Metal Sulfides@Carbon Microfiber Networks for Boosting Lithium Ion

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Energy, Environmental, and Catalysis Applications

Metal Sulfides@Carbon Microfiber Networks for Boosting Lithium/SodiumIon Storage via A General Metal-Aspergillus Niger Bioleaching Strategy Junzhi Li, Lili Wang, La Li, Chunxiao Lv, Igor V Zatovsky, and Wei Han ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21976 • Publication Date (Web): 05 Feb 2019 Downloaded from http://pubs.acs.org on February 6, 2019

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ACS Applied Materials & Interfaces

Metal Sulfides@Carbon Microfiber Networks for Boosting General

Lithium/Sodium-Ion Metal-Aspergillus

Storage

Niger

via

A

Bioleaching

Strategy Junzhi Li,† Lili Wang,*, ‡ La Li,† Chunxiao Lv,§ Igor. V. Zatovsky,† Wei Han*,†,‖ †Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun, 130012, China. ‡State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun 130012, PR China. §Collaborative Innovation Center for Marine Biomass Fibers, Materials and Textiles of Shandong Province, School of Environmental Science and Engineering, Qingdao University, Qingdao 266071, P. R. China ‖International Center of Future Science, Jilin University, Changchun City 130012, PR China

ACS Paragon Plus Environment

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ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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ABSTRACT: Fabrication and design of electrodes that transfer more energy at high rates is very crucial for battery technology because of increasing need for electrical energy storage. Usually, reducing materials volume expansion and improving the electrical conductivity can promote electron and Li+/Na+ ion transfer in nanostructured electrodes and improve rate capability and stability. Here, we demonstrate a general metal-aspergillus niger bioleaching approach for preparing novel fungus–inspired electrode materials that may enable high performance lithium– ion/sodium–ion batteries with one–dimension architectures. The fungus function as natural templated to provide a large of nitrogen/carbon source, which are functionalized with metal sulfides

nanoparticles,

yielding

various

metal

sulfides

nanoparticles/nitrogen–doped

carbonaceous fibers (MS/NCF (MS= ZnS, Co9S8, FeS, Cu1.81S)) with high conductivity. In addition, the as–obtained MS/NCF own uniform fibers architecture and abundant porous structure, which can also enhance the storage ability for LIBs and SIBs. Taking ZnS/NCF as example, the material exhibits high specific capacity up to 715.5 mAh g-1 (100 cycles) and 455 mAh g-1 (50 cycles) at 0.1 A g-1 for LIBs and SIBs, respectively. This versatile approach for employing fungus as sustainable template to form high–performance electrodes may provide a systematic platform for implementing advanced battery designs.

KEYWORDS: Aspergillus niger fungus, biotemplate, transition–metal sulfides, N–doped, lithium/sodium ion batteries.


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1. Introduction Considerable demand for portable electronic devices has greatly sparked the progress of electrical energy storage (EES) devices.1-8 Today, most batteries have successfully been applied in electronics with mobile/portable devices making up about 60% of all electronics. Such large applications promote the demand for high–performance and long cycle stability batteries with low cost, and high safety. To date, most efforts have been made to explore a large variety of anode materials to enhance the electrical conductivity of anodes and effectively avoid volume expansion. For example, specific nanostructures (such as egg–yolk, core–shell, tube–in–tube and hollow) can alleviate the volume variation.9-18 And the fabrication of nanosized nanoparticles can augment the contact area between electrode and electrolyte and retard serious volume variation in the charge/discharge cycling, resulting in the enhancement of the cycling and rate performance.19-27 Despite the recent advances in variety anode materials design, the development of high–performance functioned particles with economic synthesis routes and environmental benignity is still a recent major challenge. Natural biomaterials have offered attractive and lasting inspirations building blocks for environmentally benign materials synthesis.28 Various biomaterials including virus, bacteria, microorganisms and peptides serve as building blocks or biotemplate, assembled into nanostructures with inorganic material, and applied in electronic devices and energy–storage development.29-34 For EES, the biotemplated synthesis can guide sophisticated assembly of materials and biological molecules into fantastic architecture that exhibit unique structural properties and biological activity. In addition, biological materials are typically environmentally friendly, plentiful in renewable supply and biocompatible—peculiarities which make them serve as a natural carbon suppliers. These carbonaceous materials derived from the biomass exhibit a


