MoS2 Nanosheets Vertically Grown on Carbonized Corn Stalks as

Subscriber access provided by UNIVERSITY OF TOLEDO LIBRARIES

Energy, Environmental, and Catalysis Applications

MoS2 Nanosheets Vertically Grown on the Carbonized Corn Stalks as Lithium-Ion Battery Anode Luxiang Ma, Binglu Zhao, Xusheng Wang, Junfeng Yang, Xin-Xiang Zhang, Yuan Zhou, and Jitao Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04170 • Publication Date (Web): 14 Jun 2018 Downloaded from http://pubs.acs.org on June 14, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 24 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

ACS Applied Materials & Interfaces

MoS2 Nanosheets Vertically Grown on the Carbonized Corn Stalks as Lithium-Ion Battery Anode Luxiang Ma,a,b,c,d Binglu Zhao,d Xusheng Wang,d Junfeng Yang,dXinxiang Zhang,d Yuan Zhou,*a,b Jitao Chen*d a

Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources,

Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, P.R. China b

Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, China

c

University of Chinese Academy of Sciences, Beijing 100049, P.R. China

d

College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871,P.R.

China

ACS Paragon Plus Environment

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

ABSTRACT. In the work, MoS2 nanosheets are vertically grown on the inside and outside surfaces of the carbonized corn stalks (CCS) by a simple hydrothermal reaction. The vertically grown structure can not only improve the transmission rate of Li+ and electrons but also avoid the agglomeration of the nanosheets. Meanwhile, a new approach of biomass source application is presented. We use CCS instead of graphite powders, which can not only avoid the exploitation of graphite resources, but also be used as a matrix for MoS2 growth to prevent the electrode from being further decomposition during long cycles and high currents density. Meanwhile, the lithium-ion batteries (LIBs) show remarkable electrochemical performance. It demonstrates a high specific capacity of 1409.5 mA g-1 at 100 mA g-1 in the initial cycle. After 250 cycles, the discharge capacity is still as high as 1230.9 mAh g-1. Even at 4000 mA g-1, it shows the special capacity reaches to 777.7 mAh g-1. Furthermore, the MoS2/CCS electrodes show excellent long cycling life, and the specific capacity is still up to ~500 mAh g-1 at 5000 mA g-1, after 1000 cycles.

KEYWORDS. MoS2; carbonized corn stalks; vertical growth structure; long-term cycling life; lithium ion battery


Page 2 of 24

Page 3 of 24 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


1. Introduction Graphite, as a traditional anode material, has been immensely used in LIBs. Despite the low price of the graphite,1 it still faces many problems, such as the low theoretical capacity and very limited rate performance.2 More importantly, with the increasing demand of graphite from artificial mining for LIBs, graphite will one day encounter the depletion of resources like oil and natural gas.3 Recently, due to its special electrochemical properties, transition-metal sulfide has attracted people's attention. Especially, the MoS2, similar to graphene with two-dimensional layered structure, has been widely used in LIBs.4-6 However, it is still full of challenges to practically apply MoS2 for LIBs in industry due to the poor electron conductivity, volume expansion, and agglomeration of nanoparticles.4,

7-9

Especially, the high surface energy of

nanoparticles makes the MoS2 nanosheets intermittently stacked together,10 hindering the transmission of Li+ and electrons. In order to overcome the consumption of graphite and the inherent shortcoming of MoS2 materials, all efforts are being made to enhance the lithium storage performance. One of the most effective strategies is to combine MoS2 with other materials to form a unique nanostructure, which not only remains the properties of each counterpart, but also is able to show unique advantages, such as electron conductivity, mechanical performance and electrochemical property. The most common strategy is the combination of MoS2 and carbon materials such as rGO,11-13 Polypyrrole,14-16 acetylene black,17 amorphous carbon,8

CNTs,18,

19

CMK-320 and

graphene-like MoS2 nanoflowers.21 Although carbon materials show excellent properties, it is not fundamentally solving the problems arising from the stacking of MoS2 nanosheets. Therefore, it is necessary to introduce new carbon materials with structure design for directing growth of MoS2 in order to solve the problem arising from MoS2 nanosheets agglomeration and



the problem of decreasing graphite resources. In this research, MoS2 nanosheets are vertically grown on the inside and outside surfaces of the carbonized corn stalks (CCS) by a simple hydrothermal reaction, forming MoS2/CCS composites. As a byproduct of corn, corn stalk is an important biological resource, which is composed of cellulose, hemicellulose, lignin and some trace elements. In this reaction, MoS2 are vertically grown on the surface of the pores. Like ivory feet, MoS2 firmly attaches to the surface (Scheme 1).

