Template-free synthesis of ultra-large V2O5 nanosheets with exceptional small thickness for high-performance lithium-ion batteries

doi:10.1016/j.nanoen.2015.01.049

Nano Energy

Volume 13, April 2015, Pages 58-66

https://doi.org/10.1016/j.nanoen.2015.01.049 Get rights and content

Highlights

•
The ultra-large VO₂ nanosheets with exceptional small thickness were successfully fabricated by a template-free solvothermal method.
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The VO₂ nanosheets can be safely converted into V₂O₅ nanosheets with well retained structures.
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The V₂O₅ nanosheets exhibited excellent cyclic stability and remarkable rate capability as cathode materials for lithium ion batteries.
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The excellent electrochemical performances were attributed to the layer-by-layer stacking of the ultra-large nanosheets with exceptional small thickness.

Abstract

Similar to graphene, transition metal oxide nanosheets have attracted a lot of attention recently owning to their unique structural advantages, and demonstrated promising chemical and physical properties for various applications. However, the synthesis of transition metal oxide nanosheets with controlled size and thickness remains a great challenge for both fundamental study and applications. The present work demonstrates a facile solvothermal synthesis of ultra-large (over 100 μm) VO₂(B) nanosheets with an exceptionally small thickness of only 2–5 nm corresponding to 3–8 layers of (001) planes. It can be readily transferred into V₂O₅ with well retained nanosheet structures when calcined, which exhibit remarkable rate capability and great cycling stability. Specifically, the as-synthesized vanadium pentoxide nanosheets deliver a specific discharge capacity of 141 mA h g⁻¹ at a current density of 0.1 A g⁻¹, which is 96% of its theoretical capacity (147 mA h g⁻¹) for one Li⁺ ion intercalation/removal per formular within a voltage window of 2.5–4 V. Even at an extreme-high current density of 5 A g⁻¹, it still can exhibit a high specific discharge capacity of 106 mA h g⁻¹. It is worthy to note that the V₂O₅ nanosheets electrode can retain 92.6% of the starting specific discharge capacity after 500 discharge/charge cycles at the current density of 1.5 A g⁻¹.

Graphical abstract

Section snippets

Introductions

Recently, two-dimensional (2D) materials have drawn considerable attention because of their distinctive electronic, photonic, magnetic and mechanical properties and promising applications in sensors, [1] catalysts, [2] and energy storage and conversion devices [3], [4], [5], [6], [7]. Intrigued by such advantages, great effort has been devoted to fabricate thinner and larger 2D nanosheets through facile methods. To date, delamination or exfoliation is the most commonly developed approaches to

Preparation of VO₂(B) uniform ultrathin nanosheets

All of the chemical reagents were of analytical grade and used without further purification. In a typical synthesis, 50 mg vanadium pentoxide (V₂O₅, ≥99.0%, Tianjin Damao Reagent Co., Ltd.) was dispersed in 5 ml deionized water by 5 min ultrasonic treatment. Then, 10 mL hydrogen peroxide (H₂O₂, ≥30%, Sinopharm Chemical Reagent Co., Ltd.) was added into the above suspension under vigorous stirring at room temperature, as it gradually turned into a bright yellow solution. And 5 min later, 10 mL

Results and discussions

The detailed color changes of the samples for each step are clearly presented in Figure S1. The color change from orange to a bright yellow solution was attributed to the reaction between V₂O₅ powders and H₂O₂ to form V₂O₅ sol. Adding isopropanol in the open beaker would not cause aparent color change at room temperature. After solverothermally treated at 180 °C for 6 h, dark blue precipitates were obtained (Figure S1d), the color of which is quite similar to that of VO₂. The blue precipitates

Conclusions

In summary, a facile one-pot solvothermal method has been developed to synthesize uniform VO₂(B) ultrathin nanosheets with a lateral size over 100 µm, which can be readily transformed into V₂O₅ nanosheets with good structural revervation, including the exceptionally small thickness and the large lateral size by calcination in air. Moreover, the layer-by-layer stacking structures are well revealed. As cathode materials for lithium ion batteries, the resulting V₂O₅ nanosheets exhibite remarkable

