Unique Reversible Conversion-Type Mechanism Enhanced Cathode

Subscriber access provided by University of Florida | Smathers Libraries

Article

Unique Reversible Conversion-Type Mechanism Enhanced Cathode Performance in Amorphous Molybdenum Polysulfide Xusheng Wang, Kuangzhou Du, Chao Wang, Luxiang Ma, Binglu Zhao, Junfeng Yang, Meixian Li, Xin-Xiang Zhang, Mianqi Xue, and Jitao Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b12709 • Publication Date (Web): 13 Oct 2017 Downloaded from http://pubs.acs.org on October 18, 2017

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 free 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 accessible to all readers and 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.

ACS Applied Materials & Interfaces 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 22

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

Unique Reversible Conversion-Type Mechanism Enhanced Cathode Performance in Amorphous Molybdenum Polysulfide Xusheng Wang,† Kuangzhou Du,† Chao Wang,† Luxiang Ma,† Binglu Zhao,† Junfeng Yang,† Meixian Li,† Xin-Xiang Zhang,† Mianqi Xue,*,§ and Jitao Chen*,† †

Beijing National Laboratory for Molecular Sciences College of Chemistry and Molecular

Engineering, Peking University, Beijing 100871, PR China §

Institute of Physics and Beijing National Laboratory for Condensed Matter Physics Chinese

Academy of Sciences, Beijing 100190, China KEYWORDS: a-MoS5.7, reversible conversion reaction, Li2S2, high capacity, high energy density

ABSTRACT: Unique reversible conversion-type mechanism is reported in the amorphous molybdenum polysulfide (a-MoS5.7) cathode material. The lithiation products of metallic Mo and Li2S2 rather than Mo and Li2S species have been detected. This process could yield a high discharge capacity of 746 mAh g-1. Characterizations of the recovered molybdenum polysulfide after the delithiaiton process manifests the high reversibility of the unique conversion reaction, in contrast with the general irreversibility of conventional conversion-type mechanism is generally

ACS Paragon Plus Environment

1


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

Page 2 of 22

irreversible. As a result, the a-MoS5.7 electrodes deliver high cycling stability with an energydensity retention of 1166 Wh kg-1 after 100 cycles. These results provide a novel model for the design of high-capacity and long-life electrode materials.

Introduction Despite the tremendous effects being made to the improvement of practical energy density, lithium-ion batteries (LIBs) still could not reach an universal technological level to meet the requirement for hybrid or electric vehicles, not to mention charge storage devices (such as traditional capacitors, electrets and supercapacitors) or other kinds of ion battery.1-7 As one of the key component in LIBs, novel cathode materials having a step change in energy density and battery chemistry should be identified and developed.8 Vanadium oxides, such as VO29-13 and V2O514-16, have been extensively investigated due to their high theoretical capacity and low cost. Despite the huge improvement in the long-term cycling stability, the vanadium oxides could not promise to exceed the theoretical energy density of LiCoO2 (550 Wh kg-1). Conversion-type cathode materials, such as FeF2,17,18 FeF3,19-21 and FeS222-26 with higher theoretical energy densities than LiCoO2, could potentially exceed this limitation if addressing the issues of low conductivity and large volume expansion. However, the large voltage hysteresis of these materials could lead to low energy efficiency.27-29 To meet the need of high energy density for hybrid or electric vehicles, amorphous metal polysulfides, such as amorphous MoSx (a-MoS3 and a-MoS3.4),30,31 a-TiS3,32 a-TiS4,33,34 and aNbS5,35 have been studied as cathode materials. Compared to the lithium-sulfur batteries, their semiconducting nature is favorable for realizing high gravimetric and volumetric energy densities, and the formed metal-sulfur bonds could suppress the dissolution of polysulfide.34 The


2

Page 3 of 22

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


study of a-MoS3.4 material has revealed excellent characterizations of the active material and the anion-redox-driven electrochemical processes,31 but the issues of limited capacity delivery and poor cycling stability (mainly induced by the volume change and structural pulverization) still remain unsolved. Here, we develop a new a-MoS5.7 cathode material with unique conversion-type mechanism to achieve high energy density and excellent cycling stability. This conversion reaction involves the lithiation product of Li2S2 instead of the conventional conversion-type products, such as Li2S,36 Li2O,37 Li2Se,38 and Na2S2,39,40 (in sodium-ion batteries). And the delithiation process demonstrates high reversibility with the re-formation of the disulfide bond and tetravalent molybdenum. Furthermore, the morphology of the delithiation product has no obvious change compared to that of the initial a-MoS5.7 material, indicating the strong resistance of this conversion reaction to the volume change and structural pulverization. Results and discussion


