Investigation of the Sodium Ion Pathway and Cathode Behavior in

Sep 11, 2014 - Na 3 V 2 (PO 4 ) 2 F 3 @C dispersed within carbon nanotube frameworks as a high tap density cathode for high-performance sodium-ion ...
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Investigation of the Sodium Ion Pathway and Cathode Behavior in Na3V2(PO4)2F3 Combined via a First Principles Calculation Weixin Song,† Xiaoyu Cao,‡ Zhengping Wu,† Jun Chen,† Yirong Zhu,† Hongshuai Hou,† Qing Lan,† and Xiaobo Ji*,† †

College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China

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A B S T RA C T : The electrochemical properties o f Na3V2(PO4)2F3 cathode utilized in the sodium ion battery are investigated, and the ion migration mechanisms are proposed as combined via the first principles calculations. Two different Na sites, namely, the Na(1) and Na(2) sites, could cause two sodium ions of Na3V2(PO4)2F3 to be extracted or inserted by a two-step electrochemical process accompanied by structural reorganization that could be responsible for the redox reaction of V3+/4+. Because the calculated average voltage (Vavg) of the second charging plateau is 4.04 V for the optimized system but 4.38 V for the unoptimized one, the reorganization of the cathode system can make a stable configuration and lower the extraction energy. Three designed pathways for sodium ions along the x, y, z directions in Na3V2(PO4)2F3, known as a 3D ions transport tunnel, have activation energies (Ea) of 0.449, 0.2, and 0.323 eV, respectively, by using DFT calculations, demonstrating the different feasibilities of the migration directions. make cathode components are $150/ton and $5000/ton,3 respectively, from which it could be deduced that the cost of NIBs would be reasonably reduced. Moverover, the cathode composition available for NIBs could share common aspects with those for LIBs, and the opportunities for fast-advancing NIB research can be found in accordance with state-of-the-art LIB technologies.10 With respect to NIBs, the cathode consists of a series of materials that can accommodate Na cations reversibly at a considerable voltage greater than 2 V positive against that of Na metal, whereas materials with lower voltages (0.449 0.20 >0.323

4. CONCLUSIONS NASICON Na3V2(PO4)2F3 utilized as cathode in a sodium ion battery has been studied, and the high-voltage batteries with two obvious discharge-voltage plateaus at around 3.6 and 4.0 V vs Na/Na+ gave initial specific capacities of 115, 112, 107, 100, and 92 mA h g−1 at different current densities of 0.045, 0.09, 0.18, 0.45, and 0.91 C, respectively. It is the different Na sites, namely Na(1) and Na(2) sites, that cause two of the three ions in Na3V2(PO4)2F3 to be extracted or inserted by a two-step electrochemical process accompanied by structural reorganization which would be responsible for the one identical redox reaction of V3+/4+. The capacity could remain at 110 mA h g−1 with a Coulombic efficiency of 94% for the 50th cycle at 0.09 C and at 102 mA h g−1 with an efficiency of 92% for the 102th cycle at 0.91C, from which the possible 3D channels for ion migration may play an important role in the excellent cycling performance. The change in the ion configuration and possible pathways is shown, with the help of first principles calculations. Ion reorganization during charge/discharge is proposed to take place, and the three designed pathways for sodium ions along the x, y, and z directions in Na3V2(PO4)2F3 are demonstrated with different passing abilities for ion migration.

i.e., the activation energies (Ea),39−41 for these pathways, from which the pathway through the interspace constructed by each of two bioctahedrons connected to four octahedrons via two tetrahedrons defined as the y direction has the lowest Ea of 0.2 eV. Ion migration along the z direction denotes the tunnel originating from the composition of a bioctahedron and one octahedron corner-shared with one tetrahedron, and the corresponding Ea which is much greater than 0.323 eV could propose a possible path for ion migration. The x direction across the channel fabricated by six octahedrons along the x−y plane has presented a larger Ea value than 0.449 eV, in which this way might be considered to be relatively difficult for ion migration due to the strong induced effects from the surrounding fluorine atoms. Furthermore, according to the DFT calculations, the cell lattice parameters of Na3V2(PO4)2F3 are a=b=9.034 Å, c=10.679 Å, V=871.5 Å3. Thus, these smaller structural parameters from DFT when compared to the experimental values can make the value of Ea during sodium ion migration a little lower. However, the regulation of Ea values among the x, y, and z directions should not change a lot even for the actual migration. Therefore, the capability to accommodate the ions to migrate along the x, y, and z directions within a 3D NASICON Na3V2(PO4)2F3 is found to display much distinction, which is considered to be highly structure-dependent. The possibly 3D migration paths for sodium ions in Na3V2(PO4)2F3 are thought to be beneficial to the improvement of its cycling performance. As shown in Figure 13, the

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AUTHOR INFORMATION

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS Financial support from the NNSF of China (no. 21473258), the Program for the New Century Excellent Talents in University (no. NCET-11-0513), Funds for Distinguished Young Scientists of Hunan Province, China (no. 13JJ1004), Fundamental Research Funds for Central South University (nos. 2013zzts159 and 2012zzts059), and the Innovation and Entrepreneurship Training Program of China for University Students is greatly appreciated. 12444

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