C Composite as High-Performance Anode Materials

Subscriber access provided by READING UNIV

Letter 2

5

Amorphous PS/C Composite as High-Performance Anode Materials for Sodium-Ion Batteries XIANG LI, Shaohua Guo, Kezhu Jiang, Yu Qiao, Masayoshi Ishida, and Haoshen Zhou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b14673 • Publication Date (Web): 22 Dec 2017 Downloaded from http://pubs.acs.org on December 23, 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 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

ACS Applied Materials & Interfaces

Amorphous P2S5/C Composite as High-Performance Anode Materials for Sodium-Ion Batteries Xiang Li, †, §, ‡ Shaohua Guo *, †, ‡ Kezhu Jiang, † Yu Qiao, §, ‡ Masayoshi Ishida § and Haoshen Zhou *, †, §, ‡

† National Laboratory of Solid State Microstructures & Department of Energy Science and Engineering, Nanjing University, Nanjing, 210093, P. R. China. §Graduate School of System and Information Engineering, University of Tsukuba, Tennoudai 1-1-1, Tsukuba, 305-8573, Japan ‡ Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, 305-8568, Japan. KEY WORDS: P2S5/C composite; anode materials; amorphous; sodium-ion batteries; high-performance

ABSTRACT We show a general method for achieving high-performance sodium storage materials via transforming crystalline P2S5 to amorphous P2S5 adhered to carbon matrix. The amorphous P2S5/C composite shows unique structural characteristics differing from the crystalline, which is identified by Xray diffraction (XRD), Raman spectroscopy, transmission electron microscope (TEM) and so on. The amorphous P2S5/C composite exhibits a safe average potential of 0.82 V, a reversible capacity of 400 mA h g-1, a remarkable capacity retention of 89.4 % over 4000 cycles as well as good rate capability. Our findings open up opportunities to design of advanced anodes for room-temperature sodium-ion batteries.

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

Page 2 of 15

Lithium-ion batteries (LIBs) have been extensively used surrounding our lives.1 However, the limitation of lithium resources and high cost of lithium cannot match our increasing requirement.2 With the extensive and low-cost sodium sources, and similar chemistry to lithium, sodium-ion batteries (SIBs) have received widespread attention.3 It is more difficult comparing with LIBs when hunting for a suitable electrode material for SIBs because of the larger and heavier Na+ than Li+.4 It is known that the formation of dendrite and instability in fast charging-discharging make the metallic sodium not suitable for the anode.5 P2-type Na2/3Co1/3Ti2/3O2 6 with outstanding cycle stability (84.8 % capacity retention for 3000 cycles) and Na0.66Ni0.17Co0.17Ti0.66O27 serving as both anode and cathode have also been reported. Molybdenum-based oxides like Na0.3MoO28 is proved a promising anode material for SIBs. Many materials such as Sn,9-10 Sb,11 Ge, 12 P13 and binary/ternary composites14-18 have also been developed as SIBs anode by conversion and/or alloying/dealloying processes. Herein, we demonstrate a low-cost P2S5/C composite anode for SIBs, exhibiting a high capacity of  400 mA h g-1, a safe average potential of  0.82 V, and ultrastable cycling performance without detectable capacity decay. It is acknowledged that crystalline graphite is widely-used in LIBs but electrochemically inactive in SIBs. 19 When non-graphitic hard carbon with disordered structure is employed as sodium storage materials, a large capacity is delivered despite that most of capacity of 300 mA h g-1 corresponds to sodium plating, associated with the safety concern. Herein, we present an amorphization method in P2S5/C composite for high-safety and stable-cycling sodium storage materials, which can be applied to other negative materials.20 The structure of P2S5 (more accurate: P4S10) is built from P4 in tetrahedral form, all six sides made of P-P bonds broken by the addition of one sulfur atom between each P atom (turned to P-S-P bonds).21 The ball-milling time shows a great influence on the X-ray diffraction (XRD) patterns of crystalline and amorphous P2S5, as shown in Figure 1a. XRD reflection of the commercial P2S5 (without mixed acetylene black (AB) and ball-milling) exhibits a well-crystallized phase (black line) symbolized by the sharp peaks at around 2θ = 30o and 53o. When the time increases to 70 h, the feature peaks of P2S5 completely disappear and only one broad peak at 2θ = 26o exists (blue line) which belongs to AB, suggesting a transformation of crystalline P2S5 to amorphous P2S5 in the composite. We also synthesized P2S5/C ACS Paragon Plus Environment