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higher capacity for energy storage than carbon nanotubes and graphene because of their natural biological architectures.35-38 All these factors have motivated the development of novel composites based on biomass derived carbons with economic synthesis routes. Nevertheless, the researchers paid little attention to Aspergillus niger. Aspergillus Niger as a special species can be used for bioleaching, which can mobilize most metals by microbial metabolism. In addition, the hydroxyl groups (-OH) in the chitin of cell wall can also adsorb metal ions (Figure 1A). This is a fascinating natural biologic system, which can efficiently localize substances. However, there is no work based on the metal-Aspergillus niger bioleaching strategy to fabricate carbon composites for electrochemical energy storage devices. Thus, it arouses our great interest to explore the promising material. Herein, we first develop a facile and general metal-Aspergillus niger bioleaching approach to prepare a series of metal–sulfides nanoparticles (MS–NPs) embedded in biomass derived onedimensional carbonaceous fibers (1D NCF) with nitrogen–rich. The 1D NCF can prevent the volume variations of MS–NPs and avoid the direct reaction with electrolyte. Due to these features, the obtained MS/NCF (MS=ZnS, Co9S8, FeS, Cu1.81S) show excellent cycling and rate performance as anodes for lithium/sodium storage. Taking ZnS/NCF for an example, When evaluated as anode for lithium storage, the ZnS/NCF shows high reversible capacity of 715.5 mAh g-1 at 0.1 A g-1, high rate capability (302.4 mAh g-1 at 5 A g-1) and long cycling capability (91% and 78% reversible capacity retention after 700 and 1000 cycles). Furthermore, the ZnS/NCF also show excellent rate performance (231.7 mAh g-1 at 5 A g-1) and stable cycling capability of 455 mAh g-1 at 0.1 A g-1 for 50 cycles and 365.2 mAh g-1 at 1 A g-1 for 180 cycles for SIBs.


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2. Experimental section 2.1.1 Synthesis of Aspergillus Niger: In a 500 mL conical flask, glucose (10 g) and peptone (8 g) were added in deionized water (500 mL). The resulting culture medium was sterilized at high– temperature (121 °C), and the cooled down to room temperature. The spores of aspergillus niger were added to the culture medium in a ultra–clean paltform. After that, the conical flask was placed in oscillation incubator for 3 days at 35 °C. 2.1.2 Synthesis of MS/NCF: 0.1 M zinc nitrate hexahydrate and 0.1 M thioacetamide (TAA) were mixed with 300 mL ethanol solution in the conical flask. The prepared aspergillus niger was transferred into the solution and put into the oscillation incubator for 3 days. The resulting product was washed with ethanol solution, and then freeze–dried at −80 °C in vacuum. The dried precursors pyrolyzed at the temperature of 700 °C for 2 h ( 2 °C min-1) under nitrogen. The final product was denoted as ZnS/NCF. The Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF were prepared with cobalt nitrate hexahydrate, iron chloride hexahydrate, and cupric nitrate trihydrate by the same method. 2.2 Characterization: The microstructure and XRD patterns of MS/NCF product were investigated using scanning electron microscopy (SEM, Magellan 400), transmission electron microscopy (TEM, JEOL JSM–2010F) and powder diffractometer (RIGAKU, D/MAX 2550 V). Raman spectra and X–ray photoelectron spectroscopy (XPS) were recorded on Raman spectroscopy (Renishaw), using a 514.5 nm laser excitation and VG ESCALAB MK II electron spectrometer. Thermogravimetry analyses (Henven Scientific Instrument, HCT-3) were tested between 30 and 900 °C (10 K/min) in Ar atmosphere. Nitrogen adsorption-desorption isotherms were carried out through a Brunauer–Emmett–Teller (BET, Beijing JW–BK132F).


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2.3 Electrochemical measurements: The electrodes were obtained by mixing 70% active material, 20% acetylene black, and 10% polyvinylidene difluoride in N–methylpyrrolidone. Subsequently, the homogeneous slurry was coated on a Cu foil. The average mass loading of each electrode was 1.05-1.12 mg/cm2. For LIBs, lithium foil and Celgard 2400 were used as the counter electrode and separator. 1 M LiPF6 dissolved in 1:1 ethylene carbonate(EC), and dimethyl carbonate (DMC) was used as electrolyte. As for the SIBs, sodium foil and Whatman glass fiber (GF/D) was used as counter electrode and the separator. The electrolyte was 1 M NaCF3SO3 in diethylene glycol dimethyl. The cells (CR2032) were assembled in an Ar-glovebox. The discharge–charge cycling measurements were conducted on a LAND CT2001A system. The CV and EIS tests were performed on a electrochemical workstation (IVIUM, Netherlands) at 0.2 mV s-1.