Scheme 1 Schematic illustration of the formation process of MoS2/CCS composites 2. Results and discussion The structure information and phase identification of MoS2/CCS are obtained by X-ray powder diffraction (XRD). From Figure 1a, it is clearly visible that the diffraction peaks of MoS2/CCS and bare MoS2 coincide well together without any other visible phases. Similarly, the diffraction peaks of these two samples can correspond to the major peaks of the index MoS2 (JCPDS NO. 98-002-400).4,8,17 In particular, the (002) crystalline plane at 14.2°indicates S-Mo-S layers are orderly stacked, which is consistent with the TEM results (Figure S1).22 Notably, the (002) diffraction peak becomes relatively weak in the MoS2/CCS composites, indicating that the (002) plane growth of MoS2 in the composites materials are inhibited by the incorporation of the carbon.13,23, 24 Meanwhile, the broad (002) peak of the CCS is not observed in the MoS2/CCS,


Page 4 of 24

Page 5 of 24 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


implying a highly dispersive state of carbon in the composites, which is beneficial for electronic transmission.25 In addition to the broad peaks (2θ = 23°), no extra peaks are observed on the CCS, indicating that the substrate is amorphous carbon,24 suggesting that the MoS2 nanosheets arrays have been successfully implanted on the CCS.

Figure 1 (a) Profiles of the X-ray diffraction patterns of the bare MoS2, MoS2/CCS composites and CCS. (b) SEM image of pure MoS2 nanosheets. (c-e) SEM images of the MoS2/CCS. (f) TEM image of the MoS2/CCS composites, (g-h) Low and high magnifications of the TEM image of the MoS2/CCS composites. The microscopic morphologies of the electrode materials are obtained by scanning electron microscopy (SEM). MoS2 and MoS2/CCS show different morphologies. In Figure 1b, the MoS2 exhibits a two-dimensional layered-structure, and these layers are closely stacked together. Figures S2a and b are the top view and the sectional view of the CCS, respectively. In Figure S2a, the surface of the CCS has some rectangular grid. It is obvious that the surface of CCS is occupied by rows of uniform boxes. These lattices are surrounded by wall-like cell walls and the size of each lattice length and width are 40 um and 60 um, respectively. The cross section of the CCS in Figure S2b clearly shows that the rows of tubular material are densely packed together



and the tube diameter is between 2 and 8 µm. In addition, the tubulars are cut open from the middle. It is clear that a concave-shaped tube trough in turn side by side. Figures 1c-e show the morphology of MoS2/CCS composites. Obviously, the column of the tube is present in CCS (Figure 1c) in the cross-sectional view. Simultaneously, the tube is covered with a thick layer of MoS2 (Figure 1d). Figure 1e is an enlarged view of the catheter wall, indicating that the MoS2 is enveloped in the tube wall as the thickness of the outer layer reaches 831 nm. MoS2 is firmly attached on the tube wall, akin to plants’ root system. Compared to Figure 1b, the MoS2 in the Figure 1c is more evenly distributed and uniform in size. The transmission electron microscopy (TEM) plays a critical role in investigating the structure characteristics of the prepared MoS2/CCS composites. Obviously, MoS2 uniformly covers the surface of the CCS in Figure 1f. In contrast, the pure MoS2 is stacked together in the SEM (Figure 1b), suggesting that there is a specific interface between MoS2 and CCS.26 In Figure 1f, the bright and dark parts are the CCS and MoS2, respectively. The Mo and S elements are distributed on the CCS as demonstrated by the EDX result (Figure S3) Both Figures 1g and 1h come from the red line frame in Figure 1f. The lattice spacing of MoS2 is 0.63 nm, corresponding to (002) plane. 27-30 The result indicates that MoS2 nanosheets are vertically grown on the surface of CCS, rather than lie down or grown in other patterns.26, 29 Moreover, the lattice pacings of 0.27 nm and 0.63 nm from the Figure 4S correspond to the (100) and (002) planes, respectively.26, 30 The presence of the (100) plane is due to the curl of MoS2, which reduces the surface energy of the system and makes the nanostructure of MoS2 more stable.26, 31


Page 6 of 24

Page 7 of 24 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


Figure 2 (a) Raman spectra of the MoS2/CCS composites and pristine MoS2; (b) the D and G bands of the MoS2/CCS composites and CCS.

