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

Title: Synthesis of layered cathode material Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} from layered double hydroxides precursors

Abstract

Cathode materials Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} for lithium secondary batteries have been prepared by a new route-precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH.H{sub 2}O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li{sup +} into the lattice, resulting in the formation of layered Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} with {alpha}-NaFeO{sub 2} structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2}, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} have been investigated by XRD and electrochemical tests.more » It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g{sup -1} for the layered material Li[Co{sub 0.80}Mn{sub 0.20}]O{sub 2}. - Graphical abstract: In situ HT-XRD and TG-MS were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH.H{sub 2}O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then intercalation of Li{sup +} occurred, which results in the formation of layered Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} with {alpha}-NaFeO{sub 2} structure. The structure and the electrochemical properties of Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} were studied.« less

Authors:
 [1];  [2];  [1];  [3]
  1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)
  2. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China), E-mail: weimin@mail.buct.edu.cn
  3. Beijing Key Laboratory, Beijing Institute of Clothing Technology, Beijing 100029 (China), E-mail: clycongjuli@bict.edu.cn
Publication Date:
OSTI Identifier:
21015836
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 5; Other Information: DOI: 10.1016/j.jssc.2007.04.001; PII: S0022-4596(07)00136-3; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ABSORPTION SPECTROSCOPY; COBALT COMPOUNDS; ELECTRIC BATTERIES; ELECTROCHEMISTRY; FINE STRUCTURE; LITHIUM; LITHIUM COMPOUNDS; LITHIUM HYDROXIDES; LITHIUM IONS; MANGANESE COMPOUNDS; MASS SPECTROSCOPY; OXIDES; SPINELS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION; X-RAY PHOTOELECTRON SPECTROSCOPY; X-RAY SPECTROSCOPY