3


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

Page 4 of 22

Figure 1. Characterizations of the raw (NH4)2Mo2S12·2H2O and the a-MoS5.7 materials. (a) XRD patterns of the raw (NH4)2Mo2S12·2H2O and the a-MoS5.7 materials. Lower figure depicts the standard pattern of (NH4)2Mo2S12·2H2O (ICSD no. 98-002-3341). (b) SEM image of the aMoS5.7 material. (c) HRSEM image of the a-MoS5.7 material. (d) TEM and EDX mapping images of the a-MoS5.7 material. The scale bars in panels (b-d) are severally 5, 0.2, and 0.2 µm. Figure 1a shows the X-ray diffraction (XRD) pattern of the raw (NH4)2Mo2S12·2H2O material, in which all the main peaks are well-aligned with that of the standard. The scanning electron microscopy (SEM) image of the raw (NH4)2Mo2S12·2H2O material (Figure S1, Supporting Information) demonstrates a rod-like morphology. From the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) tests of the raw (NH4)2Mo2S12·2H2O material (Figure S2), the temperature of 220 °C was chosen to prepare the molybdenum polysulfide so as to remove hydrogen, nitrogen, and oxygen elements. The as-prepared molybdenum polysulfide was completely soluble in concentrated nitric acid (inset in Figure S2), and then the molar ratio of molybdenum and sulfur elements was determined to be MoS5.7 by the inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The amorphous nature of the MoS5.7 material is documented by the XRD pattern (Figure 1a), where no crystal peaks associated with molybdenum sulphide was distinguished. The morphology of the a-MoS5.7 material (Figure 1b) is consistent with that of the raw (NH4)2Mo2S12·2H2O material despite the heat treatment.7 The high-resolution SEM (HRSEM) image of the a-MoS5.7 material (Figure 1c) demonstrates that the rod is in an ordered configuration assembled with tightly stacked lamellas (less than 30 nm in thickness). The energy-dispersive X-ray spectroscopy (EDX) elemental mapping images of the a-MoS5.7 material (Figure S3) only reveal the existence of molybdenum and sulfur elements (nitrogen and oxygen elements were not detected; hydrogen element could not be detected).


4

Page 5 of 22

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 1d illustrates the transmission electron microscopy (TEM) and corresponding EDX mapping images of the a-MoS5.7 material. The rod with homogeneous distribution of molybdenum and sulfur elements is integrated with chiaroscuro, which is in accordance with the tightly stacked lamellas. The EDX images convey a molar ratio of 5.8 between the molybdenum and sulfur elements, which is close to the result of ICP-AES. The high-resolution TEM (HRETM) image of the a-MoS5.7 material (Figure S4) also confirms the amorphous nature by the indiscernible crystal planes and selected area electron diffraction (SAED) pattern (the inset).

Figure 2. XPS spectra of the raw (NH4)2Mo2S12·2H2O and the a-MoS5.7 materials. (a) Mo 3d region of the raw (NH4)2Mo2S12·2H2O material. (b) S 2p region of the raw (NH4)2Mo2S12·2H2O material. (c) Mo 3d region of the a-MoS5.7 material. (d) S 2p region of the a-MoS5.7 material. For further evaluation, the survey X-ray photoelectron spectroscopy (XPS) spectra of the raw (NH4)2Mo2S12·2H2O and the a-MoS5.7 materials are severally displayed in Figure S5a and S5b. Both exhibit the peaks associated with carbon, oxygen, molybdenum, and sulfur elements


5


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

Page 6 of 22

(carbon and oxygen elements signals are partially from the absorbed air). The peak of oxygen element for the raw (NH4)2Mo2S12·2H2O material is stronger than that of the a-MoS5.7 material. The molar ratio of molybdenum and sulfur elements is fitted to be 5.5, which is consistent with the result of ICP-AES. In Figure 2a, the Mo 3d region of the raw (NH4)2Mo2S12·2H2O material, where one doublet peaks fitted at 229.8/232.9 eV (3d5/2/3d3/2, respectively) correspond to Mo (IV),41 is interfered by the S 2s region. Similarly, the doublet peaks of Mo (IV) for the a-MoS5.7 material are located at 229.5/232.6 eV (Figure 2c).42 The deconvolution of the S 2p region for the raw (NH4)2Mo2S12·2H2O and the a-MoS5.7 materials are shown in Figure 2b and 2d, respectively.