The structure information of pure MoS2 and MoS2/CCS will be further obtained by Raman spectroscopy. Figure 2a shows the Raman scattering of the composite sample. The spectra of pure MoS2 and MoS2/CCS composite have identical peaks between 350 and 450 cm-1.22 The two peaks of the bare MoS2 at ~ 377 and ~401 cm-1 correspond to the E12g mode and A1g mode.30, 32 In addition, we found the E12g and t A1g modes of MoS2/CCS at ~379 and 403 cm-1 .Comparing with each other, we found that the wavelengths increase by 2 and 3cm-1 in their respective modes. This result is consistent with the classical mode of coupled harmonic oscillators, which is believed due to the softening of the E12g and A1g vibration modes with an increase in layer numbers.22, 33



To further study the structural characteristics of the CCS, the Raman spectrum of the samples are measured in the region from 1000 to 1800 cm-1, as shown in Figure 3b. In both samples, two main peaks are detected and the peak at 1328 and 1597 cm-1, which can be assigned to the D the G bands, respectively.

13

Since the ID /IG measured by Raman spectroscopy can be a graphene

quality indicator,9, 34 the ratios of CCS and MoS2/CCS composites are calculated respectively as 1.04 and 1.07, suggesting the formation of MoS2 layers on the CCS promotes disorder in the carbon structure in the composites.


Page 8 of 24

Page 9 of 24 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


Figure 3 X-ray photoelectron spectroscopy. (a) XPS spectra of MoS2/CCS composites. (b) f Mo 3d, (c) S 2p and (d) C 1s. The surface compositions of MoS2/CCS are examined by X-ray photoelectron spectroscopy (XPS). As shown in Figure 3a, the C, O, Mo, and S can be observed in the XPS spectrum of MoS2/CCS. Obviously, Mo4+ 3d5/2 and 3d3/2 are observed at about 228.6 and 232.9 eV in the MoS2 in the Figure 3b, respectively.26 Additional peaks (~234.1 eV and ~236.3 eV) for Mo6+ are found in the Figure 3b.7, 9, 35, 36 Moreover, a small peak at around ~225.8 eV is observed, which is ascribed to the S 2s component.7,

24

As shown in Figure 3c, S2p exhibits two contributions,

2p3/2 and 2p1/2, located at ~163.3 and ~164.5 eV, respectively.16, 36, 37 From Figure 3d, it can be observed that the C1s peaks of CCS are composed of four components: Csp2 (~285.1 eV), Csp3 (~286.0 eV), C-O bonds (~288.0 eV), and π-π* (~290.1 eV).12, 22, 38 According to the results, the CCS shows high graphitization degree.



Figure 4 Electrochemical characterization of MoS2/CCS: (a) CV curves in a potential range of 0.1-3.0 V at different scan rates. (b) Log (i) vs. log (v) plots of change in peak current for absolute value of cathodic and anodic peaks vs. change in scan rate. Inset: b-values of the cathodic and anodic sweeps. (c) Cathodic and anodic peaks current dependence on the scan ratederived from CV and used to determine the capacitive and intercalation contributions to the energy storage. (d) Quantitative contribution of the capacitive and intercalation to Li+ storage at the scan rate of the 1.0 mV s-1 estimated from Figure 4c.

Figure 4a displays the cyclic voltammorgrams of the MoS2/CCS batteries at the different scan rates from 0.2 - 1.0 mV s-1 (the scan rates from the red line to the green line is 0.2 - 1.0 mV s-1). The peak in Figure 4a corresponds to the charge-discharge curve (Figure S5). According to previous studies, the charge-storage mechanism consists of three components39: 1.pseudocapacitors; 2.the Li+ ion insertion process; 3.non-faradaic contribution from the electric double layer capacitors. When the size of the particles decreases to nanoscale, the two storage mechanisms of pseudo-capacitance and double layer charging will contribute to the storage energy due to the high specific surface area.39 According to the Equation (1), we can calculate the capacitive effect of the battery system. 39-43 i=avb

(1)

The battery system is mainly controlled by capacitive (b value close to 1) and the Li+ insertion process (b value close to 0.5), respectively.39,43 Figure 4b shows the b value approaches to 1.0, the capacitive process has control over Li-MoS2 battery . Capacitive process is beneficial to the rate performance and cyclic stability of LIBs. In order to quantitatively separate the contribution


Page 10 of 24

Page 11 of 24 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


of the Li+ insertion process and pseudo-capacitance respectively to the Li-MoS2 battery, the Equation (2)

39, 43, 44

is used to estimate the contribution from the Li+ insertion process and

pseudo-capacitance. i = k1v + k2v1/2

(2)

Here k1v and k2v represent the pseudo-capacitance and Li+ insertion process, respectively. A line with a slop of constant k1 and the y-intercept of constant k2 is obtained by calculating. The line will provide quantitative information of the pseudo-capacitance and Li+ insertion process (Figure 4c).39 The electrochemical reactions are divided into four regions by quantitative analysis in Figure 4d, it is shown that the b and c among the four regions of capacitance-based contribution are close to 100% on the scanning speed of 1.0 mV s-1. `



