www.sciencedirect.com /science/article/pii/S1388248122001278
A biomass-based cathode for long-life lithium-sulfur batteries
L. Borchardt, M. Oschatz, S. Kaskel43-54 minutes 7/20/2022https://doi.org/10.1016/j.elecom.2022.107325Get rights and content
Highlights
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The obtained biomass-derived carbons possess an appropriate ratio of pore volume.
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LSBs with biomass-derived carbon host exhibited promising rate capability.
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Biomass-derived sulfur cathodes retained 80% of initial capacity after 400 cycles.
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The promising LSB performance is ascribes to the unique pore structure of carbon host.
Abstract
With the advantages of high conductivity and low cost, porous carbons have been considered as the most attractive host materials of sulfur cathodes in lithium-sulfur batteries (LSBs). However, LSBs always suffer short cycle life due to the “shuttle effect” of lithium polysulfide species (polysulfides), which are intermediate products during the charge/discharge processes. The weak interaction between carbon and polysulfides results in the dissolution of polysulfides from the cathodes, loss of active material of sulfur and eventually fast capacity fading. To overcome these drawbacks, we employed a biomass-derived carbon as the host material in sulfur cathodes. Results from X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen sorption reveals that this biomass-derived product is amorphous carbon and is composed of both large (>10 nm) and small (<5 nm) pores at an appropriate ratio. Using as hosts of cathodes in LSBs, the biomass-derived carbons deliver a high reversible capacity of >800 mAh/g and retain >80% of initial capacity after 200 cycles. Especially, the activated carbons exhibited an unprecedently high durability with 80% capacity retention after 400 cycles. The promising LSB performance can be ascribed to the unique porous architecture of biomass-derived carbons. The small pores in biomass-derived carbons provide more sites to anchor sulfur and polysulfides, while large pores provide channels for fast transport of ions. This is corroborated by the results from the electrochemical impedance spectroscopy (EIS), the thermogravimetric analysis (TGA) and absorption measurements.
Keywords
Biomass
Porous carbon
Lithium-sulfur battery
1. Introduction
With the advantages of high electronic conductivity and low cost, the carbonaceous materials have been considered as the most attractive hosts of sulfur cathodes in lithium-sulfur batteries (LSBs) [1], [2], [3], [4]. However, the derived LSBs always suffer the fast capacity decay due to the “shuttle effect” of soluble lithium polysulfide species (polysulfides), which are intermediate products during the charge/discharge processes, arising from the weak interaction between carbon and polysulfides. This promotes the efforts on developing advanced carbon-based hosts, such as nanostructured carbons with confining effect and carbon composites with chemical affinity to polysulfides. Successful examples including carbon nanotubes (CNTs) [5], [6], [7], [8], [9], micro/mesoporous carbon spheres [10], [11], [12], [13], [14], porous carbon with functional groups [15], [16]and metal oxides/sulfides/nitrides decorated carbons [7], [9], [17], [18], [19], [20], [21] greatly elongate the cycle life of derived LSBs. However, the complexity of fabricating processes [6], [12], [22] and the high cost of special precursors [16], [19], [23] limit the commercialization of LSBs with advanced carbon-based hosts. Therefore, there is a critical need to develop a new carbonaceous host with low cost and strong constrains to polysulfides to booster the LSB performance and thus accelerate its wide adoption to the electronic device market.
The biomass-derived carbon possesses the advantages of large specific surface area (SSA), high porosity and low cost, and has been considered as one of the most promising host materials [24], [25] since it was first employed as the host of sulfur cathode in LSBs in 2011 [26]. The large SSA can enhance the sulfur content, improve the dispersion of elemental sulfur in the conductive carbon matrix, and thus increase the utilization of sulfur [27]. However, the SSA of carbon materials has little effect on alleviating the polysulfide dissolution. The small pores, especially micropores (pore width of < 2 nm), can provide spatial constrains, mitigate the polysulfide dissolution from the sulfur cathodes and eventually improve the durability of LSBs [28]. For instance, the microporous graphic carbon (MGC) synthesized from peanut shell has the predominant pore width <0.4 nm and the strong confinement of polysulfides in the micropores enables the derived LSBs the high capacity of 826 mAh/g at 1C after 1000 cycles [29]. However, the low pore volume limits the mass ratio of sulfur loaded into the cathodes and the utilization of sulfur at high rates. Therefore, it is necessary to develop a biomass-derived carbon host having balanced trapping ability and utilization of active material for energy-dense LSBs with long cycle life.
