High-Performance LiCoO2 from Scalable Template Processing

Colin (Zhaoxiang) Qi Advisor: Gary Koenig

Department of Chemical Engineering, University of Virginia

1. Research Background and Goal 2. Template Based Synthesis Procedure 3. Powder Morphology
Active materials typically have low electronic and ionic conductivities. CoC2O4 · 2H2O LCO Fired at 750 °C LCO Fired at 800 °C

Smaller active material particles offer higher rate-capabilities and round

trip energy efficiencies. Co2+ and C2O42- Solutions

Co-Precipitation

CoC2O4 · 2H2O Rods LCO Fired at 850 °C LCO Fired at 900 °C

Milled LCO from
800 °C Sample
Calcination
Interconnected LCO

Soft Milling

A scalable method to synthesis sub-micrometer or nano-sized active material Discrete LCO Particles • Particle morphology was maintained under 800 °C.
particles with low energy consumption and low cost is needed.
• Particles sinter and size increases under high calcination temperature.
This work aims to demonstrate such an approach with LiCoO2 (LCO) synthesis • The loose connection between the calcined particles broken using soft milling.
via a template based method.

4. X-Ray Diffraction on LCO 5. First Charge and Discharge Profile 6. High Rate Capability on a Graphite/LCO Cell

4.5 Charge
180 Charge

Voltage (V, vs Li/Li+)

Discharge
4.0 150

Capacity (mAh g-1)

0.2C
Discharge 0.5C
3.5 120 1C 2C
5C
3.0 90 10C
2.5 60

2.0 30

1.5 0
0 30 60 90 120 150 180 0 4 8 12 16 20 24
Capacity, mAh g-1 Cycle Number
• First discharge achieved 172 mAh gLCO-1 at 0.1C on a Li/LCO cell.
• The discharge capacity at 10C maintained 88.1% of the 0.2C capacity.
• First cycle had 12.5% irreversible capacity loss due to high surface area
• Small particle size contributed to the high rate capability by providing high
• Both pre- & post-milled LCO match the reference pattern with minor residual Co3O4. and high cutoff voltage.
surface area and short Li+ transport distance.

7. Cycle Life 8. Summary 9. References and Acknowledgement

• Z. Qi and G. M. Koenig, ChemistrySelect, 1 (13), 3992-3999 (2016).
100 • Z. Qi, A. L. Liu, and G. M. Koenig, Electrochim. Acta, 228 91-99 (2017).
180
• Demonstrated a sub-micrometer lithium-ion active material synthesis • https://www.toyota.co.nz
Coulombic Efficiency (%)

150 80 M. Okubo, et al., J. Am. Chem. Soc., 129 7444-7452 (2007).

Capacity (mAh g-1)

method adaptable in current industrial methods and applicable to •

• M. Gaberscek, et al., Electrochem. Commun., 9 (12), 2778-2783 (2007).
120 other active materials with LCO as an example.
60 Acknowledgement:
90 Special thanks to Professor Geoffrey Geise, Joshua Choi, David Green and Robert Kelly
40
60 • Synthesized LCO achieved good electrochemical performance,
20 including capacity, rate capability and cycle life.
30

0 0
0 80 160 240 320 400 480
Cycle Number • The soft milling procedure requires relatively low energy input.

• Cycle life of a Graphite/LCO cell at 1C.

• ~100 mAh gLCO-1 LCO (79%) capacity was maintained after 100 cycles.