Proceedings of the 4th International Conference on

Nanostructures (ICNS4)

Invited Papers

12-14 March 2012, Kish Island, I.R. Iran

INV 21

The Fast Diffusion of the Lithium Ions in Carbon Nanotubes

Ya-Pu Zhao
State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics,
Chinese academy of Sciences, Beijing 100190, China
yzhao@imech.ac.cn

With the development of advanced energy storage technologies, investigation of high-power and long-life batteries becomes more and
more important. Because of an outstanding combination of high-energy density and reversibility, rechargeable lithium (Li) ion batteries
are widely used as power sources, which have lots of advantages such as low cost and environment-friendly. Plenty of materials can be
adopted for the Li ions storage. at the present, the choke point for the high density storage of Li ions is the anode material. The most
widely used anode material is graphite, whose capacity is 372 mahg-1. The low energy density makes the graphite fails to become the
new candidates of the anode material. Some new materials, such as antimony (660 mahg-1) [1], tin (994 mahg-1) [2], silicon (4200 mahg-1)
[3] have been investigated. However, during the insertion of the Li ions into these materials, the crystal structure changes and enormous
volume changes make the materials have the poor capacity retention and irreversible crystalline structure change. The excellent mechanics properties of the carbon nanotube (CNT) make it becomes a candidate for the electrode reinforcement [4]. However, within the CNT
encapsulated, the CNT become the first obstacle or energy barrier for the Li ions diffusion. How to make the Li ions get through into the
CNT becomes a critical issue.
Here, ab initio simulations and molecular dynamics simulations are adopted to investigate the Li ion diffusion mechanism in CNT. Firstly,
ab initio simulations are used to find the diffusion pass way of the Li ion. Two kinds of diffusion ways are considered: wall-ring diffusion
and tube end diffusion. In the wall-ring diffusion, the curvature and chirality of the CNT are analyzed. Fig 1 provides some possible diffusion ways of Li ions. The results demonstrate that the Li ions can permeate CNT through the tube end freely under the normal charge
voltage (~3.6 V).

Figure 1. Possible diffusion ways of Li ion in CNT

Sencondly, molecular dynamics simulations are adopted to find the fast diffusion ways of Li ions with an external electric field. The electric field is applied on CNT arrays. Fig 2(a) is the simulation model. Fig 2(b) shows the direction of external electric filed which are applied along the axis of the tube (z-direction) and perpendicular direction (y-direction). The uniform and alternating electric filed are used.
The results show that the alternating electric filed applied on the y-direction will accelerate the diffusion and more ions will be stored in
the CNTs. The simulation results will provide a new charging method for the Li ion battery.

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Abstract Book |INST| Sharif University of Technology| 

Proceedings of the 4th International Conference on

Nanostructures (ICNS4)

Invited Papers

12-14 March 2012, Kish Island, I.R. Iran

Figure 2. The external electric field is applied on CNTs to accelerate the diffusion of the Li ions

References
[1] He X M, Pu W H, Wang L, Ren J G, Jiang C Y, Wan C R. Synthesis of nano Sb-encapsulated pyrolytic polyacrylonitrile composite for
anode material in lithium secondary batteries. Electrochimica acta, 2007,52: 3651-3653.
[2] Kwon Y, Kim M G, Kim Y, Lee Y, Cho J P. Effect of capping agents in tin nanoparticles on electrochemical cycling. Electrochemical
and Solid State Letters, 2006,9: a34-a38.
[3] Boukamp B a, Lesh G C, Huggins R a. all-solid lithium electrodes with mixed-conductor matrix. Journal of the Electrochemical
Society, 1981,128: 725-729.
[4] Zang J-L, Zhao Y-P. Silicon nanowire reinforced by single-walled carbon nanotube and its applications to anti-pulverization electrode
in lithium ion battery. Composites Part B: Engineering, 2012,43: 76-82.

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Abstract Book |INST| Sharif University of Technology|

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