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Title: Effects of the particle properties on electrochemical performance of nanocrystalline LiAl 0.1 Cu 0.1 Mn 1.8 O 4 cathode materials prepared by ultrasonic spray pyrolysis

Authors:
; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1397970
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 792; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-04 22:38:13; Journal ID: ISSN 1572-6657
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Ebin, Burçak, Doeff, Marca, and Battaglia, Vincent. Effects of the particle properties on electrochemical performance of nanocrystalline LiAl 0.1 Cu 0.1 Mn 1.8 O 4 cathode materials prepared by ultrasonic spray pyrolysis. Netherlands: N. p., 2017. Web. doi:10.1016/j.jelechem.2017.03.031.
Ebin, Burçak, Doeff, Marca, & Battaglia, Vincent. Effects of the particle properties on electrochemical performance of nanocrystalline LiAl 0.1 Cu 0.1 Mn 1.8 O 4 cathode materials prepared by ultrasonic spray pyrolysis. Netherlands. doi:10.1016/j.jelechem.2017.03.031.
Ebin, Burçak, Doeff, Marca, and Battaglia, Vincent. Mon . "Effects of the particle properties on electrochemical performance of nanocrystalline LiAl 0.1 Cu 0.1 Mn 1.8 O 4 cathode materials prepared by ultrasonic spray pyrolysis". Netherlands. doi:10.1016/j.jelechem.2017.03.031.
@article{osti_1397970,
title = {Effects of the particle properties on electrochemical performance of nanocrystalline LiAl 0.1 Cu 0.1 Mn 1.8 O 4 cathode materials prepared by ultrasonic spray pyrolysis},
author = {Ebin, Burçak and Doeff, Marca and Battaglia, Vincent},
abstractNote = {},
doi = {10.1016/j.jelechem.2017.03.031},
journal = {Journal of Electroanalytical Chemistry},
number = C,
volume = 792,
place = {Netherlands},
year = {Mon May 01 00:00:00 EDT 2017},
month = {Mon May 01 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jelechem.2017.03.031

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  • Nonstoichiometric spinel oxides, LiAl{sub x}Mn{sub 2-x}O{sub 4-{delta}} (x=0.1,0.2), were synthesized under controlled partial pressure of oxygen, and their elecrochemical performances were investigated. As an Al content increases, solubility limit of the oxygen nonstoichiometry, {delta}, increased, while partial molar enthalpy {delta}H-bar {sub O{sub 2}} of the formation of oxygen nonstoichiometry decreased. Cycle performance of LiAl{sub x}Mn{sub 2-x}O{sub 4} showed significant improvement comparing with that of LiMn{sub 2}O{sub 4} cathode. However, the decrease of theoretical capacity was accompanied with Al doping. Nonstoichiometric LiAl{sub x}Mn{sub 2-x}O{sub 4-{delta}} showed the increase in capacity with keeping good cycle performances as well as stoichiometric LiAl{sub x}Mn{submore » 2-x}O{sub 4}. Although the introduction of oxygen nonstoichiometry leads to the increase of Mn{sup 3+} which is known as Jahn-Teller ion, DSC curves for LiAl{sub x}Mn{sub 2-x}O{sub 4-{delta}} showed no exothermic peak due to phase transition arising from Jahn-Teller distortion around room temperature.« less
  • Graphical abstract: Display Omitted Highlights: ► Spherical shape Li{sub 2}MnO{sub 3}·LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} composite cathode powders are prepared by large-scale spray pyrolysis with droplet classifier. ► Boric acid improves the morphological and electrochemical properties of the composite cathode powders. ► The discharge capacity of the composite cathode powders decreases from 217 to 196 mAh g{sup −1} by the 30th cycle. -- Abstract: Spherically shaped 0.3Li{sub 2}MnO{sub 3}·0.7LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} composite cathode powders with filled morphology and narrow size distribution are prepared by large-scale spray pyrolysis. A droplet classification reduces the standard deviation of the size distribution of themore » composite cathode powders. Addition of boric acid improves the morphological properties of the product powders by forming a lithium borate glass material with low melting temperature. The optimum amount of boric acid dissolved in the spray solution is 0.8 wt% of the composite powders. The powders prepared from the spray solution with 0.8 wt% boric acid have a mixed layered crystal structure comprising Li{sub 2}MnO{sub 3} and LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} phases, thus forming a composite compound. The initial charge and discharge capacities of the composite cathode powders prepared from the 0.8 wt% boric acid spray solution are 297 and 217 mAh g{sup −1}, respectively. The discharge capacity of the powders decreases from 217 to 196 mAh g{sup −1} by the 30th cycle, in which the capacity retention is 90%.« less
