Abstract
Na3V2(PO4)3 (NVP) is one of the most promising candidates for use as cathodes in room-temperature sodium ion batteries owing to its high structural stability and rapid Na+ transportation kinetics. The cationic doping of foreign ions at Na or V sites in the NVP lattice has proven to be an effective approach for enhancing the electrochemical performance of NVP. In this work, we present a first-principles density functional theory investigation of the impact of polyanionic boron doping at P sites on the structural and electrochemical behavior of NVP. Our simulation results suggest that B doping considerably increases the structural stability of NVP while shrinking its lattice size to some extent. Since B donates far fewer electrons to connected O atoms, the surrounding V atoms become more positive, causing the operating voltage to increase with B content. However, the reduction in lattice size is not beneficial for the Na+ transportation kinetics. As demonstrated by a search for the transition state, a concerted ion-exchange mechanism is preferred for Na+ transportation, and increased B doping leads to a higher Na+ diffusion barrier. Improvements in electrochemical performance due to B doping see (Hu et al. Adv Sci 3(12):1600112, 2016) appear to originate mainly from the resulting increased electrical conductivity.
Similar content being viewed by others
References
Slater MD, Kim D, Lee E, Johnson CS (2013) Sodium-ion batteries. Adv Funct Mater 23(8):947–958. https://doi.org/10.1002/adfm.201200691
Li W-J, Han C, Wang W, Gebert F, Chou S-L, Liu H-K, Zhang X, Dou S-X (2017) Commercial prospects of existing cathode materials for sodium ion storage. Adv Energy Mater 7(24):1700274. https://doi.org/10.1002/aenm.201700274
Kim SW, Seo DH, Ma X, Ceder G, Kang K (2012) Electrode materials for rechargeable sodium-ion batteries: potential alternatives to current lithium-ion batteries. Adv Energy Mater 2(7):710–721. https://doi.org/10.1002/aenm.201200026
Wong LL, Chen H, Adams S (2017) Design of fast ion conducting cathode materials for grid-scale sodium-ion batteries. Phys Chem Chem Phys 19(11):7506–7523. https://doi.org/10.1039/C7CP00037E
Bui KM, Dinh VA, Okada S, Ohno T (2016) Na-ion diffusion in a NASICON-type solid electrolyte: a density functional study. Phys Chem Chem Phys 18(39):27226–27231. https://doi.org/10.1039/C6CP05164B
Saravanan K, Mason CW, Rudola A, Wong KH, Balaya P (2012) The first report on excellent cycling stability and superior rate capability of Na3V2(PO4)3 for sodium ion batteries. Adv Energy Mater 3(4):444–450. https://doi.org/10.1002/aenm.201200803
Jian Z, Han W, Lu X, Yang H, Hu YS, Zhou J, Zhou Z, Li J, Chen W, Chen D, Chen L (2013) Superior electrochemical performance and storage mechanism of Na3V2(PO4)3 cathode for room-temperature sodium-ion batteries. Adv Energy Mater 3(2):156–160. https://doi.org/10.1002/aenm.201200558
Noguchi Y, Kobayashi E, Plashnitsa LS, Okada S, Yamaki J-i (2013) Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds. Electrochim Acta 101:59–65. https://doi.org/10.1016/j.electacta.2012.11.038
Chen S, Wu C, Shen L, Zhu C, Huang Y, Xi K, Maier J, Yu Y (2017) Challenges and perspectives for NASICON-type electrode materials for advanced sodium-ion batteries. Adv Mater 29(48):1700431. https://doi.org/10.1002/adma.201700431
Fang Y, Zhang J, Xiao L, Ai X, Cao Y, Yang H (2017) Phosphate framework electrode materials for sodium ion batteries. Adv Sci 4(5):1600392. https://doi.org/10.1002/advs.201600392
Duan W, Zhu Z, Li H, Hu Z, Zhang K, Cheng F, Chen J (2014) Na3V2(PO4)3@C core-shell nanocomposites for rechargeable sodium-ion batteries. J Mater Chem A 2(23):8668–8675. https://doi.org/10.1039/C4TA00106K
Song W, Ji X, Pan C, Zhu Y, Chen Q, Banks CE (2013) A Na3V2(PO4)3 cathode material for use in hybrid lithium ion batteries. Phys Chem Chem Phys 15(34):14357–14363. https://doi.org/10.1039/C3CP52308J
Fang Y, Xiao L, Ai X, Cao Y, Yang H (2015) Hierarchical carbon framework wrapped Na3V2(PO4)3 as a superior high-rate and extended lifespan cathode for sodium-ion batteries. Adv Mater 27(39):5895–5900. https://doi.org/10.1002/adma.201502018
