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Title: A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode

Abstract

VOPO 4 is an example of a Li-ion battery cathode that can achieve over 300 Ah/kg when two Li-ions are intercalated. A two phase β-VOPO 4/ε-VOPO 4 composite was found to improve the cycling capacity of ε-VOPO 4 from tetragonal H 2VOPO 4, particularly as the rate is increased. In the potential range of 2.0–4.5 V, this composite showed an initial electrochemical capacity of 208 mAh/g at 0.08 mA/cm 2, 190 mAh/g at 0.16 mA/cm 2, and 160 mAh/g at 0.41 mA/cm 2.

Authors:
 [1]; ORCiD logo [2];  [2];  [3];  [3];  [4];  [3]
  1. Central South Univ., Changsha (China); State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Central South Univ., Changsha (China)
  3. State Univ. of New York (SUNY), Binghamton, NY (United States)
  4. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics. Beijing National Lab. for Condensed Matter Physics (BNLCP-CAS)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1228872
Report Number(s):
BNL-110947-2015-JA
Journal ID: ISSN 1388-2481
DOE Contract Number:
SC00112704
Resource Type:
Journal Article
Resource Relation:
Journal Name: Electrochemistry Communications; Journal Volume: 46; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Chen, Zehua, Chen, Qiyuan, Wang, Haiyan, Zhang, Ruibo, Zhou, Hui, Chen, Liquan, and Whittingham, M. Stanley. A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode. United States: N. p., 2014. Web. doi:10.1016/j.elecom.2014.06.009.
Chen, Zehua, Chen, Qiyuan, Wang, Haiyan, Zhang, Ruibo, Zhou, Hui, Chen, Liquan, & Whittingham, M. Stanley. A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode. United States. doi:10.1016/j.elecom.2014.06.009.
Chen, Zehua, Chen, Qiyuan, Wang, Haiyan, Zhang, Ruibo, Zhou, Hui, Chen, Liquan, and Whittingham, M. Stanley. Mon . "A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode". United States. doi:10.1016/j.elecom.2014.06.009.
@article{osti_1228872,
title = {A β-VOPO4/ε-VOPO4 composite Li-ion battery cathode},
author = {Chen, Zehua and Chen, Qiyuan and Wang, Haiyan and Zhang, Ruibo and Zhou, Hui and Chen, Liquan and Whittingham, M. Stanley},
abstractNote = {VOPO4 is an example of a Li-ion battery cathode that can achieve over 300 Ah/kg when two Li-ions are intercalated. A two phase β-VOPO4/ε-VOPO4 composite was found to improve the cycling capacity of ε-VOPO4 from tetragonal H2VOPO4, particularly as the rate is increased. In the potential range of 2.0–4.5 V, this composite showed an initial electrochemical capacity of 208 mAh/g at 0.08 mA/cm2, 190 mAh/g at 0.16 mA/cm2, and 160 mAh/g at 0.41 mA/cm2.},
doi = {10.1016/j.elecom.2014.06.009},
journal = {Electrochemistry Communications},
number = C,
volume = 46,
place = {United States},
year = {Mon Sep 01 00:00:00 EDT 2014},
month = {Mon Sep 01 00:00:00 EDT 2014}
}
  • Graphical abstract: MnO{sub 2} was blended into pristine Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2} and Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}/MnO{sub 2} composite was obtained. We can observe that the adding MnO{sub 2} in the composite participates in the electrochemical reaction and provide more active sites for lithiation/delithiation. - Highlights: • Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}/MnO{sub 2} composite was synthesized by incorporation of MnO{sub 2} into spherical Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}. • Properties of spherical Li-rich layered oxide can be greatly improved by adding MnO{sub 2}. • The reason for the improvement of Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{submore » 0.18}]O{sub 2}/MnO{sub 2} by adding MnO{sub 2} was explained. - Abstract: Spherical Li-rich layered Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2} with high tap density and low specific surface area was synthesized. Furthermore, low cost and environmental benign MnO{sub 2} was blended into it and Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}/MnO{sub 2} composite was obtained. The properties of the materials were investigated by XRD, SEM and electrochemical method. The results showed that the existence of MnO{sub 2} in the composites can't change the structure of the pristine Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}. The electrochemical characteristics of Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}/MnO{sub 2} such as the initial coulombic efficiency, discharge capacity, rate characteristics and cyclability are much better than those of the pristine Li[Li{sub 0.2}Mn{sub 0.44}Ni{sub 0.18}Co{sub 0.18}]O{sub 2}. The contribution of MnO{sub 2} to the excellent characteristics of the cathode is as follows: the existence of MnO{sub 2} (i) provides more active site for lithiation/delitiation and (ii) suppresses side interaction between cathode particle surface and electrolyte.« less
  • Kinetic characteristics of Li{sup +} intercalation/deintercalation into/from individual LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} particles in a composite cathode were studied in-situ using Raman microscopy during electrochemical charge-discharge in 1.2 M LiPF{sub 6}, ethylene carbonate (EC): ethyl-methyl carbonate (EMC), 3:7 by volume. Spectroscopic analysis of a cathode that was removed from a tested high-power Li-ion cell, which suffered substantial power and capacity loss, showed that the state of charge (SOC) of oxide particles on the cathode surface was highly non-uniform despite deep discharge of the Li-ion cell at the end of the test. In-situ monitoring of the SOC of selected oxidemore » particles in the composite cathode in a sealed spectro-electrochemical cell revealed that the rate at which particles charge and discharge varied with time and location. The inconsistent kinetic behavior of individual oxide particles was attributed to degradation of the electronically conducting matrix in the composite cathode upon testing. These local micro-phenomena are responsible for the overall impedance rise of the cathode and contribute to the mechanism of lithium-ion cell failure.« less