It has been well recognized that the porous architecture of biomass-derived carbons plays a crucial role in determining the LSB performance. The small pores (micropores) have strong absorption to polysulfides [30], while large pores (mesopores with pore width of 2–50 nm) allow the high sulfur load [31] and provide channels for the ion diffusion [32]. In light of this, carbonaceous hosts possessing both micropores and mesopores and an appropriate pore size distribution (or volume ratio between micropore and mesopore) can make derived sulfur cathodes exhibit high sulfur utilization and strong trapping capability to polysulfides. This has been confirmed by the excellent performance of LSBs containing biomass-derived carbon hosts with hierarchically porous architectures [30], [31], [32], [33]. These prior achievements inspired us to develop a new carbon with dual porosity from gallic acid (GA) and use it as the host material for high performance LSBs. As a member in the biomass family, GA is one of the main natural phenolic components widely presented in plants [34] and has the advantages of low cost, low toxicity and natural abundance [35]. As the supercapacitor electrodes, GA-derived porous carbon exhibited the highest electrical conductivity among different types of plant-derived polyphenols [36]. Therefore, it is rational to anticipate that the sulfur cathodes with GA-derived carbon hosts will inherit these advantages and render LSBs promising performance.
Here, we synthesized a new porous carbon with dual porosity via a solvent-free approach with GA as the carbon source. The properties of obtained porous carbon were characterized. Used as the host of sulfur cathode, the promises of GA-derived carbon host in improving the LSB performance were demonstrated and the effect of porous structure on the LSB performance was discussed.
2. Material and methods
2.1. Material preparation
The porous carbons were prepared through a solvent-free synthesis approach, as shown in Fig. 1. GA was used as a carbon source, the Pluronic surfactant F127 was used as a soft template, and zinc acetate was used as a crosslinking agent. The precursor GA, the Pluronic surfactant F127 and zinc acetate (GA/F127/zinc acetate = 1/1/0.5, w/w/w) were mixed and mechanically ground by using a high energy hardened steel ball miller with four stainless steel balls added (8000 M Mixer/Mill SPEX Sample Prep). The grinding process was carried out for twenty minutes, resulting in a homogeneous mixture. After milling, the mixture was heated under N2 atmosphere (100 mL/min) in a tubular fixed-bed oven (OTF-1200X MTI Corporation). The oven was heated to 400 °C with a ramp of 5 °C/min and kept at the targeted temperature for 1 h for the removal of the Pluronic surfactant F127. The oven temperature was then increased to 950 °C at the same heating rate and the temperature was kept constant for another 1 h for the evaporation of metallic Zn. The material was purified with a 3 M HCl solution in an ultrasound bath for 30 min. The porous carbon was obtained after washed with distillated water until pH 7 and was named as MC-GA.
A porous carbon with a larger surface area was also produced through a CO2 activation approach. The obtained MC-GA above was placed in a tubular fixed-bed oven and the oven was heated to 900 °C at a heating rate of 10 °C/min and the temperature was kept constant for 1 h. The activation process was conducted under CO2 atmosphere (200 mL/min) and the obtained material was named as MC-GA-A.
2.1.1. Material characterizations
Crystal phase: X-Ray diffraction (XRD) patterns were collected on Rigaku SmartLab diffractometer using a Cu Kα radiation (λ = 1.54 Å) at room temperature to reveal the crystal structures of obtained samples. The step scan mode with step size of 1° in 2θ range of 10° −90° has been adopted for the investigation.
Microstructures and element analysis: The morphological information was collected on a scanning electron microscopy (SEM, JEOL ITL-200) with an accelerating voltage of 15 kV and equipped with energy dispersive spectroscopy (EDS) for chemical analysis. The analysis of microstructures was performed on a scanning transmission electron microscope (STEM, Talos F200X G2) with an accelerating voltage of 200 kV.
Composition of active materials: The thermogravimetric analysis (TGA) was conducted on a Thermogravimetric Analyzer (Q500, TA Instruments) to determine the content of sulfur in the cathode active material within a temperature range of 25-450℃ at a heating rate of 5 ℃/min under nitrogen atmosphere.