The lower binding-energy doublets

at

162.2/163.4

eV

for the raw

(NH4)2Mo2S12·2H2O material and 162.1/163.3 eV for the a-MoS5.7 material arise from the terminal S22- ligands, and the higher binding-energy doublets at 163.5/164.7 eV for the raw (NH4)2Mo2S12·2H2O material and 163.5/164.6 eV for the a-MoS5.7 material correspond to the bridging S22- and apical S2- ligands.41,43 These results indicate the almost unchanged surface chemical states of molybdenum and sulfur elements from the raw (NH4)2Mo2S12·2H2O material to the a-MoS5.7 material (the heat treatment only reduced the ratio of the terminal S22- ligands). Thus the possible chemical structure change from the raw (NH4)2Mo2S12·2H2O to a-MoS5.7 is illustrated in Figure S6. We have also collected the Raman spectra (Figure S7) and Infrared (IR) spectra (Figure S8) of the raw (NH4)2Mo2S12·2H2O material and the a-MoS5.7 material. According to the previous works of (NH4)2Mo3S13·H2O,44 (NH4)2MoS4,45 and a-MoS346 materials, the Raman peaks at the lower shift range and the higher shift range should be severally attributed to the Mo–S vibration and the S–S vibration. In the IR spectra, the peak groups at lower and higher wavenumber for the raw (NH4)2Mo2S12·2H2O material should be separately assigned to the bending vibration and stretching vibration of the N–H and O–H bonds.47 And


6

Page 7 of 22

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


these peaks disappear in the a-MoS5.7 material, indicating the successful removal of nitrogen and oxygen elements.

Figure 3. XPS spectra of the discharged-state and recharged-state a-MoS5.7 electrodes. Mo 3d region (a) and S 2p region (b) of the discharged-state a-MoS5.7 electrode. Mo 3d region (c) and S 2p region (d) of the recharged-state a-MoS5.7 electrode. XPS was also used to investigate the lithiation/delithiation mechanisms48 of the a-MoS5.7 material. Firstly, the spectra of the discharge-state a-MoS5.7 electrode were collected (Figure 3a and 3b). In Figure 3a, the Mo 3d region shows one doublet at 228.1/231.1 eV, which demonstrates a red shift comapred to that of the a-MoS5.7 material and corresponds to Mo(0).49,50 The lower binding-energy S 2p region shown in Figure 3b only contains one doublet at 161.5/162.6 eV, which could be assigned to the S element in Li2S2 species rather than the S22ligands.51,52 Unlike the conventional conversion-type mechanism with the reaction products of zero-valent metal and Li2S,27 the conversion reaction in the a-MoS5.7 material reveals the


7


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

Page 8 of 22

lithiation produts of metallic Mo and Li2S2. The hexavalent sulfur species should be generated from the oxidation effect.53 In general, the mild calcination temperature will not lead to the sulfur vacancy.54 For the delithiation process, the XPS spectra of the a-MoS5.7 electrodes recharged to 3.0 V were analyzed to evaluate the reversibility of the conversion-type mechanism. As shown in Figure 3c, the doublet peaks of the Mo (IV) located at 229.4/232.5 eV reappear with almost the same peak positions compared to that of the initial a-MoS5.7 material (229.5/232.6 eV). As for the lower binding-energy S 2p region (Figure 3d), the deconvolution shows two doublets with the positions at 162.1/163.3 eV and 163.4/164.5 eV. Despite the change in peak intensity, this suggests the good recovery of the S22- ligands (162.1/163.3 eV and 163.5/164.6 eV for the initial a-MoS5.7 material). The conventional conversion-type mechanism generally shows poor reversibility,27 but the conversion reaction of the a-MoS5.7 material is highly reversible. To further consolidate the reversibility, SEM images of the initial a-MoS5.7 electrode and the recharged a-MoS5.7 electrode were compared. In Figure 4a, the initial electrode shows a hybrid of a-MoS5.7 rods and carbon black particles, and the lamellas in the rods are clearly visible in Figure 4b. The recharged a-MoS5.7 electrode (Figure 4c) still displays the hybrid morphology without structural pulverization. And the SEM image of a typical rod (Figure 4d) manifests the maintenance of the stacked lamellas. Therefore, the conversion reaction causes no damage to the morphology and chemical structure of the a-MoS5.7 material.


8

Page 9 of 22

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 4. (a) SEM image of the initial a-MoS5.7 electrode. (b) Typical SEM image of the initial a-MoS5.7 rod. (c) SEM image of the recharged a-MoS5.7 electrodes. (d) Typical SEM image of the recharged a-MoS5.7 rod. The a-MoS5.7 material exhibits almost no morphological and structural change after the lithiation/delithiation process. The scale bars in panels (a-d) are separately 5, 1, 5, and 0.3 µm. Electrochemical performances of the a-MoS5.7 electrodes were investigated to further assess the conversion-type mechanism. Figure 5a shows the galvanostatic voltage curves (1.5-3.0 V) with a wide plateau of around 2 V, which should be attributed to the conversion reaction. The electrodes reveal a high discharge capacity of 746 mAh g-1 and a high coulombic efficiency of 86%. The reaction of MoS5.7 + 5.7Li+ + 5.7e- → Mo + 2.85Li2S2 takes place during the lithiation process, and the Mo nanoclusters are integrated with the Li2S2 matrix. Due to the high reversibility of the conversion reaction, the reversed reaction takes place during the delithiation process.55 The electrochemical impedance spectroscopies (EIS) of the initial and recharged aMoS5.7 electrodes are exhibited in Figure 5b. The top inset, in which Rb, Cdl, Rct, and Zw severally