Acknowledgments

This work was supported by the National High Technology Research and Development Program of China (863 Program) (No. 2013AA110106), the National Natural Science Foundation of China (No. 51374255, 51302323), Program for New Century Excellent Talents in University (NCET-13–0594), Research Fund for the Doctoral Program of Higher Education of China (No. 201301621200), Natural Science Foundation of Hunan Province, China (14JJ3018), Lie-Ying and Sheng-Hua Program of Central South University, and

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Improvement of cycle performance of the high nickel cathode material LiNi<inf>0.88</inf>Co<inf>0.07</inf>Al<inf>0.05</inf>O<inf>2</inf> for lithium-ion batteries by the spray drying of V<inf>2</inf>O<inf>5</inf>
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Citation Excerpt :
In Fig. 3(g), there is a cladding layer of about 4 nm, and the interplanar spacing of the cladding layer is 0.205 nm, which corresponds to the (104) crystal plane of α-LiAlO2 (JCPDS NO.74-2232), this is the feature of using C9H21AlO3 hydrolysis to prepare NCA materials, which is the same as the previous work[25]. Through Fig. 3(h), it can be clearly seen that a cladding layer of about 10 nm with a crystal plane spacing of 0.186 nm, corresponding to the (012) crystal plane of V2O5 (JCPDS NO.41–1426) [26]. Fig. 3 The cladding layer in Fig. 3(i-j) surprisingly reaches about 25 nm.
LiNi_xCo_yAl_1−x-yO₂ (NCA), as high nickel cathode material, has a high capacity and is one of the most promising cathode materials for lithium-ion batteries. However, the disadvantages such as more residual lithium compounds and serious capacity decay have hindered the industrial application of this material. In order to reduce the residual lithium compound on the surface of the material and restrain the capacity degradation, we designed and prepared a high nickel cathode material by pretreatment washing and subsequent spray drying, which has high cycle life and high discharge specific capacity. Compared to the first discharge specific capacity of 196.6 mAh g⁻¹(0.2 C) for the raw material and 131.4 mAh g⁻¹ after 100 cycles of 1 C, the discharge specific capacity of the modified sample 2V₂O₅@NCA was increased to 210.4 and 163.8 mAh g⁻¹, respectively. Microstructure observation revealed that V₂O₅ not only uniformly covers the surface of the secondary particles, but also the presence of electrochemically active LiV₃O₈, which avoids the direct contact between the active material and electrolyte, thus significantly suppressing the interfacial side reactions between the cathode material and electrolyte and improving the structural stability of the material. Our exploration may pave a way for developing high cycle stability of high nickel cathode materials.
V<inf>2</inf>O<inf>5</inf> nanocrystals: Chemical solution synthesis, hydrogen thermal treatment and enhanced rate capability as cathode materials for lithium-ion batteries
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Citation Excerpt :
In addition, higher contact interfaces between electrode and electrolyte, and better accommodation of strain upon lithium intercalations/deintercalations for nanostructured cathode materials also constitute advantages to obtaining enhanced electrochemical performance. Various nanostructured V2O5 such as nanoparticles [27,28], nanosheets [29–32], and nanorods/nanowires/nanotubes [33–36] have been prepared to alleviate the aforementioned kinetic limitations. The introduction of oxygen vacancies in materials is also a valuable method to enhance the ion and electron conductivities of nanostructured cathode materials [37–39].
Vanadium pentoxide (V₂O₅) is regarded as a promising cathode material for high-performance lithium-ion batteries (LIBs). In this study, V₂O₅ nanocrystals with an elongated plate-like morphology are prepared via a chemical solution approach that involves the hydrolyzation of vanadyl sulfate in alkaline solution. Oxygen vacancies are intentionally created by thermal treating the V₂O₅ samples under hydrogen-containing gases at different temperatures. Although the annealing process does not change the shape, morphology and crystalline structure of V₂O₅ nanocrystals, it does bring about a small amount of oxygen vacancies, as evidently from the results of XRD patterns and Raman spectra. The presence of oxygen vacancies has positive effects on the electrochemical properties. A higher initial discharge capacity, and excellent rate capability and cycling stability are observed on the oxygen vacancy-containing V₂O₅ samples. Especially, the sample annealed at 350 °C is found to have an initial capacity of 284 mAh g⁻¹and the capacity still maintains at about 153 mAh g⁻¹ even at 10 C. The combination of nanoscale dimension and oxygen vacancies in V₂O₅ nanocrystals presents a simple way to improve their rate capability and cycling stability for potential high-performance LIB applications.