Figure 5 (a) Cycling performances for the MoS2/CCS, MoS2 and CCS at 100 mA g-1(b) Rate capability for the MoS2/CCS sample. (c) Long cycling performance of MoS2/CCS at 5 A g-1. MoS2/CCS not only has a special morphology, but also shows excellent electrochemical performances. Based on the total mass, the MoS2/CCS delivers initial specific capacity of 1409.5 with coulomb efficiency of 72.06% (vs. 54.34% of the CCS and 70% of the annealed bare MoS2 nanosheets) (Figure 5a). The solid electrolyte interface (SEI) layer on the electrode surface is responsible for the results, corresponding with the result of the charge and discharge curves of the MoS2/CCS composite (Figure S4a).45, 46 After the third cycle, Coulomb efficiency has been maintained at more than 98%. Furthermore, the capacity of the MoS2/CCS can still maintain at 1230.9 mAh g-1 after 250 cycles with a 87.3% discharge capacity retention of the first cycle.


Page 12 of 24

Page 13 of 24 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


Compared with the previous reported MoS2, the MoS2/CCS has a higher capacity and more stable long-term cycling process (Figure 6S). Since the surface of MoS2/CCS composites have more defects and active sites conducive to lithium-ion storage, and gel-like polymeric layer is formed, it is obvious that the capacity of the MoS2/CCS increased significantly during the cycling.47, 48 In contrast, the specific capacities of bare MoS2 and the CCS are 1414 and 381.7 mAh g-1 in the initial cycle. The initial specific capacity of bare MoS2 is very close to MoS2/CCS but after 250 cycles decays to 121.5 mAh g-1. The CCS has relatively low capacities compared to bare MoS2, but exhibits excellent cycling performance. Thus, the bare MoS2 and the CCS are perfectly combined together to form the MoS2/CCS composite where the bare MoS2 and the CCS complement with each other so that MoS2/CCS has a synergetic performance beyond MoS2 and CCS (1 + 1 > 2). The MoS2/CCS also shows excellent rate performance (Figure 5b). The MoS2/CCS electrode delivers reversible capacities of 1071.0, 950.0, 889.0, 846.3, 777.7 and 1062.7 mAh g-1 at 100, 500, 1000, 2000, 4000 and 100 mA g-1, respectively. The Figure 5c shows the long cycling life performance of MoS2/CCS at 5000 mA g-1. The reversible capacity -1

remains ~500 after 1000 cycles, which is higher than that of CCS at 100 mA g . After 500

cycles, , bare MoS2 has only ~147.5 mAh g-1 at 100 mA g-1 similarly (Figure S7). Therefore, the MoS2/CCS performs better in long-term cycling stability. The weight fraction of MoS2 in the MoS2/CCS is detected by thermos gravimetric analysis (TGA) (Figure S8). According to previous reports, a stable SEI layer is formed on the carbon surface to prevent the electrode from being further decomposition.49 Once again, CCS is beneficial to the cyclic stability of MoS2/CCS. As shown in Figure S9, SEM analysis of the electrode materials after 250 cycles was carried out. The complete electrode can be observed from the Figure S9a. In the Figure S9b, MoS2 is



firmly attached on either side of the wall, indicating that the MoS2/CCS electrode-electrolyte interface is stable.50, 51 In contrast, the bare MoS2 electrode has been cracked after 250 dischargecharge cycles, and some of it has been detached from the Cu foil (Figure S9c-d). The SEM images (Figure S9a-d) correspond to the electrochemical properties of MoS2/CCS and pure MoS2, respectively, which once again proves that the structure of MoS2 vertically grown on the CCS can maintain cycling stability.

Figure 6 Nyquist plots of the MoS2/CCS and bare MoS2 electrodes at the open potential of 2.7 V before cycling. Inset: the equivalent circuit model. To better understand the outstanding electrochemical properties of the MoS2/CCS and bare MoS2 electrodes, we performed an analysis of the impedance. The assembled coin battery will be tested after CV. From Figure 6, we compare the EIS plots of MoS2/CCS and bare MoS2. The collected EIS spectra contain two depressed semicircles (they are not clearly separated.) in the high-frequency region and a sloped line in the low frequency region. The two semicircles include that SIE film formed on the surface of the electrode (Rf) and the charge transfer reaction (Rct) separately. The oblique line is controlled by the diffusion process of lithium ions in the crystal


Page 14 of 24

Page 15 of 24 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


(Zw).26

According to the Figure 7, the semicircle diameter of MoS2/CCS electrode is

significantly reduced, indicating that it has a lower impedance between the SEI and MoS2/CCS electrode.