9


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

Page 10 of 22

represents the bulk resistance, constant phase element, charge-transfer resistance, and Warburg impedance, shows the equivalent circuit. The Rct value of the recharged electrode is much smaller than that of the initial electrode. The rate capability was tested with the current densities form 50 to 4000 mA g-1 (Figure 5c). A high discharge capacity of 270 mAh g-1 is still delivered even at 4000 mA g-1. It also realizes a good capacity recovery along with the recovered current density. Figure 5d reveals the good cycling stability of the a-MoS5.7 electrodes. A high capacity retention of 588 mAh g-1 is delivered after 100 cycles. This manifests that the unique conversiontype mechanism has a positive effect on the cycling stability. The initial capacity fading should be attributed to the continuous formation and mechanical degradation of unstable solidelectrolyte interface (SEI) layer.55,56 The capacity becomes stabilized during cycling along with the gradual stabilization of SEI layer. And, obviously, the in-situ introduction of metal/carbonbased conductive network or conducting polymer may further improve the cycling performance.57-60 Meanwhile, the corresponding energy density illustrated in Figure 5e still delivers 1166 Wh kg-1 after 100 cycles. The comparison between the a-MoS5.7 electrodes and some previously reported vanadium oxides, iron fluorides, and iron sulfides cathodes (only works with over 50 cycle numbers are listed) is displayed in Figure 5f.9-26 Both the capacity and energy density retention of the a-MoS5.7 electrodes rank the top among these reported cathodes. The long-term cycling performance of the a-MoS5.7 electrode has also been assessed at 200 mA g-1. As shown in Figure S9, a high capacity of 355 mAh g-1 is delivered after 300 cycles. The SEM images of the a-MoS5.7 electrode after the long-term cycling test are exhibited in Figure S10. Despite the coated layer, which should be assigned to the SEI layer, the a-MoS5.7 material maintains the rod-like morphology, and the tightly stacked lamellas are still visible, indicating that no structural pulverization happens during the long-term cycling test. The galvanostatic


10

Page 11 of 22

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


voltage curves of the a-MoS5.7 electrode within the voltage range of 1.0-3.0 V are shown in Figure S11. A higher capacity delivery of 939 mAh g-1 is achieved. The S 2p region in the XPS spectra of the a-MoS5.7 electrode discharged to 1.0 V has been collected (Figure S12). The Li2S species could be detected,51,52 and it should be generated from the Li2S2 species.61

Figure 5. Electrochemical performances of the a-MoS5.7 electrodes. (a) Galvanostatic voltage curves of the a-MoS5.7 electrodes (1.5-3.0 V). (b) EIS patterns of the initial and recharged aMoS5.7 electrodes (1.5-3.0 V). The inset shows the equivalent circuit. (c) Rate capability of the aMoS5.7 electrodes. (d) Cycling performances of the a-MoS5.7 electrodes. (e) Cycling energy density of a-MoS5.7 electrodes. (f) Comparison between the a-MoS5.7 electrodes and some reported cathodes (only works with the cycle number over 50 are listed).


11


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

Page 12 of 22

Conclusions In conclusion, a unique conversion-type mechanism has been studied through the lithiation/delithiation process of the a-MoS5.7 material. The lithiation products of metallic Mo and Li2S2 are confirmed, in contrast with the products of Mo and Li2S in the conventioal conversion reaction. Molybdenum polysulfide are able to recover after the delithiation process, indicating the good reversibility of the conversion reaction. High energy density and enhanced cycling stability are realized in the a-MoS5.7 electrodes. This study offers a new design model for the development of electrode materials with high energy-density delivery and long-term cycling stability. ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Experimental procedures and supplementary SEM images, TGA-DSC curves, EDX images, HRTEM image, XPS spectra, schematic structural change, Raman spectra, IR spectra, cycling performance, and galvanostatic voltage curves (PDF). AUTHOR INFORMATION Corresponding Author * Jitao Chen: [email protected]; * Mianqi Xue: [email protected]. Author Contributions All authors have given approval to the final version of the manuscript.


12

Page 13 of 22

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


Notes The authors declare no competing financial interests. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21622407, 21673008), the National Key Research and Development Program of China (2016YFB0700604) and Guangdong Innovative and Entrepreneurial Research Team Progress (2013N080). REFERENCES (1)

Grey, C.; Tarascon, J. Sustainability and In Situ Monitoring in Battery Development. Nat.