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Prof. Shuquan Liang received his Ph.D. degree from Central South University (PR China) in 2000. He has been the Dean of School of Materials Science and Engineering at Central South University since 2010. He is the winner of Monash University Engineering Sir John Medal. In the last five years, he developed a research group on the Vanadium-based nanomaterials as cathodes for lithium batteries. He hosted 5 state research projects including national 973 and national 863 projects. He has published more than 60 papers in peer-reviewed journals such as Energy & Environmental Science and Journal of Materials Chemistry. Currently, his main research interests include micro/nanostructured functional materials, nanocomposites and energy storage and conversion devices.

Yang Hu received his B.E. in Materials Science and Engineering from Central south university (PR China) in 2013. Currently, under the guidance of Prof. Liang, he is studying for his Ph.D. Degree in Materials Physics and Chemistry in Central South University. His current research interest is nanostructured cathode materials for lithium ion batteries.

Zhiwei Nie is now a postgraduate student at the School of Materials Science and Engineering, Central South University (PR China). His current research interest is the synthesis of hollow-structured materials for lithium ion batteries.

Dr. Han Huang received his BE degree at National University of Defense Technology China in 2002 and Ph.D degree from Physics Department at Zhejiang University, China in 2008. He is currently a professor of physics at Central South University in Changsha China following a six-year research career in National University of Singapore. His current research interests include molecule–substrate interface problems associated with molecular electronics, as well as fabrication and modification of graphene, graphene nanoribbons and other 2-dimensional materials.

Tao Chen received the M.A. from Central South University in 2013, and B.S. from Shanxi University of Science and Technology of China (PR China) in 2010. Currently, he is a Ph.D. candidate under the supervision of Prof. Shuquan Liang at the School of Materials Science and Engineering of Central South University (PR China). His research interests focus on the synthesis of nanostructured materials for lithium ion batteries.

Anqiang Pan received his B. E. (2005) and D. Phil. (2011) degrees in Materials Physics and Chemistry from Central South University in Prof. Shuquan Liang׳s group. In 2008, he worked in Prof. Guozhong Cao׳s group at University of Washington as an exchange student (2008–2009). Then, he got the chance to work in PNNL as a visiting scholar in Dr. Ji-Guang Zhang and Dr. Jun Liu׳s group (2009–2011). After getting the PhD degree, he joined Prof. Xiongwen (David) Lou׳s group at Nanyang Technological University as a research fellow (2011–2012). He joined the faculty at Central South University in 2012 and was promoted to a Sheng-Hua Professor in 2013. His current interests are the controllable synthesis of nanostructured materials and their applications in energy storage and conversion devices, such as lithium ion batteries, and supercapacitors.

Guozhong Cao is Boeing-Steiner professor of Materials Science and Engineering, professor of Chemical Engineering and adjunct professor of Mechanical Engineering at the University of Washington, Seattle, WA, and also a senior professor at Beijing Institute of Nanoenergy and Nanosystems and a professor at Dalian University of Technology, China. His current research focused on chemical processing of nanomaterials for solar cells, batteries, and supercapacitors as well as actuators and sensors.

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Rapid communicationTemplate-free synthesis of ultra-large V2O5 nanosheets with exceptional small thickness for high-performance lithium-ion batteries

Highlights

Abstract

Graphical abstract

Section snippets

Introductions

Preparation of VO2(B) uniform ultrathin nanosheets

Results and discussions

Conclusions

Acknowledgments

J. Power Sources

Electrochem. Commun.

J. Solid State Chem.

Spectrochim. Acta Part A Mol.. Spectrosc.

J. Power Sources

J. Solid State Chem.

J. Power Sources

Mater. Res. Bull.

Curr. Appl. Phys.

Small

Nature

ACS Nano

Adv. Mater.

Angew. Chem. Int. Ed.

Nanoscale

Small

Angew. Chem. Int. Ed.

Adv. Mater.

Rapid communication
Template-free synthesis of ultra-large V₂O₅ nanosheets with exceptional small thickness for high-performance lithium-ion batteries

Preparation of VO₂(B) uniform ultrathin nanosheets