TY - JOUR
T1 - Na 3 MnZr(PO 4 ) 3
T2 - A High-Voltage Cathode for Sodium Batteries
AU - Gao, Hongcai
AU - Seymour, Ieuan D.
AU - Xin, Sen
AU - Xue, Leigang
AU - Henkelman, Graeme
AU - Goodenough, John B.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/12/26
Y1 - 2018/12/26
N2 - Sodium batteries have been regarded as promising candidates for large-scale energy storage application, provided cathode hosts with high energy density and long cycle life can be found. Herein, we report NASICON-structured Na 3 MnZr(PO 4 ) 3 as a cathode for sodium batteries that exhibits an electrochemical performance superior to those of other manganese phosphate cathodes reported in the literature. Both the Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox couples are reversibly accessed in Na 3 MnZr(PO 4 ) 3 , providing high discharge voltage plateaus at 4.0 and 3.5 V, respectively. A high discharge capacity of 105 mAh g -1 was obtained from Na 3 MnZr(PO 4 ) 3 with a small variation of lattice parameters and a small volume change on extraction of two Na + ions per formula unit. Moreover, Na 3 MnZr(PO 4 ) 3 exhibits an excellent cycling stability, retaining 91% of the initial capacity after 500 charge/discharge cycles at 0.5 C rate. On the basis of structural analysis and density functional theory calculations, we have proposed a detailed desodiation pathway from Na 3 MnZr(PO 4 ) 3 where Mn and Zr are disordered within the structure. We further show that the cooperative Jahn-Teller distortion of Mn 3+ is suppressed in the cathode and that Na 2 MnZr(PO 4 ) 3 is a stable phase.
AB - Sodium batteries have been regarded as promising candidates for large-scale energy storage application, provided cathode hosts with high energy density and long cycle life can be found. Herein, we report NASICON-structured Na 3 MnZr(PO 4 ) 3 as a cathode for sodium batteries that exhibits an electrochemical performance superior to those of other manganese phosphate cathodes reported in the literature. Both the Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox couples are reversibly accessed in Na 3 MnZr(PO 4 ) 3 , providing high discharge voltage plateaus at 4.0 and 3.5 V, respectively. A high discharge capacity of 105 mAh g -1 was obtained from Na 3 MnZr(PO 4 ) 3 with a small variation of lattice parameters and a small volume change on extraction of two Na + ions per formula unit. Moreover, Na 3 MnZr(PO 4 ) 3 exhibits an excellent cycling stability, retaining 91% of the initial capacity after 500 charge/discharge cycles at 0.5 C rate. On the basis of structural analysis and density functional theory calculations, we have proposed a detailed desodiation pathway from Na 3 MnZr(PO 4 ) 3 where Mn and Zr are disordered within the structure. We further show that the cooperative Jahn-Teller distortion of Mn 3+ is suppressed in the cathode and that Na 2 MnZr(PO 4 ) 3 is a stable phase.
UR - http://www.scopus.com/inward/record.url?scp=85059524267&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b11388
DO - 10.1021/jacs.8b11388
M3 - Article
C2 - 30501177
AN - SCOPUS:85059524267
SN - 0002-7863
VL - 140
SP - 18192
EP - 18199
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 51
ER -
