Research Papers

Probing the Effect of High Energy Ball Milling on the Structure and Properties of LiNi1/3Mn1/3Co1/3O2 Cathodes for Li-Ion Batteries

[+] Author and Article Information
Malcolm Stein, IV, Chien-Fan Chen

Department of Mechanical Engineering,
Texas A&M University,
College Station, TX, 77843

Matthew Mullings

2501 Earl Rudder Freeway South,
College Station, TX 77845

David Jaime, Audrey Zaleski

Department of Chemistry and Biochemistry,
Texas State University,
601 University Drive,
San Marcos, TX 78666

Partha P. Mukherjee

Department of Mechanical Engineering,
Texas A&M University,
College Station, TX, 77843
e-mail: pmukherjee@tamu.edu

Christopher P. Rhodes

Department of Chemistry and Biochemistry,
Texas State University,
601 University Drive,
San Marcos, TX 78666
e-mail: cprhodes@txstate.edu

1Corresponding authors.

Manuscript received April 7, 2016; final manuscript received September 14, 2016; published online October 20, 2016. Assoc. Editor: George Nelson.

J. Electrochem. En. Conv. Stor. 13(3), 031001 (Oct 20, 2016) (10 pages) Paper No: JEECS-16-1046; doi: 10.1115/1.4034755 History: Received April 07, 2016; Revised September 14, 2016

Particle size plays an important role in the electrochemical performance of cathodes for lithium-ion (Li-ion) batteries. High energy planetary ball milling of LiNi1/3Mn1/3Co1/3O2 (NMC) cathode materials was investigated as a route to reduce the particle size and improve the electrochemical performance. The effect of ball milling times, milling speeds, and composition on the structure and properties of NMC cathodes was determined. X-ray diffraction analysis showed that ball milling decreased primary particle (crystallite) size by up to 29%, and the crystallite size was correlated with the milling time and milling speed. Using relatively mild milling conditions that provided an intermediate crystallite size, cathodes with higher capacities, improved rate capabilities, and improved capacity retention were obtained within 14 μm-thick electrode configurations. High milling speeds and long milling times not only resulted in smaller crystallite sizes but also lowered electrochemical performance. Beyond reduction in crystallite size, ball milling was found to increase the interfacial charge transfer resistance, lower the electrical conductivity, and produce aggregates that influenced performance. Computations support that electrolyte diffusivity within the cathode and film thickness play a significant role in the electrode performance. This study shows that cathodes with improved performance are obtained through use of mild ball milling conditions and appropriately designed electrodes that optimize the multiple transport phenomena involved in electrochemical charge storage materials.

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Fig. 1

Comparison of powder X-ray diffraction (XRD) data for CM01, CM02, and CM08: (a) full scan range; (b) expanded range for 2θ° = ∼18 to 19 showing the change in the peak width for ball-milled samples CM02 and CM08 compared with unmilled base sample CM01

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Fig. 2

Comparison of effect of milling time and speed on crystallite size obtained X-ray diffraction data using the Scherrer equation

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Fig. 3

Scanning electron microscopy (SEM) images of baseline (CM01) and ball-milled NMC samples: (a) CM01, (b) CM02, (c) CM03, (d) CM04, (e) CM05, (f) CM06, (g) CM07, and (h) CM08

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Fig. 4

Discharge voltage profiles for 25 μm-thick NMC electrodes at a) 1C rate, 25 μm thick and b) 2C rate, 25 μm thick discharge rates

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Fig. 5

(Top) Electrochemical impedance data (Nyquist plot) for the 25 μm-thick CM01 and CM02 samples in discharged state; (bottom) equivalent circuit used for fitting electrochemical impedance

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Fig. 6

Experimental voltage profiles of discharge of 14 μm-thick NMC electrodes for (a) 1C and (b) 2C

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Fig. 7

Simulated discharge voltage profiles of NMC electrodes: (a) effect of electrolyte diffusivity and (b) effect of electrode thickness. Details of parameters used for the simulations are provided in Table 6 and the text.




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