2

Page 3 of 15

composite with 2 h and 40 h (Figure S1) ball-milling process to contrast. As shown in Figure 1a, the feature peaks of P2S5 still appear (pink line) after short ball-milling (with AB), merely with the reduced intensity and broadening.

2h

(c)

20

30

40 50 2(deg.)

60

zoo

m

D

in

G

P2S5/C commercial P2S5

400

70

(d)

P 2p

A1 P=S

400 500 600 700 800

0h 10

T2 P=S

70 h

P-S-P

Intensity (a.u.)

(b)

Intensity (a.u.)

(a)

800 1200 Raman shift (cm-1)

1600

S 2p

Intensity (a.u.)

Intensity (a.u.)

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


130

132 134 136 138 Binding energy (eV)

140

160

162 164 166 168 Binding energy (eV)

Figure 1. XRD patterns of commercial P2S5 (black line), P2S5/C composite after 2 h (pink line) and 70 h (blue line) ball-milling (a); Raman spectra of commercial P2S5 and P2S5/C composite after 70 h ballmilling (b); XPS spectra of P 2p (c) and S 2p (d) for the P 2S5/C composite after 70 h ball-milling. Raman spectra also show a difference between commercial P2S5 and P2S5/C composite after long-time ball-milling (Figure 1b). Raman spectrum of the commercial P2S5 shows the specific stretching vibrations of the P-S-P bond signal at ~ 390 cm-1 and P=S bond at around 686 and 712 cm-1 (red line), which are the typical Raman fingerprints of P2S5, corresponding to the T2 and A1 modes.22 The fingerprints bonds of P2S5 also appear after long-time ball-milling, accompanied by the weakening of the intensity and the shift


3


Page 4 of 15

to higher wavenumber (see blue line in Figure 1b, clearer in zoom in figure). The obvious carbon peaks are observed at around 1320 and 1580 cm-1 for D-band and G-band (blue line), respectively. To probe the surface chemical state of the P2S5/C composite, X-ray photoelectron spectroscopy (XPS) was employed. The structure of P2S5 is isostructural with that of P2O5. It is easy to know that there are one species of P and two species of S according to the molecular structure. As shown in the P2p XPS spectra (Figure 1c), the spectrum has been fitted to the 2p1/2 and 2p3/2 doublet, corresponding to a binding energy value 134.6 eV and a splitting value 0.9 eV. Similarly, there are two sulfur species with the binding energy values of 165.3 eV and 164.2 eV respectively. Thermogravimetry (TG) and differential thermoanalysis (DTA) were further employed to reveal the proportion of P2S5 in P2S5/C composite. Figure S2 shows the TG-DTA curves of the commercial P 2S5 and P2S5/C composite after long-time ball-milling. From the curve (Figure S2b) of commercial P2S5, it can be found that there is one typical endotherm peak at approximately 270 oC which is attributed to the melting process of P2S5. And there are two main peaks of DTA in the curve of P2S5/C composite (Figure S2a), which represent the melting process and oxidation process (720 oC), respectively. The proportion of P2S5 in P2S5/C composite is about 66.7% which can be easily estimated from the comparison of two figures, and this value is consistent with the initial mass ratio of P2S5/AB.