Guo J-Z, Wu X-L, Wan F, Wang J, Zhang X-H, Wang R-S (2015) A superior Na3V2(PO4)3-based nanocomposite enhanced by both N-doped coating carbon and graphene as the cathode for sodium-ion batteries. Chem Eur J 21(48):17371–17378. https://doi.org/10.1002/chem.201502583
Rui X, Sun W, Wu C, Yu Y, Yan Q (2015) An advanced sodium-ion battery composed of carbon coated Na3V2(PO4)3 in a porous graphene network. Adv Mater 27(42):6670–6676. https://doi.org/10.1002/adma.201502864
Zhang W, Liu Y, Chen C, Li Z, Huang Y, Hu X (2015) Flexible and binder-free electrodes of Sb/rGO and Na3V2(PO4)3/rGO nanocomposites for sodium-ion batteries. Small 11(31):3822–3829. https://doi.org/10.1002/smll.201500783
Xu Y, Wei Q, Xu C, Li Q, An Q, Zhang P, Sheng J, Zhou L, Mai L (2016) Layer-by-layer Na3V2(PO4)3 embedded in reduced graphene oxide as superior rate and ultralong-life sodium-ion battery cathode. Adv Energy Mater 6(14):1600389. https://doi.org/10.1002/aenm.201600389
Li H, Yu X, Bai Y, Wu F, Wu C, Liu L-Y, Yang X-Q (2015) Effects of Mg doping on the remarkably enhanced electrochemical performance of Na3V2(PO4)3 cathode materials for sodium ion batteries. J Mater Chem A 3(18):9578–9586. https://doi.org/10.1039/C5TA00277J
Lalere F, Seznec V, Courty M, David R, Chotard JN, Masquelier C (2015) Improving the energy density of Na3V2(PO4)3-based positive electrodes through V/Al substitution. J Mater Chem A 3(31):16198–16205. https://doi.org/10.1039/C5TA03528G
Klee R, Lavela P, Aragón MJ, Alcántara R, Tirado JL (2016) Enhanced high-rate performance of manganese substituted Na3V2(PO4)3/C as cathode for sodium-ion batteries. J Power Sources 313:73–80. https://doi.org/10.1016/j.jpowsour.2016.02.066
Aragón MJ, Lavela P, Ortiz GF, Tirado JL (2015) Benefits of chromium substitution in Na3V2(PO4)3 as a potential candidate for sodium-ion batteries. ChemElectroChem 2(7):995–1002. https://doi.org/10.1002/celc.201500052
Aragón MJ, Lavela P, Ortiz GF, Tirado JL (2015) Effect of iron substitution in the electrochemical performance of Na3V2(PO4)3 as cathode for Na-ion batteries. J Electrochem Soc 162(2):A3077–A3083. https://doi.org/10.1149/2.0151502jes
Lim S-J, Han D-W, Nam D-H, Hong K-S, Eom J-Y, Ryu W-H, Kwon H-S (2014) Structural enhancement of Na3V2(PO4)3/C composite cathode materials by pillar ion doping for high power and long cycle life sodium-ion batteries. J Mater Chem A 2(46):19623–19632. https://doi.org/10.1039/C4TA03948C
Serras P, Palomares V, Alonso J, Sharma N, López del Amo JM, Kubiak P, Fdez-Gubieda ML, Rojo T (2013) Electrochemical Na extraction/insertion of Na3V2O2x(PO4)2F3–2x. Chem Mater 25(24):4917–4925. https://doi.org/10.1021/cm403679b
Park Y-U, Seo D-H, Kim H, Kim J, Lee S, Kim B, Kang K (2014) A family of high-performance cathode materials for Na-ion batteries, Na3(VO1−xPO4)2F1+2x(0 ≤ x ≤ 1): combined first-principles and experimental study. Adv Funct Mater 24(29):4603–4614. https://doi.org/10.1002/adfm.201400561
Shakoor RA, Seo D-H, Kim H, Park Y-U, Kim J, Kim S-W, Gwon H, Lee S, Kang K (2012) A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries. J Mater Chem 22(38):20535–20541. https://doi.org/10.1039/C2JM33862A
Park Y-U, Seo D-H, Kim B, Hong K-P, Kim H, Lee S, Shakoor RA, Miyasaka K, Tarascon J-M, Kang K (2012) Tailoring a fluorophosphate as a novel 4 V cathode for lithium-ion batteries. Sci Rep 2:704. https://doi.org/10.1038/srep00704
Serras P, Palomares V, Goñi A, Gil de Muro I, Kubiak P, Lezama L, Rojo T (2012) High voltage cathode materials for Na-ion batteries of general formula Na3V2O2x(PO4)2F3-2x. J Mater Chem 22(41):22301–22308. https://doi.org/10.1039/C2JM35293A
Park Y-U, Seo D-H, Kwon H-S, Kim B, Kim J, Kim H, Kim I, Yoo H-I, Kang K (2013) A new high-energy cathode for a Na-ion battery with ultrahigh stability. J Am Chem Soc 135(37):13870–13878. https://doi.org/10.1021/ja406016j
Serras P, Palomares V, Goñi A, Kubiak P, Rojo T (2013) Electrochemical performance of mixed valence Na3V2O2x(PO4)2F3−2x/C as cathode for sodium-ion batteries. J Power Sources 241:56–60. https://doi.org/10.1016/j.jpowsour.2013.04.094