Citation Formats

Lu Yanluo, Wei Min, Yang Lan, and Li Congju. Synthesis of layered cathode material Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} from layered double hydroxides precursors. United States: N. p., 2007. Web.
Lu Yanluo, Wei Min, Yang Lan, & Li Congju. Synthesis of layered cathode material Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} from layered double hydroxides precursors. United States.
Lu Yanluo, Wei Min, Yang Lan, and Li Congju. Tue . "Synthesis of layered cathode material Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} from layered double hydroxides precursors". United States. doi:.
@article{osti_21015836,
title = {Synthesis of layered cathode material Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} from layered double hydroxides precursors},
author = {Lu Yanluo and Wei Min and Yang Lan and Li Congju},
abstractNote = {Cathode materials Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} for lithium secondary batteries have been prepared by a new route-precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH.H{sub 2}O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li{sup +} into the lattice, resulting in the formation of layered Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} with {alpha}-NaFeO{sub 2} structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2}, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} have been investigated by XRD and electrochemical tests. It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g{sup -1} for the layered material Li[Co{sub 0.80}Mn{sub 0.20}]O{sub 2}. - Graphical abstract: In situ HT-XRD and TG-MS were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH.H{sub 2}O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then intercalation of Li{sup +} occurred, which results in the formation of layered Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} with {alpha}-NaFeO{sub 2} structure. The structure and the electrochemical properties of Li[Co {sub x} Mn{sub 1-} {sub x} ]O{sub 2} were studied.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 5,
volume = 180,
place = {United States},
year = {Tue May 15 00:00:00 EDT 2007},
month = {Tue May 15 00:00:00 EDT 2007}
}
  • Lithium ion (Li-ion) batteries are currently the energy source of choice for cell phones, laptops, and other mobile electronic devices due to their balance of high energy density with high power density compared to other electrochemical energy carriers. In the present study, mixed hydroxide method is used to prepare Li[Ni{sub 0.5}Co{sub 0.25}Mn{sub 0.25}]O{sub 2} from the precursors and analyze qualitatively and studied the electrochemical properties. The XRD spectrum exhibited predominant (003) orientation at 2θ =18.39{sup o} corresponding to hexagonal layered structure of R3m symmetry with evaluated lattice parameters are a= 2.84 Å, c= 14.43 Å. Raman measurements were performed tomore » understand the microstructure and vibrational modes of the prepared sample. From the electrochemical (EC) studies an initial discharge capacity of about 140 mAhg{sup −1} with good cyclic stability was observed for the prepared sample in the potential range 0.0 −1.0V in aqueous medium.« less
  • In this paper, a series of pure Ni{sub 1-x}Zn {sub x}Fe{sub 2}O{sub 4} (0 {<=} x {<=} 1) spinel ferrites have been synthesized successfully using a novel route through calcination of tailored hydrotalcite-like layered double hydroxide molecular precursors of the type [(Ni + Zn){sub 1-x-y}Fe {sub y} {sup 2+}Fe {sub x} {sup 3+}(OH){sub 2}] {sup x+}(SO{sub 4} {sup 2-}) {sub x/2}.mH{sub 2}O at 900 deg. C for 2 h, in which the molar ratio of (Ni{sup 2+} + Zn{sup 2+})/(Fe{sup 2+} + Fe{sup 3+}) was adjusted to the same value as that in single spinel ferrite itself. The physico-chemical characteristicsmore » of the LDHs and their resulting calcined products were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Moessbauer spectroscopy. The results indicate that calcination of the as-synthesized LDH precursor affords a pure single Ni{sub 1-x}Zn {sub x}Fe{sub 2}O{sub 4} (0 {<=} x {<=} 1) spinel ferrite phase. Moreover, formation of pure ferrites starting from LDHs precursors requires a much lower temperature and shorter time, leading to a lower chance of side-reactions occurring, because all metal cations on the brucite-like layers of LDHs can be uniformly distributed at an atomic level.« less
  • Graphical abstract: Cycle behavior of Li{sub 1+x}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} cells (x = 0, 0.05, 0.10 and 0.15) obtained during cycling within the potential of 2.5-4.3 V. Highlights: Black-Right-Pointing-Pointer The spherical Li{sub 1+x}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} were synthesized by coprecipitation method. Black-Right-Pointing-Pointer Excess lithium improved the electrochemical performance. Black-Right-Pointing-Pointer Li{sub 1.10}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} showed the best electrochemical performance. Black-Right-Pointing-Pointer Li{sub 1.10}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} had the lowest charge transfer resistance. -- Abstract: In this work, layered lithium-excess materials Li{sub 1+x}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} (x = 0, 0.05, 0.10 and 0.15), of spherical morphology withmore » primary nanoparticles assembled in secondary microspheres, were synthesized by a coprecipitation method. The effects of lithium content on the structure and electrochemical performance of these materials were evaluated by employing X-ray diffraction (XRD), inductive coupled plasma (ICP), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge tests. It is found that Li{sub 1.10}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}}, i.e., Li[(Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}){sub 0.95}Li{sub 0.05}]O{sub 2} showed the best electrochemical performance due to the highly ordered layered structure, reduced cation mixing and the lowest charge transfer resistance. Li{sub 1.10}Ni{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2+{delta}} delivered a discharge capacity of 145 mA h g{sup -1} at 125 mA g{sup -1} in the cut-off voltage of 2.5-4.3 V, and had a capacity retention of 100% after 50 cycles at room temperature.« less
  • Layered Li(Ni{sub 0.5-x}Mn{sub 0.5-x}M'{sub 2x})O{sub 2} materials (M'=Co, Al, Ti; x=0, 0.025) were synthesized using a manganese-nickel hydroxide precursor, and the effect of dopants on the electrochemical properties was investigated. Li(Ni0.5Mn0.5)O2 exhibited a discharge capacity of 120 mAh/g in the voltage range of 2.8-4.3 V with a slight capacity fade up to 40 cycles (0.09% per cycle); by doping of 5 mol% Co, Al, and Ti, the discharge capacities increased to 140, 142, and 132 mAh/g, respectively, and almost no capacity fading was observed. The cathode material containing 5 mol% Co had the lowest impedance, 47 {Omega} cm2, while undoped,more » Ti-doped, and Al-doped materials had impedance of 64, 62, and 99 {Omega} cm2, respectively. Unlike the other dopants, cobalt was found to improve the electronic conductivity of the material. Further improvement in the impedance of these materials is needed to meet the requirement for powering hybrid electric vehicle (HEV, <35 {Omega} cm2). In all materials, structural transformation from a layered to a spinel structure was not observed during electrochemical cycling. Cyclic voltammetry and X-ray photoelectron spectroscopy (XPS) data suggested that Ni and Mn exist as Ni{sup 2+} and Mn{sup 4+} in the layered structure. Differential scanning calorimetry (DSC) data showed that exothermic peaks of fully charged Li(Ni{sub 0.5-x}Mn{sub 0.5-xM'}{sub 2x})O{sub 2} appeared at higher temperature (270-290 C) than LiNiO{sub 2}-based cathode materials, which indicates that the thermal stability of Li(Ni{sub 0.5-x}Mn{sub 0.5-x}M'{sub 2x})O{sub 2} is better than those of LiNiO{sub 2}-based cathode materials.« less