Mater. 2017, 16, 45-56. (2)

Wang, X.; Chen, D.; Yang, Z.; Zhang, X.; Wang, C.; Chen, J.; Zhang, X.; Xue, M. Novel

Metal Chalcogenide SnSSe as a High-Capacity Anode for Sodium-Ion Batteries. Adv. Mater. 2016, 28, 8645-8650. (3)

Xue, M.; Chen, D.; Wang, X.; Chen, J.; Chen, G. Carbonized Poly (vinylidene

fluoride)/Graphene Oxide with Three-Dimensional Multiscale-Pore Architecture as an Advanced Electrode Material. J. Mater. Chem. A 2015, 3, 7715-7718. (4)

Ma, X.; Xue, M.; Li, F.; Chen, J.; Chen, D.; Wang, X.; Pan, F.; Chen, G. Gradual-Order

Enhanced Stability: a Frozen Section of Electrospun Nanofibers for Energy Storage. Nanoscale 2015, 7, 8715-8719. (5)

Li, F.; Chen, J.; Wang, X.; Xue, M.; Chen, G. Stretchable Supercapacitor with Adjustable

Volumetric Capacitance Based on 3D Interdigital Electrodes. Adv. Funct. Mater. 2015, 25, 46014606.


13


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

(6)

Page 14 of 22

Koketsu, T.; Ma, J.; Morgan, B. J.; Body, M.; Legein, C.; Dachraoui, W.; Giannini, M.;

Demortière, A.; Salanne, M.; Dardoize, F. Reversible Magnesium and Aluminium Ions Insertion in Cation-Deficient Anatase TiO2. Nat. Mater. doi:10.1038/nmat4976. (7)

Ma, X.; Zhao, D.; Xue, M.; Wang, H.; Cao, T. Selective Discharge of Electrostatic

Charges on Electrets Using a Patterned Hydrogel Stamp. Angew. Chem. Int. Ed. 2010, 49, 55375540. (8)

Eames, C.; Islam, M. S. Ion Intercalation into Two-Dimensional Transition-Metal

Carbides: Global Screening for New High-Capacity Battery Materials. J. Am. Chem. Soc. 2014, 136, 16270-16276. (9)

Niu, C.; Meng, J.; Han, C.; Zhao, K.; Yan, M.; Mai, L. VO2 Nanowires Assembled into

Hollow Microspheres for High-Rate and Long-Life Lithium Batteries. Nano Lett. 2014, 14, 2873-2878. (10)

Chao, D.; Zhu, C.; Xia, X.; Liu, J.; Zhang, X.; Wang, J.; Liang, P.; Lin, J.; Zhang, H.;

Shen, Z. X. Graphene Quantum Dots Coated VO2 Arrays for Highly Durable Electrodes for Li and Na Ion Batteries. Nano Lett. 2014, 15, 565-573. (11)

Balogun, M.-S.; Luo, Y.; Lyu, F.; Wang, F.; Yang, H.; Li, H.; Liang, C.; Huang, M.;

Huang, Y.; Tong, Y. Carbon Quantum Dot Surface-Engineered VO2 Interwoven Nanowires: A Flexible Cathode Material for Lithium and Sodium Ion Batteries. ACS Appl. Mater. Interfaces 2016, 8, 9733-9744. (12)

Ren, G.; Hoque, M. N. F.; Pan, X.; Warzywoda, J.; Fan, Z. Vertically Aligned VO2(B)

Nanobelt Forest and Its Three-Dimensional Structure on Oriented Graphene for Energy Storage. J. Mater. Chem. A 2015, 3, 10787-10794.


14

Page 15 of 22

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


(13)

Xia, X.; Chao, D.; Ng, C. F.; Lin, J.; Fan, Z.; Zhang, H.; Shen, Z. X.; Fan, H. J. VO2

Nanoflake Arrays for Supercapacitor and Li-Ion Battery Electrodes: Performance Enhancement by Hydrogen Molybdenum Bronze as an Efficient Shell Material. Mater. Horiz. 2015, 2, 237244. (14)

Afyon, S.; Krumeich, F.; Mensing, C.; Borgschulte, A.; Nesper, R. New High Capacity

Cathode Materials for Rechargeable Li-Ion Batteries: Vanadate-Borate Glasses. Sci. Rep. 2014, 4, 7113. (15)

Liu, Q.; Li, Z.-F.; Liu, Y.; Zhang, H.; Ren, Y.; Sun, C.-J.; Lu, W.; Zhou, Y.; Stanciu, L.;

Stach, E. A. Graphene-Modified Nanostructured Vanadium Pentoxide Hybrids with Extraordinary Electrochemical Performance for Li-Ion Batteries. Nat. Commun. 2015, 6, 6127. (16)