Hu P, Wang X, Wang T, Chen L, Ma J, Kong Q, Shi S, Cui G (2016) Boron substituted Na3V2(P1−xBxO4)3 cathode materials with enhanced performance for sodium-ion batteries. Adv Sci 3(12):1600112. https://doi.org/10.1002/advs.201600112
Lim SY, Kim H, Shakoor RA, Jung Y, Choi JW (2012) Electrochemical and thermal properties of NASICON structured Na3V2(PO4)3 as a sodium rechargeable battery cathode: a combined experimental and theoretical study. J Electrochem Soc 159(9):A1393–A1397. https://doi.org/10.1149/2.015209jes
Wang Q, Zhang M, Zhou C, Chen Y (2018) Concerted ion-exchange mechanism for sodium diffusion and its promotion in Na3V2(PO4)3 framework. J Phys Chem C 122(29):16649–16654. https://doi.org/10.1021/acs.jpcc.8b06120
Aydinol MK, Ceder G (1997) First-principles prediction of insertion potentials in Li-Mn oxides for secondary Li batteries. J Electrochem Soc 144(11):3832–3835. https://doi.org/10.1149/1.1838099
Ji Z, Han B, Liang H, Zhou C, Gao Q, Xia K, Wu J (2016) On the mechanism of the improved operation voltage of rhombohedral nickel hexacyanoferrate as cathodes for sodium-ion batteries. ACS Appl Mater Interfaces 8(49):33619–33625. https://doi.org/10.1021/acsami.6b11070
Mills G, Jónsson H, Schenter GK (1995) Reversible work transition state theory: application to dissociative adsorption of hydrogen. Surf Sci 324(2):305–337. https://doi.org/10.1016/0039-6028(94)00731-4
Kresse G, Hafner J (1993) Ab initio molecular dynamics for open-shell transition metals. Phys Rev B 48(17):13115–13118. https://doi.org/10.1103/PhysRevB.48.13115
Kresse G, Furthmüller J (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6(1):15–50. https://doi.org/10.1016/0927-0256(96)00008-0
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77(18):3865–3868. https://doi.org/10.1103/PhysRevLett.77.3865
Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50(24):17953–17979. https://doi.org/10.1103/PhysRevB.50.17953
Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59(3):1758–1775. https://doi.org/10.1103/PhysRevB.59.1758
Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13(12):5188–5192. https://doi.org/10.1103/PhysRevB.13.5188
Henkelman G, Arnaldsson A, Jónsson H (2006) A fast and robust algorithm for Bader decomposition of charge density. Comput Mater Sci 36(3):354–360. https://doi.org/10.1016/j.commatsci.2005.04.010
Edward S, KS D, Roger S, Graeme H (2007) Improved grid-based algorithm for Bader charge allocation. J Comput Chem 28(5):899–908. https://doi.org/10.1002/jcc.20575
Ellis BL, Makahnouk WRM, Makimura Y, Toghill K, Nazar LF (2007) A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries. Nat Mater 6:749. https://doi.org/10.1038/nmat2007
Song W, Cao X, Wu Z, Chen J, Huangfu K, Wang X, Huang Y, Ji X (2014) A study into the extracted ion number for NASICON structured Na3V2(PO4)3 in sodium-ion batteries. Phys Chem Chem Phys 16(33):17681–17687. https://doi.org/10.1039/C4CP01821D
Song W, Ji X, Wu Z, Zhu Y, Yang Y, Chen J, Jing M, Li F, Banks CE (2014) First exploration of Na-ion migration pathways in the NASICON structure Na3V2(PO4)3. J Mater Chem A 2(15):5358–5362. https://doi.org/10.1039/C4TA00230J
Bui KM, Dinh VA, Okada S, Ohno T (2015) Hybrid functional study of the NASICON-type Na3V2(PO4)3: crystal and electronic structures, and polaron–Na vacancy complex diffusion. Phys Chem Chem Phys 17(45):30433–30439. https://doi.org/10.1039/C5CP05323Dz
Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant 21773217) and Wuhan Science & Technology Project 2018010401011276. Support from the High-Performance Computing Platform, China University of Geosciences, is also gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Wang, Q., Wang, Q., Zhang, M. et al. A first-principles investigation of the influence of polyanionic boron doping on the stability and electrochemical behavior of Na3V2(PO4)3. J Mol Model 25, 96 (2019). https://doi.org/10.1007/s00894-019-3971-1
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00894-019-3971-1