  • A series of electroactive spinel compounds, LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} (0.1{le}x{le}0.5), has been studied by crystallographic, spectroscopic, and electrochemical methods and by electron microscopy. These spinels are nearly identical in structure to cubic LiMn{sub 2}O{sub 4} and successfully undergo reversible Li intercalation. The electrochemical data show a remarkable reversible electrochemical process at 4.9 V which is attributed to the oxidation of Cu{sup 2+} to Cu{sup 3+}. The inclusion of Cu in the spinel structure enhances the electrochemical stability of these materials upon cycling. The initial capacity of LiMn{sub 2{minus}x}Cu{sub x}O{sub 4} spinels decreases with increasing x from 130 mAh/g inmore » LiMn{sub 2}O{sub 4} (x = 0) to 70 mAh/g in LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} (x = 0.5). The data also show slight shifts to higher voltage for the delithiation reaction that normally occurs at 4.1 V in standard Li{sub 1{minus}x}Mn{sub 2}O{sub 4} electrodes (1{ge}x{ge}0) corresponding to the oxidation of Mn{sup 3+} to Mn{sup 4+}. Although the powder X-ray diffraction pattern of LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} shows a single-phase spinel product, neutron diffraction data show a small but significant quantity of an impurity phase, the composition and structure of which could not be identified. X-ray absorption spectroscopy was used to gather information about the oxidation states of the manganese and copper ions. The composition of the spinel component in the LiMn{sub 1.5}Cu{sub 0.5}O{sub 4} was determined from X-ray diffraction and X-ray absorption near-edge spectroscopy to be Li{sub 1.01}Mn{sub 1.67}Cu{sub 0.32}O{sub 4}, suggesting to a best approximation that the impurity in the sample was a lithium-copper-oxide phase. The substitution of manganese by copper enhances the reactivity of the spinel structure toward hydrogen: the compounds are more easily reduced at moderate temperature ({approximately} 200 C) than LiMn{sub 2}O{sub 4}.« less
  • The high voltage cathode material, LiMn 1.6Ni 0.4O 4, was prepared by a polymer-assisted method. The novelty of this paper is the substitution of Ni with Mn, which already exists in the crystal structure instead of other isovalent metal ion dopants which would result in capacity loss. The electrochemical performance testing including stability and rate capability was evaluated. The temperature was found to impose a change on the valence and structure of the cathode materials. Specifically, manganese tends to be reduced at a high temperature of 800 °C and leads to structural changes. The manganese substituted LiMn 1.5Ni 0.5O 4more » (LMN) has proved to be a good candidate material for Li-ion battery cathodes displaying good rate capability and capacity retention. Finally, the cathode materials processed at 550 °C showed a stable performance with negligible capacity loss for 400 cycles.« less
  • Layer-structured cathode material for lithium ion batteries LiNi{sub 0.375}Co{sub 0.25}Mn{sub 0.375-x}Cr{sub x}O{sub 2-x}F{sub x} (0 {<=} x < 0.1) has been synthesized from sol-gel precursors. Its structure and electrochemical properties were investigated by X-ray diffraction (XRD) and a variety of electrochemical techniques. The XRD results reveal that LiNi{sub 0.375}Co{sub 0.25}Mn{sub 0.375-x}Cr{sub x}O{sub 2-x}F{sub x} has typical hexagonal structure without impurity. The Cr-F co-doped materials show higher specific discharge capacity and improved cycling performance compared with the raw materials as x in the range of 0.00-0.06. LiNi{sub 0.375}Co{sub 0.25}Mn{sub 0.315}Cr{sub 0.06}O{sub 1.94}F{sub 0.06} demonstrates an initial discharge capacity of 168.5 mAhmore » g{sup -1} with 20th capacity retention about 93.7%. It has been confirmed that the improved cycling performance is derived from the little increase of electrochemical impedance during the cycling.« less