Mateti, S.; Rahman, M. M.; Li, L. H.; Cai, Q.; Chen, Y. In Situ Prepared V2O5/Graphene

Hybrid as a Superior Cathode Material for Lithium-Ion Batteries. RSC Adv. 2016, 6, 3528735294. (17)

Zhou, J.; Zhang, D.; Zhang, X.; Song, H.; Chen, X. Carbon-Nanotube-Encapsulated FeF2

Nanorods for High-Performance Lithium-Ion Cathode Materials. ACS Appl. Mater. Interfaces 2014, 6, 21223-21229. (18)

Gu, W.; Borodin, O.; Zdyrko, B.; Lin, H. T.; Kim, H.; Nitta, N.; Huang, J.; Magasinski,

A.; Milicev, Z.; Berdichevsky, G. Lithium–Iron Fluoride Battery with In Situ Surface Protection. Adv. Funct. Mater. 2016, 26, 1507-1516. (19)

Bao, T.; Zhong, H.; Zheng, H.; Zhan, H.; Zhou, Y. In-Situ Synthesis of FeF3/Graphene

Composite for High-Rate Lithium Secondary Batteries. Electrochim. Acta 2015, 176, 215-221.


15


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

(20)

Page 16 of 22

Jiang, J.; Li, L.; Xu, M.; Zhu, J.; Li, C. M. FeF3@Thin Nickel Nmmine Nitrate Matrix:

Smart Configurations and Applications as Superior Cathodes for Li-Ion Batteries. ACS Appl. Mater. Interfaces 2016, 8, 16240-16247. (21)

Pohl, A.; Faraz, M.; Schröder, A.; Baunach, M.; Schabel, W.; Guda, A.; Shapovalov, V.;

Soldatov, A.; Chakravadhanula, V. S. K.; Kübel, C. Development of a Water Based Process for Stable Conversion Cathodes on the Basis of FeF3. J. Power Sources 2016, 313, 213-222. (22)

Liu, J.; Wen, Y.; Wang, Y.; van Aken, P. A.; Maier, J.; Yu, Y. Carbon-Encapsulated

Pyrite as Stable and Earth-Abundant High Energy Cathode Material for Rechargeable Lithium Batteries. Adv. Mater. 2014, 26, 6025-6030. (23)

Evans, T.; Piper, D. M.; Kim, S. C.; Han, S. S.; Bhat, V.; Oh, K. H.; Lee, S. H. Ionic

Liquid Enabled FeS2 for High-Energy-Density Lithium-Ion Batteries. Adv. Mater. 2014, 26, 7386-7392. (24)

Zhu, Y.; Fan, X.; Suo, L.; Luo, C.; Gao, T.; Wang, C. Electrospun FeS2@Carbon Fiber

Electrode as a High Energy Density Cathode for Rechargeable Lithium Batteries. ACS Nano 2015, 10, 1529-1538. (25)

Walter, M.; Zünd, T.; Kovalenko, M. V. Pyrite (FeS2) Nanocrystals as Inexpensive High-

Performance Lithium-Ion Cathode and Sodium-Ion Anode Materials. Nanoscale 2015, 7, 91589163. (26)

Tan, R.; Yang, J.; Hu, J.; Wang, K.; Zhao, Y.; Pan, F. Core–Shell Nano-FeS2@N-Doped

Graphene as an Advanced Cathode Material for Rechargeable Li-Ion Batteries. Chem. Commun. 2016, 52, 986-989. (27)

Wu, F.; Yushin, G. Conversion Cathodes for Rechargeable Lithium and Lithium-Ion

Batteries. Energy Environ. Sci. 2017, 10, 435-459.


16

Page 17 of 22

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


(28)

Wu, F.; Borodin, O.; Yushin, G. In Situ Surface Protection for Enhancing Stability and

Performance of Conversion-Type Cathodes. MRS Energy Sustain. 2017, 4, E9. (29)

Ding, J.; Zhao, Y.; Cui, L.; Cui, H.; Song, C.; Zhang, Z.; Zhan, X.; Xu, G. Conversion

Reaction Mechanisms of Cubic Bismuth Phosphate Bi13.1POδ as Cathode in Lithium-Ion Batteries. J. Mater. Sci. 2016, 51, 7598-7606. (30)

Matsuyama, T.; Hayashi, A.; Ozaki, T.; Mori, S.; Tatsumisago, M. Electrochemical

Properties of All-solid-state Lithium Batteries with Amorphous MoS3 Electrodes Prepared by Mechanical Milling. J. Mater. Chem. A 2015, 3, 14142-14147. (31)

Doan-Nguyen, V. V.; Subrahmanyam, K. S.; Butala, M. M.; Gerbec, J. A.; Islam, S. M.;

Kanipe, K. N.; Wilson, C. E.; Balasubramanian, M.; Wiaderek, K. M.; Borkiewicz, O. J. Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries. Chem. Mater. 2016, 28, 8357-8365. (32)

