skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: LiMnPO 4 ·Li 3 V 2 (PO 4 ) 3 composite cathode material derived from Mn(VO 3 ) 2 nanosheet precursor

Authors:
; ; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1411496
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Alloys and Compounds
Additional Journal Information:
Journal Volume: 695; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-12-06 13:22:08; Journal ID: ISSN 0925-8388
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Lei, Zhihong, Yang, Jun, He, Yang, Shao, Yuyan, Mao, Scott X., Wang, Chongming, Nuli, Yanna, and Wang, Jiulin. LiMnPO 4 ·Li 3 V 2 (PO 4 ) 3 composite cathode material derived from Mn(VO 3 ) 2 nanosheet precursor. Netherlands: N. p., 2017. Web. doi:10.1016/j.jallcom.2016.11.013.
Lei, Zhihong, Yang, Jun, He, Yang, Shao, Yuyan, Mao, Scott X., Wang, Chongming, Nuli, Yanna, & Wang, Jiulin. LiMnPO 4 ·Li 3 V 2 (PO 4 ) 3 composite cathode material derived from Mn(VO 3 ) 2 nanosheet precursor. Netherlands. doi:10.1016/j.jallcom.2016.11.013.
Lei, Zhihong, Yang, Jun, He, Yang, Shao, Yuyan, Mao, Scott X., Wang, Chongming, Nuli, Yanna, and Wang, Jiulin. Wed . "LiMnPO 4 ·Li 3 V 2 (PO 4 ) 3 composite cathode material derived from Mn(VO 3 ) 2 nanosheet precursor". Netherlands. doi:10.1016/j.jallcom.2016.11.013.
@article{osti_1411496,
title = {LiMnPO 4 ·Li 3 V 2 (PO 4 ) 3 composite cathode material derived from Mn(VO 3 ) 2 nanosheet precursor},
author = {Lei, Zhihong and Yang, Jun and He, Yang and Shao, Yuyan and Mao, Scott X. and Wang, Chongming and Nuli, Yanna and Wang, Jiulin},
abstractNote = {},
doi = {10.1016/j.jallcom.2016.11.013},
journal = {Journal of Alloys and Compounds},
number = C,
volume = 695,
place = {Netherlands},
year = {Wed Feb 01 00:00:00 EST 2017},
month = {Wed Feb 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jallcom.2016.11.013

Save / Share:
  • Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K[sub 3](VO)(V[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]) and K[sub 3](VO)(HV[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO][sub n] chains connected through phosphate groups to a [V[sub 2]O[sub 3]] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV)more » centers. Crystal data: for K[sub 3](VO)(V[sub 2]O[sub 3])(PO[sub 4])[sub 2] (HPO[sub 4]), M[sub r] = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) [angstrom], b = 13.309(7) [angstrom], c = 14.294(7) [angstrom], V = 1336(2) [angstrom][sup 3], Z = 4, R = 5.02%, and R[sub w] = 5.24% for 1238 observed reflections [I > 3[sigma](I)]; for K[sub 3](VO)(HV[sub 2]O[sub 3])(PO[sub 4])[sub 2](HPO[sub 4]), M[sub r] = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) [angstrom], b = 13.559(7) [angstrom], c = 14.130(7) [angstrom], V = 1336(1) [angstrom][sup 3], Z = 4, R = 6.02%, and R[sub w] = 6.34% for 1465 observed reflections [I > 3[sigma](I)].« less
  • A new phase, Li{sub 4}VO(PO{sub 4}){sub 2} was synthesized by a lithium ion exchange reaction from protonic phase, VO(H{sub 2}PO{sub 4}){sub 2}. The structure was determined from neutron and synchrotron powder diffraction data. The exchange of lithium causes a stress, leading to a change in the dimensionality of the structure from 3D to 2D by the displacement of oxygen atoms. Thus, Li{sub 4}VO(PO{sub 4}){sub 2} crystallizes in P4/n space group with lattice parameters a=8.8204(1) A and c=8.7614(2) A. It consists of double layers [V{sub 2}P{sub 4}O{sub 18}]{sub {infinity}} formed by successive chains of VO{sub 6} octahedra and VO{sub 5} pyramidsmore » with isolated PO{sub 4} tetrahedra. The lithium ions located in between the layers promote mobility. Furthermore, the ionic conductivity of 10{sup -4} S/cm at 550 deg. C for Li{sub 4}VO(PO{sub 4}){sub 2} confirms the mobility of lithium ions in the layers. On the other hand, VO(H{sub 2}PO{sub 4}){sub 2} exhibits a conductivity of 10{sup -4} S/cm at room temperature due to the presence of protons in tunnels. - Graphical abstract: Li{sub 4}VO(PO{sub 4}){sub 2} was synthesized by a lithium ion exchange reaction from VO(H{sub 2}PO{sub 4}){sub 2}. The structure, determined from neutron and synchrotron powder diffraction data, changes in dimensionality from 3D to 2D. VO(H{sub 2}PO{sub 4}){sub 2} exhibits a protonic conductivity of 10{sup -4} S/cm at room temperature while Li{sub 4}VO(PO{sub 4}){sub 2} is a lithium conductor.« less