Pore size and surface area: A Tristar 3000 (Micromeritics Instrument Corporation) automatic gas sorption analyzer was used to determine the porous structure of synthesized samples. Specific surface area (SSA) and pore-size distribution of various carbonaceous materials were calculated from nitrogen adsorption isotherms using the Brunauer-Emmett-Teller (BET), and Barrett-Joyner-Halenda (BJH) methods respectively.
Adsorption test: To measure the adsorption capability, 0.2 g tested powders were added into 10 mL electrolyte solution with 1 mM Li2S6. The mixtures were stirred for 6 h to have tested sample powders fully contact with Li2S6, and then kept at room temperature for 12 h for visual inspections. The Li2S6 electrolyte was prepared through mixing Li2S and elemental sulfur with a stoichiometrically ratio of 1,3-dioxolane (DOL)/1,2-dimethoxyethane (DME) (1/1, v/v).
2.1.2. Electrochemical characterizations
Active materials: The synthesized MC-GA and MC-GA-A porous carbons were used as host materials, and the active materials with sulfur impregnated host materials were prepared through a melt-diffusion approach. Typically, 1.1 g commercial sulfur powders and 0.9 g host material were mixed and then ground in an agate mortar. The mixture then was transferred into a glass vessel, sealed, and placed in an oven. The oven was then heated to 155 ℃ and held at the target temperature for 12 h. After cooled down to room temperature, the sulfur infiltrated host material was used as the active material for electrode fabrication and further characterizations. For comparison, the same approach was used to prepare the baseline active materials with commercial 600JD carbon as the host material.
Electrode fabrication: The coating slurries were firstly prepared through mixing active material, carbon black (super C45) and binder solution containing polyvinylidene fluoride (PVDF, Solvay) dissolved in 1-Methyl-2-pyrrolidinone (NMP). Typically, the slurry was mixed in a Thinky AR-100 mixer and then was hand-casted onto aluminum foil. The coating on Al foil was then dried at 60 °C for 12 h under vacuum. The dried electrodes were composed of 80% active material, 5% conductive carbon and 15% binder and had the mass loading of around 1.6 mg-S /cm2.
Cell assembly: The dried electrode was punched into disc with the diameter of 9/16 in. and assembled into coin (CR2032) cells with lithium metal as the counter electrode and polyolefin membrane (Celgard 2325) as separator. The solution containing 1 M lithium bis(trifluoromethane)sulfonimide (LiTFSI) and 2 wt% LiNO3 dissolved in DOL/DME (1/1, v/v) was used as the electrolyte. The cells were assembled inside a glovebox filled with Argon.
Electrochemical characterizations: Galvanostatic cycling tests of assembled cells were conducted on a NEWARE battery tester (BTS-CT-4008) by applying a constant current at room temperature. Initially, three formation cycles with an approximate C/10 current were applied to obtain the exact capacity of the cells for following rate and cycling tests. After the formation cycles, the rate capability of cells was tested following the protocol: charge the cells to 2.8 V with a constant current density of C/10, then discharge to 1.8 V with incremental current densities from 0.1C, 0.2C, 0.5C, 1C to 2C. At each current density, cells underwent three cycles. After the rate test, the cycling test was conducted with the constant current density of 0.5C. The same voltage window of 1.8–2.8 V was applied during the formation, rate and cycling tests.
Before the formation tests, cyclic voltammetry (CV) tests were conducted on cells using a frequency response analyzer (Gamry, 1010E) with a scanning rate of 0.05 mV/s and voltage range of 1.8–2.8 V.
After the formation tests, electrochemical impedance spectroscopy (EIS) was collected on cells using a frequency response analyzer (Gamry, 1010E) with a potential amplitude of 5 mV over the frequency range from 20 Hz to 1.6 MHz.