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3. RESULTS AND DISUSSION

Figure 1. (A) Illustration of the bioleaching in a cellular biologic system of Aspergillus niger. (B) Schematic illustration on the formation of the MS/NCF (MS= ZnS, Co9S8, FeS, and Cu1.81S). Figure 1B illustrates the fabrication process of MS/NCF. First, the aspergillus niger was obtained by the method of shake culture. The microstructure of the filamentous aspergillus niger is shown in Figure S1. After that, the prepared aspergillus niger was dipped in the ethanol solution including metal (Mn+) and TAA for 3 days at 35 °C. In the process, aspergillus niger can mobilize the metal by microbial metabolism. In addition, the multitudinous active groups – OH exist in chitin can stablely combine with the Mn+.39 It can be understood that the Mn+ is compactly coated by the chitin. The precursor products were treated by freeze–drying. After subsequent pyrolysis, various MS/NCFs were obtained. Figure 2A shows the advantages of


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MS/NCF in enhancing LIBs and SIBs. As is known, carbon–coated and N–doped have been considered as an excellent approach to increase the electrical conductivity and stability of the electrode materials. The cell wall of the aspergillus niger is primarily composed of chitin and glucan that possess abundant natural nitrogen and carbon. Thus, the direct pyrolysis of the aspergillus niger can acquire homogeneous high quality N–doped carbonaceous fibers. Figure 2B reveals a typical 1D fibrous structure of ZnS/NCF with the diameter of about 2 μm. It can be seen that the ZnS nanoparticles were embedded in the carbonaceous fibers. Moreover, the interconnected porous channels can be observed within the fibers (inset of Figure 2B). The particular structure can provide enough contact area of electrode with electrolyte. This is properly beneficial for increasing the transfer rates of Li+/Na+ and electrons. The 1D fibrous structure of ZnS/NCF with a rough surface was confirmed by the scanning transmission electron microscopy (STEM) image (Figure 2C), which is in agreement with the SEM image. The corresponding selected–area electron diffraction (SAED) pattern (inset of Figure 2C) reveals several concentric rings, corresponding to the ZnS phase, demonstrating the good crystallinity of the ZnS/NCF. To further investigate the detailed structure, the HRTEM and inverse fast Fourier transform (IFFT) are investigated. Figure 2D exhibits obvious lattice fringes of 0.291 nm, which can be assigned to the (101) plane of ZnS. In addation, the HRTEM also shows that the ZnS NPs are embedded into the carbonaceous fiber. Figure 2E presents the STEM mapping result, revealing that the Zn, C, S, and N elements are homogeneously distributed along the fiber.


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Figure 2. (A) Schematic diagram of the features of MS/NCF in boosting LIBs and SIBs performance. (B) SEM image, (C) STEM image, SAED (inset), (D) HRTEM image, (E) the STEM mapping images and (F) XRD pattern of ZnS/NCF. X–ray powder diffraction (XRD) pattern further confirmed the presence of ZnS (JCPDS: 65– 7411) and graphite (2θ=25.0°) phase (Figure 2F). Raman spectrum measurement on the ZnS/NCF composites in Figure 3A indentifies the defective carbon (D–band) and graphitic carbon (G–band) located at about 1354 cm-1 and 1588 cm-1, corresponding to the relevant reported.40 The calculated value of D to G–band (ID/IG) is about 0.9, suggesting a highly graphitic structure.29 The thermogravimetric tests (TGA, Figure 3B) was performed to determine the carbon content of the ZnS/NCF. By calculation, the content of carbonaceous fiber in ZnS/NCF is about 15.8%. The N2 sorption isotherms and pore size distribution of the ZnS/NCF are displayed in Figure 3C. The ZnS/NCF possesses a large specific surface area of 194.717 m2 g-1. Moreover, the typical type IV adsorption isotherm with a hysteresis loop indicates that the micropore and mesopore exist in the sample. The most mesopores are centered at about 2–5 nm


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(Figure 3D). Such specific surface area and mesopores can impede the volume expansion upon cycling.