4

Page 5 of 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


(d) C

(a)

1 μm (e)

(b)

P

1 μm 100 nm

(c)

100 nm

(f) S

1 μm Figure 2．Images of the amorphous P2S5/C composite after 70 h ball-milling. SEM image (a), TEM image (b), selected area electron-diffraction pattern (c), and EDX mapping of carbon (d), phosphorus (e), and sulfur (f). Scanning electron microscope (SEM) images of commercial P2S5 (Figure S3) and P2S5/C composite (Figure 2a) after 70 h ball-milling show agglomerated particles with nanoparticles. EDX (energy dispersive X-ray spectroscopy)-mapping (the area selected in Figure S4) indicates the homogeneous distribution of C, P, and S in the P2S5/C composite (Figure 2d – 2f). No typical Scherrer rings of P2S5 are observed after long-time ball-milling (Figure 2c), demonstrating that the crystalline P 2S5 particles change to an amorphous-like phase. And the amorphous P2S5 particles with nanosize are uniformly encapsulated within the carbon matrix. The results are consistent with that of XRD which have been discussed before. ACS Paragon Plus Environment

5


The initial discharge specific capacity at 100 mA g-1 with 70 h ball-milling is near 1000 mA h g-1, and the charge specific capacity changes to 400 mA h g-1 (Figure S5a). The dQ/dV curve of the first cycle is shown in Figure S5b. In the first discharge, several peaks appeared between 0.01 V and 1.3 V, including one broad peak, belonging to the formation of solid electrolyte interface (SEI). There is also one small peak located at 0.03 V, which represents the insertion of sodium into AB. In contrast, the initial charge/discharge profiles of P2S5@C electrodes were also tested (Figure S6, the ball-milling time between 0 h ~ 70 h). It is obvious that there is almost no plateau for the commercial P2S5. The first discharge capacity of pure P2S5 is about 60 mA h g-1 and the stable reversible capacity is merely 14 mA h g-1. The profile of the electrode with ball-milling 40 h is similar to the electrode with ball-milling time 70 h, indicating the similar reaction mechanism. The performance of the electrode is the best when it was treated

2nd 50th 100th

1.0 0.5 0.0

100

200

300

Capacity retention (%)

Specific capacity (mAh g )

150

120 100

100

(e)

80

50 0 0

20

40

99.5 %

60

Discharge Charge Coulombic efficiency

40

60

80

20

0 100

0

(d)

-1

2nd 50th 100th

1000

-1000

400

Specific capacity (mAh g-1)

0

(c)

2000

0.0

0.5

1.0

1.5

2.0

+

Potential (V vs. Na /Na)

400

100mA/g 200mA/g

300

400mA/g

200

1 A/g 2 A/g

100 0

Cycle number

Discharge Charge

10

20

30

40

50

Cycle number

150

120 100

100

80 89.4 % Discharge Charge Coulombic efficiency

50 0

0

1000

2000

3000

60 40 20 0 4000

Coulombic Efficiency (%)

1.5

dQ/dV (mAh g-1 V-1)

(b) 2.0

Coulombic efficiency (%)

(a)

Potential (V vs. Na+/Na)

with the longer ball-milling time of 70 h.