52, 53

Through the analysis of Nyquist plots, it can be concluded that the special

structure (MoS2 nanosheets are vertically grown on the CCS surface) is conducive to the transmission of lithium ions and charge, and CCS provides a stable base for MoS2 growth with high conductivity. 3. Conclusions In summary, we demonstrated a simple route to prepared MoS2 with the carbonized corn stalks (MoS2/CCS). The MoS2 nanosheets are vertically grown on the surface of CCS. This special material structure allows the MoS2/CCS to exhibit excellent electrochemical performance. The special capacity is still up to 1230.9 mAh g-1 after 250 cycles at 100 mAh g-1. At the same time, the electrode materials show excellent long-term cycling performance, which maintains about 500 mAh g-1 at 5000 mA g-1 after 1000 cycles. The present result shows that the MoS2/CCS hold tremendous potential as robust anode material for LIBs. Our studies the biocarbon materials and metal sulfide composite materials pave the way for high-performance LIBs. ASSOCIATED CONTENT Supporting Information. Experimental section for material synthesis, characterization, electrochemical measurements and additional data. AUTHOR INFORMATION Corresponding Author [email protected] [email protected]



Notes The authors declare no competing financial interests. ACKNOWLEDGMENT We acknowledge the funding support from the Nature Science Foundation of Qinghai Province (No.2015-ZJ-930Q), Applied Basic Research Program of Qinghai Province (No.2015-ZJ-740), Qinghai Province Science and Technology program (214-ZJ-948). The National Key Research and Development Program of China (Grant No.2016YFB0700604) and Program of National Natural Science Foundation of China(Grant No.21673008) and thanks for Qinghai Provincial Thousand Talents Program for High-level Innovative Professionals.

REFERENCES 1. Tang, K.; White, R. J.; Mu, X.; Titirici, M. M.; van Aken, P. A.; Maier, J., Hollow Carbon Nanospheres with a High Rate Capability for Lithium-Based Batteries. ChemSusChem 2012, 5, 400-403. 2. Zhou, X.; Chen, F.; Bai, T.; Long, B.; Liao, Q.; Ren, Y.; Yang, J., Interconnected Highly Graphitic Carbon Nanosheets Derived from Wheat Stalk as High Performance Anode Materials for Lithium Ion Batteries. Green Chem. 2016, 18, 2078-2088. 3. Jiang, J.; Zhu, J.; Ai, W.; Fan, Z.; Shen, X.; Zou, C.; Liu, J.; Zhang, H.; Yu, T., Evolution of Disposable Bamboo Chopsticks into Uniform Carbon Fibers: a Smart Strategy to Fabricate Sustainable Anodes for Li-Ion Batteries. Energy Environ. Sci. 2014, 7, 2670-2679.


Page 16 of 24

Page 17 of 24 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


4. Cui, C.; Li, X.; Hu, Z.; Xu, J.; Liu, H.; Ma, J., Growth of MoS2@C Nanobowls as a Lithium-Ion Battery Anode Material. RSC Adv. 2015, 5, 92506-92514. 5. Zhou, F.; Xin, S.; Liang, H. W.; Song, L. T.; Yu, S. H., Carbon Nanofibers Decorated with Molybdenum Disulfide Nanosheets: Synergistic Lithium Storage and Enhanced Electrochemical Performance. Angew. Chem. Int. Ed. 2014, 53, 11552-11556. 6. Wu, H.; Wu, Y.; Chen, X.; Ma, Y.; Xu, M.; Wei, W.; Pan, J.; Xiong, X., Rational Design and Preparation of Few-Layered MoSe2 Nanosheet@C/TiO2 Nanobelt Heterostructures with Superior Lithium Storage Performance. RSC Adv. 2016, 6, 23161-23168. 7. Wang, J.; Luo, C.; Gao, T.; Langrock, A.; Mignerey, A. C.; Wang, C., An Advanced MoS2 /Carbon Anode for High-Performance Sodium-Ion Batteries. Small 2015, 11, 473-481. 8. Chang, K.; Chen, W.; Ma, L.; Li, H.; Li, H.; Huang, F.; Xu, Z.; Zhang, Q.; Lee, J.-Y., Graphene-Like MoS2/Amorphous Carbon Composites with High Capacity and Excellent Stability as Anode Materials for Lithium Ion Batteries. J. Mater. Chem. 2011, 21, 6251-6257. 9. Guo, B.; Yu, K.; Song, H.; Li, H.; Tan, Y.; Fu, H.; Li, C.; Lei, X.; Zhu, Z., Preparation of Hollow Microsphere@Onion-Like Solid Nanosphere MoS2 Coated by a Carbon Shell as a Stable Anode for Optimized Lithium Storage. Nanoscale 2016, 8, 420-430. 10. Nethravathi, C.; Prabhu, J.; Lakshmipriya, S.; Rajamathi, M., Magnetic Co-Doped MoS2 Nanosheets for Efficient Catalysis of Nitroarene Reduction. ACS Omega 2017, 2, 5891-5897.