Hayashi, A.; Matsuyama, T.; Sakuda, A.; Tatsumisago, M. Amorphous Titanium Sulfide

Electrode for All-solid-state Rechargeable Lithium Batteries with High Capacity. Chem. Lett. 2012, 41, 886-888. (33)

Sakuda, A.; Ohara, K.; Fukuda, K.; Nakanishi, K.; Kawaguchi, T.; Arai, H.; Uchimoto,

Y.; Ohta, T.; Matsubara, E.; Ogumi, Z.; Okumura, T.; Kobayashi, H.; Kageyama, H.; Shikano, M.; Sakaebe, H.; Takeuchi, T. Amorphous Metal Polysulfides: Electrode Materials with Unique Insertion/Extraction Reactions. J. Am. Chem. Soc. 2017, 139, 8796-8799. (34)

Sakuda, A.; Taguchi, N.; Takeuchi, T.; Kobayashi, H.; Sakaebe, H.; Tatsumi, K.; Ogumi,

Z. Amorphous TiS4 Positive Electrode for Lithium–Sulfur Secondary Batteries. Electrochem. Commun. 2013, 31, 71-75.


17


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

(35)

Page 18 of 22

Sakuda, A.; Taguchi, N.; Takeuchi, T.; Kobayashi, H.; Sakaebe, H.; Tatsumi, K.; Ogumi,

Z. Amorphous Niobium Sulfides as Novel Positive-Electrode Materials. ECS Electrochem. Lett. 2014, 3, A79-A81. (36)

Deng, Z.; Jiang, H.; Hu, Y.; Liu, Y.; Zhang, L.; Liu, H.; Li, C. 3D Ordered Macroporous

MoS2@C Nanostructure for Flexible Li-Ion Batteries. Adv. Mater. 2017, 29, 1603020. (37)

Chen, L.; Jiang, H.; Jiang, H.; Zhang, H.; Guo, S.; Hu, Y.; Li, C. Mo-Based Ultrasmall

Nanoparticles on Hierarchical Carbon Nanosheets for Superior Lithium Ion Storage and Hydrogen Generation Catalysis. Adv. Energy Mater. 2017, 7, 1602782. (38)

Zhao, X.; Sui, J.; Li, F.; Fang, H.; Wang, H.; Li, J.; Cai, W.; Cao, G. Lamellar MoSe2

Nanosheets Embedded with MoO2 Nanoparticles: Novel Hybrid Nanostructures Promoted Excellent Performances for Lithium Ion Batteries. Nanoscale 2016, 8, 17902-17910. (39)

Wang, H.; Jiang, H.; Hu, Y.; Saha, P.; Cheng, Q.; Li, C. Interface-Engineered MoS2/C

Nanosheet Heterostructure Arrays for Ultra-Stable Sodium-Ion Batteries. Chem. Eng. Sci. 2017, 174, 104-111. (40)

Wang, H.; Jiang, H.; Hu, Y.; Li, N.; Zhao, X.; Li, C. 2D MoS2/Polyaniline

Heterostructures with Enlarged Interlayer Spacing for Superior Lithium and Sodium Storage. J. Mater. Chem. A 2017, 5, 5383-5389. (41)

Kibsgaard, J.; Jaramillo, T. F.; Besenbacher, F. Building an Appropriate Active-Site

Motif into a Hydrogen-Evolution Catalyst with Thiomolybdate [Mo3S13]2− Clusters. Nat. Chem. 2014, 6, 248-253. (42)

Wang, T.; Zhuo, J.; Du, K.; Chen, B.; Zhu, Z.; Shao, Y.; Li, M. Electrochemically

Fabricated Polypyrrole and MoSx Copolymer Films as a Highly Active Hydrogen Evolution Electrocatalyst. Adv. Mater. 2014, 26, 3761-3766.


18

Page 19 of 22

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


(43)

Huang, Z.; Luo, W.; Ma, L.; Yu, M.; Ren, X.; He, M.; Polen, S.; Click, K.; Garrett, B.;

Lu, J. Dimeric [Mo2S12]2− Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen-Evolution Electrocatalysis. Angew. Chem., Int. Ed. 2015, 54, 15181-15185. (44)

Müller, A.; Wittneben, V.; Krickemeyer, E.; Bögge, H.; Lemke, M. Studies on the

Triangular Cluster [Mo3S13]2−: Electronic Structure (Xα calculations, XPS), Crystal Structure of (Ph4As)2[Mo3S13].2CH3CN and a Refinement of the Crystal Structure of (NH4)2[Mo3S13]·H2O. Z. Anorg. Allg. Chem 1991, 605, 175-188. (45)

Weber, T.; Muijsers, J.; Niemantsverdriet, J. Structure of Amorphous MoS3. J. Phys.