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 15

Cycle number


6

Page 7 of 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


Figure 3. Electrochemical performance of P2S5/C composite after 70 h ball-milling. Typical potential profiles (a) and dQ/dV curves of the 2nd, 5th and 100th cycle (b); Cyclic performance and coulombic efficiency with 100 mA g-1 (c); Rate capacity of P2S5/C composite (d). Cyclic performance and coulombic efficiency with 2000 mA g -1(e) The cycle curves of P2S5/C composite after 70 h ball-milling are shown in Figure 3a. A reversible capacity of 396 mA h g -1 is obtained at 100 mA g -1 after the initial cycle (based on the mass of P2S5). A pattern of overlapping is remarkably found among all the cycles. Moreover, the electrode shows excellent capacity retention upon cycling. Even after 100 cycles, a specific capacity of 394 mAh g-1 with almost negligible capacity decay is still acquirable. Figure 3b shows the dQ/dV curves from Figure 3a. The well overlapping profiles can be found during cycling, indicating its high reversibility. The cycling performance and coulombic efficiency of P 2S5/C composite/Na battery can be seen in Figure 3c. The P2S5/C composite has a high coulombic efficiency ranging from 98.6% to 99.7% and the capacity has almost no attenuation. Moreover, a capacity of 308 mA h g-1 was obtained with the current density of 200 mA g-1. And even at higher rates of 400, 1000, and 2000 mA g-1, the capacity of 236, 155 and 108 mA h g-1 were accessible respectively (see Figure 3d, all capacities base on P2S5 after subtracting contribution form AB). Further, the capacity contribution from AB after 70h ball-milling was also evaluated (AB as the anode of the sodium battery) under identical test conditions as shown in Figure S7a. It is obvious that the capacity contribution of AB is negligible (about 15 mA h g -1 after the first cycle). There also exists one broad dQ/dV peak of AB near 0.37 V for the first cycle, which belongs to the decomposition of electrolyte (Figure S7b). One sharp peak near 0.03 V represents the insertion process of sodium into AB similar to Figure S5b. Moreover, we also tested a long-time cycling performance with the current density of 2 A g-1 (Figure 3e). The capacity is stable without any notable decay and the battery could retain 89.4% of the capacity even after more than 4000 cycles, indicating a superior reversible performance. To research the kinetic differences of the P2S5/C composites with different ball-milling time, electrochemical impedance spectroscopy (EIS) measurements were performed (Figure S8). The curves show the EIS of the electrodes after the initial cycle, respectively. The ball-milling time are 2 h, 40 h, and ACS Paragon Plus Environment

7


Page 8 of 15

70 h. The semicircle diameter for P2S5/C composite with ball-milling time 70 h is much smaller than that for P2S5/C composite with ball-milling time 2h and 40h, indicating the great improvement of electron conductivity (formation of the amorphous structure). The long-time ball-milling is great helpful to promote the electrode kinetics, accounting for a high-rate performance of the P2S5/C composite electrode. The initial cycle was explored by ex-situ XRD for investigating the reaction mechanism of amorphous P2S5 with Na, as shown in Figure S9. At the beginning of the reaction, there are almost no peaks appear before discharge to 1.0 V (C1). Upon sodiation to 0.3 V (C2), the electrode shows clear peaks which are assign to NaP, Na2S and S. When sodiated to 0 V (C3), the NaP signals vanish and the Na3P signals are observed. Note that there is a broad amorphous peak at ~ 23o still exists, which is assigned to S, indicating its partial activity. At reversed desodiation process, the peaks returned to their initial state, expect for an irreversible broad peak assigned to S and/or Na2S, indicating an irreversible process during cycling. The partial activity of anode, irreversible process and formation of SEI mainly account for the irreversible capacity of the initial cycle. It is likely that the reaction mechanism may base on the conversion and alloying processes as follows: Conversion: 10Na+ + 10e− + P2 S5 → 5Na2 S + 2P Alloying: 6Na+ + 6e− + 2P → 2Na3 P Table 1. Electrochemical performance of different anodes in sodium half-cells. Cycle life (cycles)

Current density (mA g-1)

Capacity retention

Reversible capacity (mAh g-1)

Hard carbon19

100

25

88.0%

250

Carbon nanofibers23

600

200

88.0%

~ 200

Na0.3MoO28

1000

500

72.4%

~ 146

NaVSnO424

1000

100

80.0%

~ 163

Na2Ti3O725

50

18

76.0%

~ 150

NaTi2(PO4)3/C26

1000

66

56.3 %

~ 110

Na3V2(PO4)3/C27

1000

1000

62.0%

~ 170

50

100

14.1%

~ 400

Samples

Phosphorus-carbon nanocomposite28


8

Page 9 of 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


Mo3Sb729

100

1700

45.4%

330

N-doped TiO230

300

840

78.1%

~ 250

Na2/3Co1/3Ti2/3O26

3000

500

84.8%

~ 50

Na0.66Ni0.17Co0.17Ti0.66O27

300

20

88.3%

~ 100

Amorphous P2S5/C (this work)