11. Huang, G.; Chen, T.; Chen, W.; Wang, Z.; Chang, K.; Ma, L.; Huang, F.; Chen, D.; Lee, J. Y., Graphene-Like MoS2/Graphene Composites: Cationic Surfactant-Assisted Hydrothermal Synthesis and Electrochemical Reversible Storage of Lithium. Small 2013, 9, 3693-3703. 12. Liu, Y.; Zhao, Y.; Jiao, L.; Chen, J., A Graphene-Like MoS2/Graphene Nanocomposite as A High Performance Anode for Lithium Ion Batteries. J. Mater. Chem. A 2014, 2, 13109-13115. 13. Ma, L.; Ye, J.; Chen, W.; Wang, J.; Liu, R.; Lee, J. Y., Synthesis of Few-Layer MoS2Graphene Composites with Superior Electrochemical Lithium-Storage Performance by an IonicLiquid-Mediated Hydrothermal Route. ChemElectroChem 2015, 2, 538-546. 14. Xie, D.; Wang, D. H.; Tang, W. J.; Xia, X. H.; Zhang, Y. J.; Wang, X. L.; Gu, C. D.; Tu, J. P., Binder-Free Network-Enabled MoS2-PPY-rGO Ternary Electrode for High Capacity and Excellent Stability of Lithium Storage. J. Power Sources 2016, 307, 510-518. 15. Ma, G.; Peng, H.; Mu, J.; Huang, H.; Zhou, X.; Lei, Z., In Situ Intercalative Polymerization of Pyrrole in Graphene Analogue of MoS2 as Advanced Electrode Material in Supercapacitor. J. Power Sources 2013, 229, 72-78. 16. Chang, C.; Yang, X.; Xiang, S.; Que, H.; Li, M. Layered MoS2/PPY Nanotube Composites with Enhanced Performance for Supercapacitors. J. Mater. Sci. - Mater. Electron. 2016, 28, 1777-1784. 17. Li, G.; Zeng, X.; Zhang, T.; Ma, W.; Li, W.; Wang, M., Facile Synthesis of Hierarchical Hollow Mos2 Nanotubes as Anode Materials for High-Performance Lithium-Ion Batteries. CrystEngComm. 2014, 16, 10754-10759.


Page 18 of 24

Page 19 of 24 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


18. Shi, Z. T.; Kang, W.; Xu, J.; Sun, L. L.; Wu, C.; Wang, L.; Yu, Y. Q.; Yu, D. Y.; Zhang, W.; Lee, C. S., In Situ Carbon-Doped Mo(Se0.85S0.15)2 Hierarchical Nanotubes as Stable Anodes for High-Performance Sodium-Ion Batteries. Small 2015, 11, 5667-5674. 19. Huang, K.-J.; Wang, L.; Zhang, J.-Z.; Wang, L.-L.; Mo, Y.-P., One-Step Preparation of Layered Molybdenum Disulfide/Multi-Walled Carbon Nanotube Composites for Enhanced Performance Supercapacitor. Energy 2014, 67, 234-240. 20. Zhou, X.; Wan, L. J.; Guo, Y. G. Facile Synthesis of MoS2@CMK-3 Nanocomposite as an Improved Anode Material for Lithium-Ion Batteries. Nanoscale 2012, 4, 5868-5871. 21. Hu, Z.; Wang, L.; Zhang, K.; Wang, J.; Cheng, F.; Tao, Z.; Chen, J. MoS2 Nanoflowers with Expanded Interlayers as High-Performance Anodes For Sodium-Ion Batteries. Angew. Chem. Int. Ed. 2014, 53, 12794-12798.

22.

Khan, M.; Yousaf, A. B.; Chen, M.; Wei, C.; Wu, X.; Huang, N.; Qi, Z.; Li, L.,

Molybdenum Sulfide/Graphene-Carbon Nanotube Nanocomposite Material for Electrocatalytic Applications in Hydrogen Evolution Reactions. Nano Res. 2016, 9, 837-848. 23. Hu, S.; Chen, W.; Zhou, J.; Yin, F.; Uchaker, E.; Zhang, Q.; Cao, G., Preparation of Carbon Coated MoS2 Flower-Like Nanostructure with Self-Assembled Nanosheets as HighPerformance Lithium-Ion Battery Anodes. J. Mater. Chem. A 2014, 2, 7862-7872. 24. Qiu, W.; Xia, J.; He, S.; Xu, H.; Zhong, H.; Chen, L., Facile Synthesis of Hollow MoS2 Microspheres/Amorphous Carbon Composites and Their Lithium Storage Properties. Electrochim. Acta 2014, 117, 145-152.