Figure 3. (A) Raman spectrum of ZnS/NCF. (B) The TGA spectra of ZnS/NCF under air atmosphere. (C) N2 sorption isotherms of ZnS/NCF. (D) corresponding pore size distribution of ZnS/NCF. XPS was carried out to analyze the elemental composition component, confirming the presence of C, N, S, and Zn elements. The Figure 4A shows the high–resolution C 1s spectrum. Three components at 284.1, 284.6, and 285.6 eV can be attributed to C–C/C=C, C–S, and C=N, which confirms the doping of nitrogen into carbonaceous fibers and effective combination between the carbonaceous fibers and MS. The XPS peak of N 1s (Figure 4B) exhibits three peaks at 398.5, 400, and 400.8 eV, corresponding to pyridinic, pyrrolic N, and graphitic N.41


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These suggest that the defects are introduced into carbonaceous fibers by N doping, thus promoting transfer of Li+/Na+. Moreover, the S 2p high–resolution spectra displays two peaks at 161.8 and 162.8 eV, which corresponds to S 2p2/3 and S 2p1/3 (Figure 4C). As regards the Zn 2p spectra, the peaks at 1022.0 and 1045.0 eV belong to Zn 2p2/3 and Zn 2p1/2 of Zn2+ (Figure 4D).

Figure 4. XPS spectras of ZnS/NCF: (A) C 1s, (B) N 1s, (C) S 2p, and (D) Zn 2p.


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Figure 5. The SEM images, HRTEM images, responding SAED pattern and STEM mapping of MS/NCFs: (A-E) Co9S8/NCF; (F-J) FeS/NCF and (K-O) Cu1.81S/NCF. More satisfactorily, the approach can be used to fabricate other MS/NCF, including Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF, as shown in Figure 5. The similar fibers can be seen in the all samples (Figure 5A-B, F-G , K-L, and S2A-C). Notably, there are no obvious porous channels in the fiber of Cu1.81S/NCF, which could be due to the electronegativity and binding energy of metal.20 The specific area and porous structure were further characterized by the BET test (Figure S3A, B). The HRTEM of Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF in Figure 5C, H, m show that the nanoparticles are distributed in the carbonaceous fiber. The enlarged HRTEM and SAED clearly display the lattice fringes, bright rings and scattered dots, corresponding to the phase of Co9S8, FeS, and Cu1.81S (Figure 5D, I, N, and inset image). XRD pattern (Figure S3C) and Raman spectrum (Figure S3D) reveal that the compound includes MS and graphite phase


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with index to Co9S8/NCF (JCPDS: 86–2273), FeS/NCF (JCPDS: 05–3526), and Cu1.81S/NCF (JCPDS: 41–0959) materials, respectively. The carbon content of the Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF composites was also determined by calculation (Figure S4). STEM elemental mapping images on each nanofiber display uniform distribution of the transition metals, S, C and N elements (Figure 5E, J, O, which is furhter comfirmed by using XPS (Figure S5-S7). All results demonstration that our reported biotemplated synthesis can be utilized as a guideline to design other nanomaterials. The MS/NCFs were evaluated as anode for lithium storage. Figure 6A shows the cyclic voltammetry (CV) curves of ZnS/NCF (0.2 mV s-1) between 0.01 and 3 V for the initial three cycles. An obvious broad cathodic peak at 0.7–0.005 V is observed during the first CV curve, which can be attributed to the insertion of Li+ and formation of solid electrolyte–interphase (SEI) layer, resulting in an irreversible capacity decay.42 In the ensuing cycles, the cathodic peak appears at 0.5–0.8 V corresponding to the formation of Li2S; the anodic peak at about 1.3 V indicates the conversion of Li2S and Zn to ZnS, and some weak peaks appear in the oxidation process, representing the multistep alloying transformation. In addition, the subsequent two CV curves show slight change, demonstrating the good stability. Figure 6B shows the galvanostatic charge/discharge profiles of ZnS/NCF at 0.1 A g-1. The first discharge and charge specific capacities are 1182.8 and 751.1 mAh g-1, and the corresponding coulombic efficiency (CE) is 63.5%. The low CE and capacity loss is mainly ascribeed to the presence of SEI layer. Because the ZnS/NCF electrode has abundant porous structure, which can consume more electrolyte to form the SEI layer at anode surfaces during the first discharge process. In addition, the conversion reaction of ZnS to Zn and Li2S is also is associated with the irreversible formation of the SEI layer. All of this leads to low CE. The rate capability of ZnS/NCF is displayed in Figure


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6C. The reversible specific capacities of 700.4, 600.9, 508.1, 449.5, 394.9, and 302.4 mAh g-1 are achieved at 0.1, 0.2, 0.5, 1, 2, and 5 A g-1. Furthermore, the ZnS/NCF can still deliver a specific capacity of 705.8 mAh g-1, when the current density is recovered to 0.1 A g-1.