3. Results and discussion
After the carbonization process, amorphous carbon products with highly porous architectures can be achieved from the biomass source. XRD patterns (Fig. 2) collected from all samples show two broad diffraction peaks, one located at around 24° and the other at 43°, which correspond to the (0 0 2) and (1 0 0) crystal planes in graphite respectively assuming a hexagonal crystal system with P63/mmc symmetry and the d002 spacing of 3.36 Å [37], [38]. This implies a predominantly amorphous structure in carbonaceous materials obtained here. Compared with 600JD, the intensity of both broad peaks on XRD patterns obtained from MC-GA and MC-GA-A is relatively higher. This indicates that GA-derived samples have a higher portion of crystalline graphite phase than 600JD does. Besides these two broad peaks, three sharp and weak peaks observed on GA-derived samples can be identified to zinc oxide, which was the residual of zinc acetate introduced into the carbonization process as a crosslinking agent. However, the reflections corresponding to zinc oxide are almost negligible on the XRD pattern obtained from MC-GA-A. This implies that the activation process at high temperature almost removed the zinc component completely, which might release additional small pores in the activated products.
The observations from SEM show that all carbonaceous samples are composed of particles with the size of < 100 nm (Fig. 3b, 3d and 3f). These fine particles aggregate together and form 1–50 μm powders with irregular morphology and porous architecture (Fig. 3a, 3c, and 3e). The observations from high-resolution TEM (HRTEM) further demonstrate that the aggregation of fine particles generate both < 5 nm (named as small pores thereafter) and > 10 nm (names as large pores thereafter) in the carbonaceous products. Fig. 4 exhibits that numerous small pores and bare large pores can be found in 600JD (Fig. 4a). However, MC-GA (Fig. 4b) and MC-GA-A (Fig. 4c) exhibit both small pores and obvious large pores. In addition, the HRTEM images also confirm the formation of amorphous structure in obtained carbonaceous products. For an individual particle, regions with both clear (circled by yellow dashed lines) and obscure lattice fringes are observable, indicative of the amorphous structure. In further, the distance between neighboring lattice fringes is measured to be 0.33 nm. Given the measuring error, this agrees well with d002 spacing of crystalline graphite phase calculated from XRD patterns.
The formation of porous structure is further corroborated through nitrogen sorption measurements. Fig. 5 clearly shows Type-IV isotherms with a hysteresis loop observable for all samples, which is a characteristic of solids with micropores and mesopores. The BJH pore size analysis performed on the adsorption branch of the isotherms shows that two distinct peaks, one below 5 nm (small pores) and the other above 10 nm (large pores), are observable for biomass-derived samples of MC-GA and MC-GA-A. The activation process has little effect on the large pores, but significantly increase the number of small pores. However, it is obvious that 600JD possesses a large number of small pores. Table 1 summarizes the pore structure properties of these carbonaceous samples including average pore sizes, pore volumes and surface area. The activation significantly reduces the average pore size of GA-derived carbon from ∼12 nm to ∼8 nm and increases the pore volume of large pores. However, the activation has little effect on the pore volume of small pores and volume ratio of small to large pores. The SSA, calculated by the BET method, is 257 m2/g for MC-GA and it increases to 533 m2/g for activated MC-GA-A. The higher surface area is the result of more small pores in MC-GA-A generated through the activation process. Otherwise, more large pores in MC-GA-A will result in the lower surface area. The large number of small pores also results in 600JD with a high surface area (868 m2/g). Among all samples, 600JD has the highest average pore size, pore volume ratio and SSA. However, the volume ratio of small to large pores in both MC-GA and MC-GA-A is ∼ 0.15 for both biomass-derived carbons, which is about half of that in 600JD. Given the different roles of large and small pores in the mass transport and polysulfide confinement, it is rational to expect that, used as host materials, the biomass-derived carbons with appropriate distribution of pores will enable LSBs with excellent electrochemical performance.
Table 1. Structure parameters of the porous carbons.