  • A facile strategy has been developed to construct unique core–shell-structured Li 2.7V 2.1(PO 4) 3 nanocomposites with a Li 3V 2(PO 4) 3 core and LiVOPO 4 shell by using nonstoichiometric design and high-energy ball milling (HEBM) treatment. The HEBM treatment supplies enough energy to drive the excess V atoms to the surface to form a V-enriched shell. Such kind of cathode can deliver a high reversible capacity of 131.5 mAhg $-$1 at 0.5 C, which is close to the theoretical capacity (133 mAhg $-$1 in 3.0–4.3 V). Even at 20 C, it still delivers an excellent discharge capacity ofmore » 116.3 mAhg $-$1, and a remarkable capacity of 111.0 mAhg $-$1 after 1000 cycles, corresponding to an ultra-small capacity-loss of 0.0046% per cycle. Finally, the significantly improved high-rate electrochemical performance can be attributed to the active shell of LiVOPO 4, which not only efficiently facilitates the electron and Li + ion transport during cycling processes, but also accommodates more Li+ ions to effectively compensate the capacity loss of the core.« less
  • Graphical abstract: Nanocrystalline Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C compound has been synthesized using a novel corn assisted combustion (CAC) method, wherein the composite prepared at 850 °C is found to exhibit superior physical and electrochemical properties than the one synthesized at 800 °C (Fig. 1). Despite the charge disproportionation of V{sup 4+} and a possible solid solution behavior of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} cathode upon insertion and de-insertion of Li{sup +} ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V (Fig. 2). An appreciable specific capacity of 174 mAhmore » g{sup −1} with an excellent columbic efficiency (99%) and better capacity retention upon high rate applications have been exhibited by Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode, thus demonstrating the feasibility of CAC method in preparing the title compound to best suit with the needs of lithium battery applications. Display Omitted Highlights: ► Novel corn assisted combustion method has been used to synthesize Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C. ► Corn is a cheap and eco benign combustible fuel to facilitate CAC synthesis. ► Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C exhibits an appreciable specific capacity of 174 mAh g{sup −1} (C/10 rate). ► Currently observed columbic efficiency of 99% is better than the reported behavior. ► Suitability of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode up to 10C rate is demonstrated. -- Abstract: Nanocrystalline Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C composite synthesized using a novel corn assisted combustion method at 850 °C exhibits superior physical and electrochemical properties than the one synthesized at 800 °C. Despite the charge disproportionation of V{sup 4+} and a possible solid solution behavior of Li{sub 3}V{sub 2}(PO{sub 4}){sub 3} cathode upon insertion and extraction of Li{sup +} ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V. An appreciable specific capacity of 174 mAh g{sup −1} and better capacity retention upon high rate applications have been exhibited by Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}/C cathode, thus demonstrating the suitability of the same for lithium-ion battery applications.« less
  • The hydrothermal syntheses, X-ray single-crystal structures, and some properties of Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} and Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O are described. Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2} contains a three-dimensional network of VO{sub 6} and (H)SeO{sub 3} polyhedra, linked via V-O-Se bonds. The Ba cation is 10-coordinate, the VO{sub 6} group contains a short vanadyl V{double_bond}O bond typical of V{sup IV}, and the (H)SeO{sub 3} groups are pyramidal. Magnetic susceptibility data are consistent with V{sup IV} and show paramagnetic behavior from 4 to 300 K. Crystal data for Ba(VO){sub 2}(SeO{sub 3}){sub 2}(HSeO{sub 3}){sub 2}:M{submore » r} = 781.06, monoclinic, space group P2{sub 1}/c (No. 14), a = 9.680(3) {angstrom}, b = 7.024(2) {angstrom}, c = 9.882(4) {angstrom}, {beta} = 116.42(3){degrees}, V = 601.75 {angstrom}{sup 3}, Z = 2, R = 3.89%, R{sub w} = 3.64% [1637 observed reflections with I > 3{sigma}(I)]. Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O contains a complex network of VO{sub 6} and PO{sub 4}/HPO{sub 4} groups, which form two different types of one-dimensional chains: one chain contains fairly regular V{sup IV}O{sub 6} and (H)PO{sub 4} groups; the other is built up from distorted V{sup IV}O{sub 6} octahedra and (hydrogen) phosphate groups. 10- and 13-coordinate Ba{sup 2+} cations complete the structure, which shows antiferromagnetic ordering of the V{sup IV} centers at {approximately}20 K. Crystal data for Ba{sub 8}(VO){sub 6}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 11}{center_dot}3H{sub 2}O: M{sub r} = 2800.05, monoclinic, space group C2/m (No. 12), a = 31.685(11) {angstrom}, b = 5.208(2) {angstrom}, c = 7.784(3) {angstrom}, {beta} = 90.59(3){degrees}, V = 1284.5(7) {angstrom}{sup 3}, Z = 1, R = 4.03%, and R{sub w} = 5.28% [1892 observed reflections with I > 3{sigma}(I)].« less