Page 20 of 24

25. Wang, R.; Gao, S.; Wang, K.; Zhou, M.; Cheng, S.; Jiang, K., MoS2@rGO Nanoflakes as High Performance Anode Materials in Sodium Ion Batteries. Sci. Rep. 2017, 7, 7963. 26. Teng, Y.; Zhao, H.; Zhang, Z.; Li, Z.; Xia, Q.; Zhang, Y.; Zhao, L.; Du, X.; Du, Z.; Lv, P.; Swierczek, K., MoS2 Nanosheets Vertically Grown on Graphene Sheets for Lithium-Ion Battery Anodes. ACS Nano 2016, 10, 8526-8535. 27.

Hsieh,

M.-H.;

Li,

G.-A.;

Chang,

W.-C.;

Tuan,

H.-Y.,

A

Germanium

Nanoparticles/Molybdenum Disulphide (MoS2) Nanocomposite as a High-Capacity, High-Rate Anode Material for Lithium-Ion Batteries. J. Mater. Chem. A 2017, 5, 4114-4121.

28. Kamila, S.; Mohanty, B.; Samantara, A. K.; Guha, P.; Ghosh, A.; Jena, B.; Satyam, P. V.; Mishra, B. K.; Jena, B. K., Highly Active 2D Layered MoS2-rGO Hybrids for Energy Conversion and Storage Applications. Sci. Rep. 2017, 7, 8378. 29. Kong, D.; Wang, H.; Cha, J. J.; Pasta, M.; Koski, K. J.; Yao, J.; Cui, Y., Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers. Nano Lett. 2013, 13, 1341-1347. 30. Dou, S.; Wu, J.; Tao, L.; Shen, A.; Huo, J.; Wang, S., Carbon-Coated MoS2 Nanosheets as Highly Efficient Electrocatalysts for the Hydrogen Evolution Reaction. Nanotechnology 2016, 27, 045402. 31. Zhang, G.; Wang, T.; Yu, X.; Zhang, H.; Duan, H.; Lu, B., Nanoforest of Hierarchical Co3O4@NiCo2O4 Nanowire Arrays for High-Performance Supercapacitors. Nano Energy 2013, 2, 586-594.


Page 21 of 24 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


32. Lin, M. W.; Kravchenko, II; Fowlkes, J.; Li, X.; Puretzky, A. A.; Rouleau, C. M.; Geohegan, D. B.; Xiao, K., Thickness-Dependent Charge Transport in Few-Layer MoS2 FieldEffect Transistors. Nanotechnology 2016, 27, 165203. 33. Li, Q. W., E. C.; van der Veer, W. E.; Murray, B. J.; Newberg, J. T.; Bohannan, E. W.; Switzer, J. A.; Hemminger, J. C.; Penner, R. M., Molybdenum Disulfide Nanowires and Nanoribbons by Electrochemical/Chemical Synthesis. J. Phys. Chem. B 2005, 109, 3169–3182. 34. Shao, J.; Qu, Q.; Wan, Z.; Gao, T.; Zuo, Z.; Zheng, H., From Dispersed Microspheres to Interconnected Nanospheres: Carbon-Sandwiched Monolayered MoS2 as High-Performance Anode of Li-Ion Batteries. ACS Appl. Mater. Interfaces 2015, 7, 22927-22934. 35. Sari, F. N. I.; Ting, J.-M., Direct Growth of MoS2 Nanowalls on Carbon Nanofibers for Use in Supercapacitor. Sci. Rep. 2017, 7, 5999. 36. Wu, M.; Zhan, J.; Wu, K.; Li, Z.; Wang, L.; Geng, B.; Wang, L.; Pan, D., Metallic 1T MoS2 Nanosheet Arrays Vertically Grown on Activated Carbon Fiber Cloth for Enhanced Li-Ion Storage Performance. J. Mater. Chem. A 2017, 5, 14061-14069. 37. Zhou, R.; Wang, J.-G.; Liu, H.; Liu, H.; Jin, D.; Liu, X.; Shen, C.; Xie, K.; Wei, B., Coaxial MoS2@Carbon Hybrid Fibers: a Low-Cost Anode Material for High-Performance LiIon Batteries. Materials 2017, 10, 174-185. 38 Kubo, S.; Tan, I.; White, R. J.; Antonietti, M.; Titirici, M.-M., Template Synthesis of Carbonaceous Tubular Nanostructures with Tunable Surface Properties. Chem. Mater. 2010, 22, 6590-6597.