Empty Cell | Average Pore Diameter (nm) | Pore Volume < 5 nm (PS, cm3/g) | Pore Volume >10 nm (PL, cm3/g) | Pore Volume Ratio (PS/PL) | Total Pore Volume (cm3/g) | SSA (m2/g) |
---|---|---|---|---|---|---|
600JD | 14.5 | 0.44 | 1.46 | 0.30 | 2.07 | 868.0 |
MC-GA | 12.0 | 0.07 | 0.47 | 0.15 | 0.56 | 257.0 |
MC-GA-A | 8.0 | 0.08 | 0.58 | 0.14 | 0.69 | 533.0 |
The promises of biomass-derived carbons can be observed from their advantages as host materials of sulfur cathodes in improving the LSB performance. Fig. 6a shows the CV curves of freshly assembled LSB cells in the initial scans. All hosts present a remarkable reduction peak at ∼2.28 V (vs Li+/Li) followed by second one at ∼2.03 V (vs. Li+/Li), corresponding to the S8 to polysulfide (Sn2−, 4 ≤ n ≤ 8) and then to lower order polysulfides, in the cathodic scans [39]. In the subsequent anodic scans, two peaks, one at ∼2.23 V (vs. Li+/Li) and the other at ∼2.38 V (Li+/Li) are observed, corresponding to the conversion of Li2S2 or Li2S into soluble polysulfides and element sulfur respectively. Compared with 600JD, GA-derived hosts have CV peaks with higher intensity, the right-shifted cathodic peaks, and the left-shifted anodic peaks. The observations from CV measurements agree well with results obtained from the initial formation tests on LSBs. Fig. 6b to 6d show that all LSBs demonstrate two plateaus at ∼2.4 V (vs. Li+/Li) and ∼2.1 V (Li+/Li) in the discharge processes, two plateaus at ∼2.2 V (vs. Li+/Li) and ∼2.3 V (Li+/L). During the initial cycle, cells with GA-derived hosts exhibit overlapped voltage profiles, but slightly lower overpotential at the 2.1 V plateau during the discharge process and at the 2.2 V plateau during the charge process than the cell with 600JD (Fig. 6e). All these are consistent with observations from the CV measurements. The lower overpotential in the initial cathodic (discharge process of cell) and anodic (charge process of cell) sweeps might be attributed to the reduced polarization caused by the unique porous structure of GA-derived hosts with improved sulfur distribution, better contacts between sulfur and hosts, and higher conductivity of cathodes. The conversion-dissolution-diffusion process of the sulfur and polysulfides in the initial cycle can rearrange the distribution of sulfur and lower the influence of the host on the conductivity of the cathodes [40]. The relatively higher ratio of crystalline graphite phase might also be a beneficial factor to reduce the polarization of cells with GA-derived hosts in the initial, given the high electronic conductivity of graphite [41], but its contribution might not be significant since all cells have almost overlapped voltage curves at every plateau during the third formation cycle (Fig. 6f). In the presence of baseline 600JD, the LSB can deliver a relatively higher capacity of ∼1000 mAh/g during the initial discharge process (Fig. 6b and 7d), while ∼910 mAh/g by both biomass-derived carbons (Fig. 6c to 6e). This implies the excellent dispersity and high utilization of sulfur in all hosts with high surface area. After three formation cycles, cells with MC-GA-A and 600JD retain the capacity of ∼820 mAh/g and ∼800 mAh/g in MC-GA (Fig. 6f). In other words, >87% of initial capacity is preserved in LSBs with both biomass-derived carbon hosts, while ∼82% for baseline 600JD, after three formation cycles. Particularly, >90% of initial capacity is retained in cells with the activated carbon of MC-GA-A. The higher capacity retention might be associated with the strong affinity of unique porous architecture in biomass-derived carbons to sulfur and polysulfides, which will be discussed below.
The superiority of biomass-based carbon hosts can also be found from the promising rate capacity and durability of LSBs. Irrespective of the host materials, the specific capacity delivered by LSBs decreases with the enhancement of current density. The specific capacity delivered by MC-GA-A is 843, 782, 721, 686 and 626 mAh/g at the current density of 0.1C, 0.2C, 0.5C, 1C and 2C respectively (Fig. 7a). The capacity delivered by MC-GA cathode is slightly lower. However, the capacity delivered by 600JD cathode drops dramatically from ∼800 mAh/g at 0.1C to ∼466 mAh/g at 0.5C and decreases gradually to ∼400 mAh/g at 2C (Fig. 7a). The advantages of biomass-derived carbon hosts can also be observed from the superior durability of LSBs (Fig. 7b). After 50 cycles, LSBs with 600JD exhibit only ∼326 mAh/g, which is ∼80% of the initial capacity and further decreases to <70% after 100 cycles (Fig. 7b). However, biomass-derived carbon hosts can retain 80% of the initial capacity (∼600 mAh/g) after 200 cycles. Especially, the activated MC-GA-A can deliver the highest capacity of ∼720 mAh/g after 200 cycles and retain 80% of the initial capacity (∼590 mAh/g) after 400 cycles. Table 2 summarizes the performance of LSBs with hosts obtained in this work and the representative biomass-derived carbon hosts reported by other researchers to date [42], [43], [44], [45], [46], [47], [48], [49], [50], [51], [52]. To the best of our knowledge, it is the first time to report such high capacity retention of a LSB with mere biomass-derived porous carbon hosts [25], [53], [54], and it is even comparable to those with catalytic hosts [55], [56], [57], [58], [59]. It is worthy to note that the zinc oxide in the GA-derived hosts might have little effect on the LSB performance since MC-GA-A demonstrated the best performance with the highest capacity, rate capability and durability here. Otherwise, the MC-GA host with more zinc oxide can demonstrate the best battery performance.