Chem. 1995, 99, 9194-9200. (46)

Chang, C.; Chan, S. Infrared and Raman Studies of Amorphous MoS3 and Poorly

Crystalline MoS2. J. Catal. 1981, 72, 139-148. (47)

Lin-Vien, D.; Colthup, N. B.; Fateley, W. G.; Grasselli, J. G. The Handbook of Infrared

and Raman Characteristic Frequencies of Organic Molecules; Academic Press: London, 1991. (48)

Chen, D.; Wang, X.; Chen, J.; Ren, Z.; Xue, M.; Chen, G. Rewriting the

Superconductivity in Iron-Based Superconductors by Lithium-Ion Insertion and Extraction. Adv. Mater. 2015, 27, 4224-4228. (49)

Bianchi, C. L.; Cattania, M. G.; Villa, P. XPS Characterization of Ni and Mo Oxides

Before and After “In Situ” Treatments. Appl. Surf. Sci. 1993, 70, 211-216. (50)

Fleisch, T.; Mains, G. An XPS Study of the UV Reduction and Photochromism of MoO3

and WO3. J. Chem. Phys. 1982, 76, 780-786. (51)

Fu, Y.; Zu, C.; Manthiram, A. In Situ-Formed Li2S in Lithiated Graphite Electrodes for

Lithium–Sulfur Batteries. J. Am. Chem. Soc. 2013, 135, 18044-18047.


19


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

(52)

Page 20 of 22

Chen, S.; Dai, F.; Gordin, M. L.; Yu, Z.; Gao, Y.; Song, J.; Wang, D. Functional

Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium–Sulfur Batteries. Angew. Chem. Int. Ed. 2016, 55, 4231-4235. (53)

Wang, C.; Wang, X.; Yang, Y.; Kushima, A.; Chen, J.; Huang, Y.; Li, J. Slurryless

Li2S/Reduced Graphene Oxide Cathode Paper for High-Performance Lithium Sulfur Battery. Nano Lett. 2015, 15, 1796-1802. (54)

Yang, Z.; Liang, H.; Wang, X.; Ma, X.; Zhang, T.; Yang, Y.; Xie, L.; Chen, D.; Long,

Y.; Chen, J.; Chang, Y.; Yan, C.; Zhang, X.; Zhang, X.; Ge, B.; Ren, Z.; Xue, M.; Chen. G. Atom-Thin SnS2–xSex with Adjustable Compositions by Direct Liquid Exfoliation from Single Crystals. ACS Nano 2015, 10, 755-762. (55)

Sun, H.; Xin, G.; Hu, T.; Yu, M.; Shao, D.; Sun, X.; Lian, J. High-Rate Lithiation-

Induced Reactivation of Mesoporous Hollow Spheres for Long-Lived Lithium-Ion Batteries. Nat. Commun. 2014, 5, 4526. (56)

Kim, C.; Jung, J.-W.; Yoon, K. R.; Youn, D.-Y.; Park, S.; Kim, I.-D. A High-Capacity

and Long-Cycle-Life Lithium-Ion Battery Anode Architecture: Silver Nanoparticle-Decorated SnO2/NiO Nanotubes. ACS Nano 2016, 10, 11317-11326. (57)

Xue, M.; Ma, X.; Xie, Z.; Duan, L.; Jiang, Y.; Zhang, M.; Cao, T. Fabrication of Gold-

Directed Conducting Polymer Nanoarrays for High-Performance Gas Sensor. Chem.–Asian J. 2010, 5 (10), 2266-2270. (58)

Xue, M.; Li, F.; Wang, Y.; Cai, X.; Pan, F.; Chen, J. Ultralow-Limit Gas Detection in

Nano-Dumbbell Polymer Sensor via Electrospinning. Nanoscale 2013, 5, 1803-1805. (59)

Xue, M.; Li, F.; Chen, D.; Yang, Z.; Wang, X.; Ji, J. High-Oriented Polypyrrole

Nanotubes for Next-Generation Gas Sensor. Adv. Mater. 2016, 28, 8265-8270.


20

Page 21 of 22

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


(60)

Xue, M.; Wang, Y.; Wang, X.; Huang, X.; Ji, J. Single-Crystal-Conjugated Polymers

with Extremely High Electron Sensitivity through Template-Assisted In Situ Polymerization. Adv. Mater. 2015, 27, 5923-5929. (61)

Park, H.; Koh, H. S.; Siegel, D. J. First-Principles Study of Redox End Members in

Lithium−Sulfur Batteries. J. Phys. Chem. C 2015, 119, 4675-4683.


21


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

Page 22 of 22

TOC graphic


22

Unique Reversible Conversion-Type Mechanism Enhanced Cathode

Recommend Documents