39. Wang, J.; Polleux, J.; Lim, J.; Dunn, B., Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles. J. Phys. Chem. C 2007, 111, 14925-14931. 40. Miao, Z.-H.; Wang, P.-P.; Xiao, Y.-C.; Fang, H.-T.; Zhen, L.; Xu, C.-Y. DopamineInduced Formation of Ultrasmall Few-Layer MoS2 Homogeneously Embedded in N-Doped Carbon Framework for Enhanced Lithium-Ion Storage. ACS Appl. Mater. Interfaces 2016, 8, 33741-33748. 41. Lindstrom, H.; Solbrand, A.; Rensmo, H.;Hjelm, J.; Hagfeldt, A.; Lindquist, S.-E., Li+ Ion Insertion in TiO2 (anatase). 2. Voltammetry on Nanoporous Films. J. Phys. Chem. B 1997, 101, 7717-7722. 42. Lesel, B. K.; Ko, J. S.; Dunn, B.; Tolbert, S. H., Mesoporous LixMn2O4 Thin Film Cathodes for Lithium-Ion Pseudocapacitors. ACS Nano 2016, 10, 7572-7581. 43. Kim, H.; Hong, J.; Park, Y.-U.; Kim, J.; Hwang, I.; Kang, K., Sodium Storage Behavior in Natural Graphite using Ether-Based Electrolyte Systems. Adv. Funct. Mater. 2015, 25, 534-541. 44. Augustyn, V.; Simon, P.; Dunn, B., Pseudocapacitive Oxide Materials for High-Rate Electrochemical Energy Storage. Energy Environ. Sci. 2014, 7, 1597-1614. 45. Sahu, T. S.; Mitra, S., Exfoliated MoS2 Sheets and Reduced Graphene Oxide-an Excellent and Fast Anode for Sodium-Ion Battery. Sci. Rep. 2015, 5, 12571. 46. An, S. J.; Li, J.; Daniel, C.; Mohanty, D.; Nagpure, S.; Wood, D. L., The State of Understanding of The Lithium-Ion-Battery Graphite Solid Electrolyte Interphase (SEI) and Its Relationship to Formation Cycling. Carbon 2016, 105, 52-76.


Page 22 of 24

Page 23 of 24 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


47. Zeng, P.; Wang, X.; Ye, M.; Ma, Q.; Li, J.; Wang, W.; Geng, B.; Fang, Z., Excellent Lithium Ion Storage Property of Porous MnCo2O4 Nanorods. RSC Adv. 2016, 6, 23074-23084. 48. Guo, J.; Li, P.; Chai, L.; Su, Y.; Diao, J.; Guo, X., Silica Template-Assisted Synthesis of SnO2@Porous Carbon Composites as Anode Materials with Excellent Rate Capability and Cycling Stability for Lithium-Ion Batteries. RSC Adv. 2017, 7, 30070-30079. 49. Zhou, X.; Dai, Z.; Liu, S.; Bao, J.; Guo, Y. G. Ultra-Uniform SnOx/Carbon Nanohybrids toward Advanced Lithium-Ion Battery Anodes. Adv Mater. 2014, 26, 3943-3949. 50. Liu, Y.; Si, L.; Du, Y.; Zhou, X.; Dai, Z.; Bao, J., Strongly Bonded Selenium/Microporous Carbon Nanofibers Composite as a High-Performance Cathode for Lithium–Selenium Batteries. J. Phys. Chem. C 2015, 119, 27316-27321. 51. Wang, P.; Qiao, B.; Du, Y.; Li, Y.; Zhou, X.; Dai, Z.; Bao, J., Fluorine-Doped Carbon Particles Derived from Lotus Petioles as High-Performance Anode Materials for Sodium-Ion Batteries. J. Phys. Chem. C 2015, 119, 21336-21344. 52. Xie, D.; Tang, W. J.; Xia, X. H.; Wang, D. H.; Zhou, D.; Shi, F.; Wang, X. L.; Gu, C. D.; Tu, J. P., Integrated 3D Porous C-MoS2/Nitrogen-Doped Graphene Electrode for High Capacity and Prolonged Stability Lithium Storage. J. Power Sources 2015, 296, 392-399. 53. Xiao, J.; Wang, X.; Yang, X.-Q.; Xun, S.; Liu, G.; Koech, P. K.; Liu, J.; Lemmon, J. P. Electrochemically Induced High Capacity Displacement Reaction of PEO/MoS2/Graphene Nanocomposites with Lithium. Adv. Funct. Mater. 2011, 21, 2840-2846.



Table of Contents Graphic:


Page 24 of 24

MoS2 Nanosheets Vertically Grown on Carbonized Corn Stalks as

Recommend Documents