4000

2000

89.4%

~ 400

Literature data of some different anodes on the electrochemical performance is exhibited in Table 1. It is obvious that P-based anodes show high capacities including the amorphous P2S5/C composite. However, the capacity has been found to decline dramatically from 1322 to 186 only after 50 cycles at 100 mA g-1 (ref. 28), corresponding a capacity retention of merely 14.1% which far lower than 89.4% in our result. There are three obvious advantages of the amorphous P2S5/C composite compared with other anodes in Table 1. The first is the capacity: the P2S5/C composite shows ~ 400 mA h g -1 during discharge process which is larger than most of the other anodes. The second is capacity retention: the P 2S5/C composite shows the best capacity retention of 99.5% after 100 cycles at 100 mA g-1, followed by 93.0% in hard carbon spherules at 30 mA g-1. The third is long-time cycling performance: the P2S5/C composite shows an excellent performance with neglectable capacity fading. Other materials show relatively poor performance, which are unsatisfactory for the commercial use. Different from these materials, our results indicate that the amorphous P2S5/C composite is capable of sustaining excellent electrochemical performance which may result from the suppression of volume expansion and the interactions between P2S5 and AB. In summary, P2S5/C composite is prepared using a simple long-time high energy ball-milling method and its reaction mechanism with Na is investigated. The electrode demonstrates a high reversible capacity of 396 mA h g-1 at 100 mA g-1, an outstanding capacity retention (99.5% after 100 cycles at 100 mA g-1), and a moderate capacity at high rate (114 mA h g-1 at 2 A g-1). Even when the amorphous P2S5/C is cycled over 4000 times at 2 A g-1, a high capacity retention of 89.4 % is achieved. The good performance may benefit from the amorphous of P2S5 and the homodisperse of P2S5 into carbon matrix. In the current drive


9


Page 10 of 15

to discover and optimize materials for specific energy storage, the P 2S5/C composite can pave a new way for the next generation of low-cost, high energy sodium-ion batteries.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. XRD patterns, SEM images, selected area electron-diffraction pattern, TG-DTA curves, chargedischarge curves, dQ/dV curves and EIS curves AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] * E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS X. Li is grateful for the financial support of the CSC (China Scholarship Council) scholarship. This work was partially supported financially by National Basic Research Program of China (2014CB932302), Natural Science Foundation of Jiangsu Province of China (BK20170630), the Fundamental Research Funds for the Central Universities (021314380076, 021314380080), and the National Natural Science Foundation of China (21673116, 2163303).


10

Page 11 of 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


REFERENCES 1. Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359-367. 2. Tarascon, J. M. Is Lithium The New Gold? Nat. Chem. 2010, 2, 510-510. 3. Cao, Y. L.; Xiao, L. F.; Wang, W.; Choi, D. W.; Nie, Z. M.; Yu, J. G.; Saraf, L. V.; Yang, Z. G.; Liu, J. Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life. Adv. Mater. 2011, 23, 3155-3160. 4. Wang, L.; Lu, Y. H.; Liu, J.; Xu, M. W.; Cheng, J. G.; Zhang, D. W.; Goodenough, J. B. A Superior Low-Cost Cathode for a Na-Ion Battery. Angew. Chem. Int. Ed. 2013, 52, 1964-1967. 5. Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; Carretero-Gonzalez, J.; Rojo, T. Na-Ion Batteries, Recent Advances and Present Challenges to Become Low Cost Energy Storage Systems. Energy Environ. Sci. 2012, 5, 5884-5901. 6. Yu, H. J.; Ren, Y.; Xiao, D. D.; Guo, S. H.; Zhu, Y. B.; Qian, Y. M.; Gu, L.; Zhou, H. S. An Ultrastable Anode for Long-Life Room-Temperature Sodium-Ion Batteries. Angew. Chem. Int. Ed. 2014, 53, 89638969. 7. Guo, S. S.; Liu, P.; Sun, Y.; Zhu, K.; Yi, J.; Chen, M. W.; Ishida, M.; Zhou, H. S. A High-Voltage and Ultralong-Life Sodium Full Cell for Stationary Energy Storage. Angew. Chem. Int. Ed. 2015, 54, 1170111705. 8. Zhu, K.; Guo, S. H.; Yi, J.; Bai, S. Y.; Wei, Y. J.; Chen, G.; Zhou, H. S. A New Layered Sodium Molybdenum Oxide Anode for Full Intercalation-Type Sodium-Ion Batteries. J. Mater. Chem. A 2015, 3, 22012-22016. 9. Xu, Y. H.; Zhu, Y. J.; Liu, Y. H.; Wang, C. S. Electrochemical Performance of Porous Carbon/Tin Composite Anodes for Sodium-Ion and Lithium-Ion Batteries. Adv. Energy Mater. 2013, 3, 128-133. 10. Mao, J.; Fan, X.; Luo, C.; Wang, C. Building Self-Healing Alloy Architecture for Stable Sodium-Ion Battery Anodes: A Case Study of Tin Anode Materials. ACS Appl. Mater. Interfaces 2016, 8, 7147-7155.