Table 2. Performance comparison of lithium-sulfur batteries with the state-of-the-art biomass-based carbon hosts.
Source | Sulfur loading (mg/cm2) | Initial discharge capacity (mAh/g) | Cycle number | Capacity of final cycle (mAh/g) | Cycling rate | References |
---|---|---|---|---|---|---|
Litchi shell | 0.8–0.96 | 1105 (0.1C) | 800 | 430 | 1C | [42] |
Coconut shell | 0.78 | 1500 (0.1C) | 400 | 517 | 2C | [43] |
Pomegranate residue | 2.1 | 1010 (0.1C) | 500 | 550 | 0.2C | [44] |
Banana peel | 1.96 | 1200 (0.2C) | 500 | 570 | 1C | [45] |
Tea waste | 1.2–1.5 | 744 (0.5C) | 100 | 499 | 0.5C | [46] |
Soybeans | 2.0 | 950 (0.1C) | 800 | 460 | 0.5C | [47] |
Tobacco stems | 1.1 | 1074 (0.1C) | 100 | 745 | 0.2C | [48] |
Yam | 1.0–1.1 | 1556 (0.2C) | 450 | 401.2 | 1C | [49] |
Ferns | N/A | 1377 (0.1C) | 100 | 500 | 0.2C | [50] |
Wood chips | 1.17–3.33 | 1302 (0.1C) | 50 | 843 | 0.1C | [51] |
Yeast | 1.12 | 800 (0.1C) | 100 | 642.7 | 1C | [52] |
Garlic acid | 1.6 | 910 (0.1C) | 400 | 590 | 0.5C | This work |
To better understand the effect of biomass-derived carbon hosts on the improved LSB performance, the chemical analysis and TGA measurements were conducted on active materials. The element mapping images (Fig. 8a to 8c) demonstrate no elemental sulfur observable between carbon particles, indicating that no sulfur was left outside the particles of all carbon hosts. TGA (Fig. 8d) results show that all active materials contained ∼50 wt% sulfur. In addition, the sublimation of pure sulfur exhibits a single-slope-like curve, which starts at ∼150 °C and ends at ∼250 °C. However, a two-slope-like feature, one steep in the region of 150 °C – 250 °C and the other gentle in the region of 250 °C–400 °C, is observable for all active materials with carbon hosts. It is believed that appearance of steep slope corresponding to the volatilization of sulfur from large pores in carbon hosts, while gentle one from small pores [60], [61]. The steeper the slope, the easier the volatilization of sulfur from the host. When the temperature is below 250 °C, TGA curves obtained from all active materials almost overlap with that of pure sulfur, indicating the negligible affinity of large pores in the hosts to sulfur. The amount of sulfur contained in small and large pores can be calculated based on the mass weight losses occurred in two temperature regions. Fig. 8e shows that MC-GA-A has ∼18 wt% sulfur (50 wt% in total) filled in small pores, ∼13 wt% for MC-GA, and only ∼8 wt% for 600JD. This suggests that the small pores have strong confinement on sulfur. However, too low ratio of large to small pores might retard the diffusion of sulfur and lower the utilization of small pores in 600JD particles for sulfur accommodation. However, the appropriate distribution of pores in biomass-derived carbons benefits the sulfur infiltration into small pores. The high accessibility of small pores to sulfur benefits can benefit the ion transport in the sulfur cathode and thus the high utilization of sulfur at high rates. This is corroborated by the superior rate capability of LSBs with GA-derived carbon hosts over those with the baseline 600JD.
