributions
Methodology, writing-review & editing, funding acquisition: Ma Y
Investigation, data curation, writing-original draft: Chang L
Formal analysis, supervision: Yi D
Investigation, validation: Liu M, Wang P
Visualization, resources: Luo S, Zhang Z
Conceptualization, project administration, funding acquisition: Yuan Y, Lu H
Availability of data and materials
Not applicable.
Financial support and sponsorship
This work is supported by the National Natural Science Foundation of China (No. 51704222), Postdoctoral Science Foundation of China (2023M742243), Key Project of Natural Science Basic Research Plan of Shaanxi Province (No. 2022JZ-25), and Special Research Program of Shaanxi Provincial Education Department (No. 22JC049).
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Copyright
© The Author(s) 2024.
Supplementary Materials
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Cite This Article
How to Cite
Ma, Y.; Chang, L.; Yi, D.; Liu, M.; Wang, P.; Luo, S.; Zhang, Z.; Yuan, Y.; Lu, H. Synergetic effect of block and catalysis on polysulfides by functionalized bilayer modification on the separator for lithium-sulfur batteries. Energy Mater. 2024, 4, 400059. http://dx.doi.org/10.20517/energymater.2023.109
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