11


Page 12 of 15

11. Wu, L.; Hu, X. H.; Qian, J. F.; Pei, F.; Wu, F. Y.; Mao, R. J.; Ai, X. P.; Yang, H. X.; Cao, Y. L. SbC Nanofibers with Long Cycle Life as an Anode Material for High-Performance Sodium-ion Batteries. Energy Environ. Sci. 2014, 7, 323-328. 12. Abel, P. R.; Lin, Y. M.; de Souza, T.; Chou, C. Y.; Gupta, A.; Goodenough, J. B.; Hwang, G. S.; Heller, A.; Mullins, C. B. Nanocolumnar Germanium Thin Films as a High-Rate Sodium-Ion Battery Anode Material. J. Phys. Chem. C 2013, 117, 18885-18890. 13. Gao, H.; Zhou, T.; Zheng, Y.; Liu, Y.; Chen, J.; Liu, H.; Guo, Z. Integrated Carbon/Red Phosphorus/Graphene Aerogel 3D Architecture via Advanced Vapor-Redistribution for High-Energy Sodium-Ion Batteries. Adv. Energy Mater. 2016, 6, 1601037. 14. Zheng, Y.; Zhou, T.; Zhang, C.; Mao, J.; Liu, H.; Guo, Z. Boosted Charge Transfer in SnS/SnO 2 Heterostructures: Toward High Rate Capability for Sodium-Ion Batteries. Angew. Chem. Int. Ed. 2016, 55, 3408-3413. 15. Zhou, T.; Pang, W. K.; Zhang, C.; Yang, J.; Chen, Z.; Liu, H. K.; Guo, Z. Enhanced Sodium-Ion Battery Performance by Structural Phase Transition from Two-Dimensional Hexagonal-SnS2 to Orthorhombic-SnS. ACS Nano 2014, 8, 8323-8333. 16. Zhang, W.; Mao, J.; Pang, W. K.; Guo, Z.; Chen, Z. Large-scale synthesis of ternary Sn5SbP3/C Composite by Ball Milling for Superior Stable Sodium-Ion Battery Anode. Electrochim. Acta 2017, 235, 107-113. 17. Wang, Y.-X.; Seng, K. H.; Chou, S.-L.; Wang, J.-Z.; Guo, Z.; Wexler, D.; Liu, H.-K.; Dou, S.-X. Reversible Sodium Storage via Conversion Reaction of a MoS2-C Composite. Chem. Commun. 2014, 50, 10730-10733. 18. Li, L.; Seng, K. H.; Li, D.; Xia, Y.; Liu, H. K.; Guo, Z. SnSb@Carbon Nanocable Anchored on Graphene Sheets for Sodium Ion Batteries. Nano Res. 2014, 7, 1466-1476. 19. Komaba, S.; Murata, W.; Ishikawa, T.; Yabuuchi, N.; Ozeki, T.; Nakayama, T.; Ogata, A.; Gotoh, K.; Fujiwara, K. Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries. Adv. Funct. Mater. 2011, 21, 3859-3867. ACS Paragon Plus Environment