The biomass-derived carbons do not only trap sulfur, but also have the capability to anchor polysulfides. The observations from adsorption measurements (Fig. 9a) demonstrate that, after contact with biomass-derived carbons, the yellowish coloration of Li2S6 solution diminished. From 600JD to MC-GA and MC-GA-A, the yellowish coloration becomes lighter, indicating the strongest affinity of MC-GA-A to the polysulfides. It has been well recognized that the porous structure of the host plays a crucial role in determining the affinity of host materials, in which the small pores provide sites to anchor polysulfides while large pores for fast mass transport [25]. Although having the highest pore volume of small pores (Fig. 5 and Table 1), too few large pores retard the polysulfide diffusion and lower the utilization of small pores in 600JD particles to trap the polysulfides. Observations from TGA and adsorption measurements agree well with results from nitrogen sorption that MC-GA-A has a suitable ratio of large to small pores and appropriate number of small pores. The strong affinity of cathodes can also benefit the kinetics of polysulfide conversion. This was corroborated by the EIS measurements (Fig. 9b). Regardless of hosts employed, EIS spectra collected from all LSBs are composed of two depressed semicircles and an inclined line. The semicircle in the high-frequency region is generally related to the charge-transfer process (Rct/CPEdl) at the interface between conductive agent and the electrolyte, while the other in the middle-frequency region associated with the formation of solid-electrolyte-interface (SEI) films (Rf/CPEf) [62]. The inclined line in low-frequency region ascribed to the diffusion of ions (CPEdiff) in the sulfur cathode. With the assistance of the equivalent circuit (insert in Fig. 9b), the simulated results show that the ohmic resistance (Re) in both biomass-derived carbons is almost identical and slightly higher than that of 600JD (Table 3). This indicates the excellent electronic conductivity in all sulfur cathodes. However, MC-GA-A sulfur cathode has the lowest value of Rct (14.05 Ω), while 16.45 Ω is for MC-GA and 22.46 Ω is for 600JD. Similar result can be found on Rf for all LSBs. Lower Rct indicates better accessibility of active material in biomass-derived carbon sulfur cathodes. Lower Rf implies that cathodes with biomass-derived carbons have thinner SEI films with less soluble polysulfides than that with 600JD. Thus, results from TGA, absorption measurement and EIS spectra confirm that the appropriate porous structure in biomass-derived carbons promotes both affinity of cathodes to sulfur/polysulfides and mass transport, leading to the significantly improved LSB performance.
Table 3. Fitted values for the equivalent circuit elements by simulations of impedance spectra in Fig. 9b.
Empty Cell | Re (Ω) | Rct (Ω) | Rf (Ω) |
---|---|---|---|
600JD | 1.81 | 22.46 | 7.74 |
MC-GA | 2.71 | 16.45 | 5.54 |
MC-GA-A | 3.04 | 14.05 | 5.07 |
4. Conclusions
Low cost and highly porous carbons were successfully prepared from biomass sources. Using as hosts of cathodes in LSBs, the biomass-based carbons deliver a high reversible capacity of > 800 mAh/g and retain > 80% of initial capacity after 200 cycles. Especially, the activated carbons exhibited 80% capacity retention after 400 cycles. The promising LSB performance can be ascribed to the unique porous architecture of biomass-based carbons. The small pores in biomass-based carbons can provide more sites to anchor sulfur and polysulfides, while large pores provide channels for fast transport of ions.
CRediT authorship contribution statement
Jian Yang: Investigation, Data curation, Writing – original draft. Guanyi Wang: Investigation. Ana Paula Teixeira: Writing – review & editing. Glaura Goulart Silva: Writing – review & editing. Zachary Hansen: Investigation. Maruj Jamal M Jamal: Investigation. Kevin Mathew: Validation, Data curation. Jie Xiong: Validation, Data curation. Tiffany Zhou: Validation. Michal Mackowiak: Resources, Project administration. Paul Dan Fleming: Writing – review & editing. Qingliu Wu: Conceptualization, Methodology, Supervision, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgement
This work was supported by the Xponential Battery Materials B. V. (“XBM”). The authors are also grateful for the carbon materials from Centro de Tecnologia em Nanomateriais e Grafeno CTNano at Federal University of Minas Gerais. This work made use of the Talos F200X G2 S/TEM that is funded in part through NSF MRI award #2018587.
Data availability
Data will be made available on request.
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