Figure 6. (A) CV curves of ZnS/NCF in the initial three cycles. (B) Galvanostatic charge– discharge curves of ZnS/NCF at 0.1 A g-1. (C) Rate performance of the ZnS/NCF at various current densities. (D) Cycle performance of ZnS/NCF, Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF


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at a current density of 0.1 A g-1. (E) Cycle performance of ZnS/NCF at a current density of 1 A g-1. The cycling performance is also a significant evaluating indicator for LIBs. As shown in Figure 6D,. the MS/NCF (ZnS/NCF, Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF) have the reversible specific capacity of 715.5, 605.0, 689.8, and 534.7 mAh g-1 after 100 cycles at 0.1 A g1,

respectively, More importantly, the ZnS/NCF reveals a increase of CE from 63.5% for the

initial discharge and charge to 97.9% for the following 100 cycles, indicating the excellent reversibility. The cycle performance of MS/NCF is much higher than the individual NCF (188.3 mAh g-1) (Figure S8), indicating the synergistic effect among MS and NCF. Moreover, even at high current densities of 1 A g-1, the ZnS/NCF also exhibits a remarkable cycle stability. As shown in Figure 6E, the ZnS/NCF still maintains a a specific capacity of 373.4 mAh g-1 after 1000 cycles. The MS/NCF presents an excellent lithium–ion storage performance compared with other MS–based materials for LIBs anodes (Table S1). The CV curves and other performance of Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF are shown in Figure S9–11. In addition to SIBs, the storage performance of MS/NCF was further evaluated. The initial three CV curves of ZnS/NCF at 0.2 mV s-1 between 0.01 and 3 V are displayed in Figure 7A. Similarly, the irreversible broad peak between 0.005 and 0.7 for the initial cycle can be ascribed to intercalation reaction of Na+ into ZnS, in which the ZnS convert to Zn, and the formation of SEI layer. The peak located at about 1.0 V for the charge scan is mainly due to the resulfurization of metallic Zn to ZnS. All the reduction/oxidation peaks in the subsequent CV curves show negligible change, demonstrating the good stability and electrochemical reversibility of ZnS/NCF. The representative galvanostatic charge/discharge profiles of ZnS/NCF at 0.1 A g-1 are illustrated in Figure 7B. The ZnS/NCF presents a specific capacities of


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835.7 and 501.6 mAh g-1 for the first discharge and charge, with a low CE of 60%. The capacity loss can be attributed to the formation of SEI film and irreversible electrolyte decomposition. As for the rate performance, the reversible capacities of ZnS/NCF are 540.2, 465.9, 386.2, 337.5, 291.5, and 231.7 mAh g-1 at 0.1, 0.2, 0.5, 1, 2, and 5 A g-1, respectively (Figure 7C). As the current density recovers to 0.1 A g-1, the ZnS/NCF electrode can resume a significant reversible capacity of 463.4 mAh g-1, which demonstrates the remarkable structural stability. The electrode of ZnS/NCF was further evaluated by the cycling stability test. Figure S12 presents the cycle performance and CE at 0.1 A g-1. The ZnS/NCF retains a reversible capacity of 455 mAh g-1 after 50 cycles, which is much better than the NCF (98.2 mAh g-1) (Figure S13). Even at a higher current density of 1 A g-1, the ZnS/NCF can still deliver a high capacity of 365.2 mAh g-1 for 180 cycles (Figure 7D). Table S2 exhibits the comparison of storage performance of MS–based materials for SIBs. In addition, the other electrochemical performances of Co9S8/NCF, FeS/NCF, and Cu1.81S/NCF can be seen in Figure S14–16. The excellent storage performance of MS/NCF can be ascribed to the supports of the biomass derived carbonaceous fibers, improving the electrical conductivity and enhancing the diffusion rate of the Li+/Na+ and electron. Further, the natural N–doped leads to the formation of imperfection in the carbonaceous fibers, which can accelerate the intercalation of Li+/Na+.43 In addition, the dispersive MS–NPs with the carbon supports have fairly short diffusion pathway compared with the normal materials, remarkably facilitating the diffusion of Li+/Na+. Meanwhile, biomass derived carbonaceous fibers greatly restrains the volumetric expansion and then reveals the excellent specific storage capacity (Figure 8).