12

Page 13 of 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. Qian, J. F.; Chen, Y.; Wu, L.; Cao, Y. L.; Ai, X. P.; Yang, H. X. High Capacity Na-Storage and Superior Cyclability of Nanocomposite Sb/C Anode for Na-ion Batteries. Chem. Commun. 2012, 48, 7070-7072. 21. Li, X.; Liang, J.; Lu, Y.; Hou, Z.; Cheng, Q.; Zhu, Y.; Qian, Y. Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries. Angew. Chem. Int. Ed. 2017, 56, 2937-2941. 22. Jensen, J. O.; Zeroka, D. Theoretical Studies of The Infrared and Raman Spectra of P4S10. J. Mol. Struc-theochem 1999, 487, 267-274. 23. Luo, W.; Schardt, J.; Bommier, C.; Wang, B.; Razink, J.; Simonsen, J.; Ji, X. L. Carbon Nanofibers Derived from Cellulose Nanofibers as a Long-Life Anode Material for Rechargeable Sodium-Ion Batteries. J. Mater. Chem. A 2013, 1, 10662-10666. 24. Li, Q.; Guo, S.; Zhu, K.; Jiang, K.; Zhang, X.; He, P.; Zhou, H. A Postspinel Anode Enabling SodiumIon Ultralong Cycling and Superfast Transport via 1D Channels. Adv. Energy Mater. 2017, 7, 1700361. 25. Rudola, A.; Saravanan, K.; Mason, C. W.; Balaya, P. Na 2Ti3O7: An Intercalation-based Anode for Sodium-Ion Battery Applications. J. Mater. Chem. A 2013, 1, 2653-2662. 26. Pang, G.; Nie, P.; Yuan, C. Z.; Shen, L. F.; Zhang, X. G.; Li, H. S.; Zhang, C. L. Mesoporous NaTi2(PO4)3/CMK-3 Nanohybrid as Anode for Long-Life Na-Ion Batteries. J. Mater. Chem. A 2014, 2, 20659-20666. 27. Wang, D. X.; Chen, N.; Li, M. L.; Wang, C. Z.; Ehrenberg, H.; Bie, X. F.; Wei, Y. J.; Chen, G.; Du, F. Na3V2(PO4)3/C Composite as The Intercalation-Type Anode Material for Sodium-Ion Batteries with Superior Rate Capability and Long-Cycle Life. J. Mater. Chem. A 2015, 3, 8636-8642. 28. Ramireddy, T.; Xing, T.; Rahman, M. M.; Chen, Y.; Dutercq, Q.; Gunzelmann, D.; Glushenkov, A. M. Phosphorus-Carbon Nanocomposite Anodes for Lithium-Ion and Sodium-Ion Batteries. J. Mater. Chem. A 2015, 3, 5572-5584. 29. Baggetto, L.; Allcorn, E.; Unocic, R. R.; Manthiram, A.; Veith, G. M. Mo 3Sb7 as A Very Fast Anode Material for Lithium-Ion and Sodium-Ion Batteries. J. Mater. Chem. A 2013, 1, 11163-11169.


13


30. Yang, Y. C.; Ji, X. B.; Jing, M. J.; Hou, H. S.; Zhu, Y. R.; Fang, L. B.; Yang, X. M.; Chen, Q. Y.; Banks, C. E. Carbon Dots Supported Upon N-doped TiO2 Nanorods Applied into Sodium and Lithium

+ Potential (V vs. Na /Na)

Ion Batteries. J. Mater. Chem. A 2015, 3, 5648-5655.

2.0 1.5 2nd 50th 100th

1.0 0.5 0.0 0

100

200

300

400 120 100

100

80 Discharge Charge

50

89.4 %

40

Coulombic efficiency 0

0

1000

2000

3000

60

20 0 4000

Coulombic Efficiency (%)

Specific capacity (h g-1) 150


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 14 of 15

Cycle number


14

Page 15 of 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


721x601mm (96 x 96 DPI)


C Composite as High-Performance Anode Materials

Recommend Documents