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Figure 7. (A) CV curves of ZnS/NCF in the initial three cycles. (B) The galvanostatic charge– discharge curves of ZnS/NCF at 0.1 A g-1. (C) Rate performance of the ZnS/NCF at various current densities. (D) Cycle performance of ZnS/NCF at 1 A g-1. To further investigate electrochemical kinetics of MS/NCFs, the electrochemical impedance spectroscopy (EIS) tests over a frequency range between 0.01 Hz and 100 kHz are shown in Figure S18 for LIBs and SIBs (the equivalent circuit is shown in Figure S17). All Nyquist plots of MS/NCF show a depressed semicircle and a inclined line in the high frequency area and low frequency area. The semicircle reflects the charge transfer (Rct) resistance. Apparently, the Rct of ZnS/NCF, Co9S8/NCF , FeS/NCF, and Cu1.81S/NCF are 100.4, 174.8.4, 151.5, and 178.3 Ω for LIBs (Figure S18A), respectively, suggesting the fast charge transfer. As for the SIBs, the EIS results display that the Rct of ZnS/NCF, Co9S8/NCF , FeS/NCF, and Cu1.81S/NCF are 9.3, 10.2,


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11.8, and 12.4 Ω (Figure S18B). Overall, these facts demonstrate that the combination of MS with the carbonaceous fibers greatly reduce the diffusion distance for Li+/Na+ and enhance the charge transfer,44 resulting in the improvement of the rate ability and cycling performance.

Figure 8. Schematic illustration of the high storage performance of MS/NCF. The structural stability of ZnS/NCF was evaluated by the TEM measurements after cycles (Figure S19–S20). Figure S19A shows the STEM of the ZnS/NCF after 50 cycles for the LIBs. Obviously, the morphology of the ZnS/NCF still maintains the original fiber structure. Furthermore, the HRTEM also can demonstrate the stability of morphology. As shown in Figure S19B, D, the obvious lattice spacing of 0.291 nm, corresponding to the (101) plane of the ZnS can still be observed. Similarly, the STEM of ZnS/NCF after cycles for SIBs is depicted in Figure S20A. The fiber structure is still well preserved during the charge/discharge process of Na+. The Figure S20B, D shows the HRTEM and IFFT of ZnS/NCF and display the identical (101) plane of ZnS. In addition, the SAED also confirms the crystallographic plane of ZnS (Figure S19C and Figure S20C). Once again, the carbonaceous fibers provide the large void to prevent the volumetric expansion. Thus, the intact morphology can be maintained during cycling.


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4. CONCLUSIONS To summarize, we have developed a general metal-aspergillus niger bioleaching approach for the first time to synthesize MS/NCFs. The 1D carbonaceous fiber–based electrode composed of metal sulfides nanoparticles and natural nitrogen/carbon source addressed the main issues of volumetric expansion and low electrical conductivity and demonstrated excellent storage ability for LIBs and SIBs. Namely, the material exhibits high specific capacity (715.5 mAh g-1 at 0.1 A g-1 for 100 cycles), exceptional rate ability (302.4 mAh g-1 at 5 A g-1), and excellent stable capacity (373.4 mAh g-1 at 1 A g-1 after 100 cycles) for LIBs, together with a outstanding specific capacity of 455 mAh g-1 at 0.1 A g-1for 50 cycles and 365.2 mAh g-1 at 1 A g-1 for 180 cycles for SIBs. More importantly, the finding in this work can be utilized as guideline to design high–performance electrodes with other nanomaterial systems for the energy storage and conversion or variety of applications. ASSOCIATED CONTENTS Supporting Information Additional, photograph, SEM, XRD, and electrochemical characterizations and additional Tables. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected] Author Contributions


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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ACKNOWLEDGMENT The authors sincerely acknowledge financial support from the National Natural Science Foundation of China (NSFC Grant No. 21571080, 51502110)

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Table of Content (TOC)

The fungus function as natural templated to provide a large of nitrogen/carbon source, which are functionalized

with

metal

sulfides

nanoparticles,

yielding

various

metal

sulfides

nanoparticles/nitrogen–doped carbonaceous fibers with high conductivity. Such design exhibits a fascinating storage ability for LIBs/SIBs.


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Metal Sulfides@Carbon Microfiber Networks for Boosting Lithium Ion

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