Lead-Copper Alloys as High Capacity Anode Materials for Lithium Ion Batteries

August 1
Rothenberger , Alan 1
Guo , Adam 2
Heller , and C. Buddie Mullins 1,2

1. Department of Chemistry, 2. Department of Chemical Engineering, University of Texas at Austin

Introduction Experimental Methods Coin Cell Testing Cyclic Voltammetry

Traditional Li-ion Battery (LIB) Synthesis Procedure Slurry Casting Background
• Li metal oxide cathode, separator, graphite anode • Lead too malleable for mechanical milling • Standard slurry composed of active material, • CV involves varying the voltage at 0.1 mA/s and
• Li ions flow from anode to cathode when discharging • Synthesize Pb0.9Cu0.1 alloy in aqueous solution polymeric binder, and conductive carbon measuring the current through a 2032 coin cell
• 9 mmol Pb(NO3)2, 1 mmol CuCl2 • 8:1:1 wt PbO-Cu:CMC90k:Super-P Carbon Black • Peaks are used to determine intermediate lithiation
• Reduced by NaBH4 • Cast onto copper foil at 1.2mg and 0.6mg stages of active material
• HCl and 1,2-diaminopropane as stabilizer and 2032 Coin Cell Results
surfactant, respectively • Constructed a half cell using lithium foil as second
• Dark grey precipitate forms after about 30 min electrode Delithiation
• Centrifuge and wash with water, dry in oven

Top Metal Cap

Materials Characterization Metal Spacer
From Roy et al. “Nanostructured anode materials for lithium ion batteries.” Royal Society of Chemistry, Published 2014.

• LIBs could increase capacity/gram with anodes made Scanning Electron Microscospy (SEM) Lithium Foil

from other group IVA elements (Si, Ge, Sn, Pb) • Synthesized material composed of “layered” lead LiPF6 FEC:DEC Electrolyte

• 6𝐶 + 𝐿𝑖 + + 𝑒 − ⇌ 𝐿𝑖𝐶6 0.167 Li per C • Mostly micron scale particles (1-100 um) Celgard PP 2400 Separator
• 2𝑃𝑏 + 7𝐿𝑖 + + 7𝑒 − ⇌ 𝐿𝑖7 𝑃𝑏2 3.5 Li per Pb LiPF6 FEC:DEC Electrolyte Lithiation

Slurry on Copper Foil

Problems with Non-carbon Group IVA Anodes
Metal Spacer
• Volume change during cycling (up to 300%) pulverizes • Cycle 1 peaks at 1.35 V and 1.55 V suggests
anode structure, decreases battery life Metal Spring chalcogenide (oxide) pre-lithiation
• Solid Electrolyte Interphase (SEI) formation Plastic Cap • Peaks from 1.0 – 0 V correspond to Pb lithiation
• Li interaction with electrolyte at anode forms SEI Bottom Metal Cap
and removes ions from battery
• Larger particles can be broken up with agitation
Stabilizing Agents • Ionic characteristic, material not pure metal Conclusions
• Additives like chalcogenides and transition metals
can buffer volume expansion, increasing battery life Cycling Performance • EDX, XRD suggests material is PbO with imbedded Cu
Agitation on vortex
• Sub-stoichiometric (9:1) ratios increase amount of plate • CV supports oxide hypothesis
available active material
Background • Performing aqueous synthesis in air forms oxides
• Copper used as tin anode stabilizer at 9:1 Largest particles decrease in
• LIB cycling is (dis)charging battery at different c-rates • Carbon from organic surfactant
size or appear more broken up • 1C means the battery is fully charged in 1 hour • Despite this, the material still cycled very well
• C/2 = charge in 2 hours, 2C = charge in 30 min
• PbO/PbO-Cu exhibit great potential as future LIB
Energy-Dispersive X-Ray Spectroscopy (EDX) • Reversible capacity is the output charge per gram
anode materials
• Lead and copper well dispersed throughout material active material (mAh/g)
• Same amount of oxygen as lead, suggests PbO Results
• Atomic ratio about 40 Pb : 40 O : 10 Cu : 10 C
SEM images showing that adding 10% selenium into germanium electrodes decreases film EDX Spectrum Scan for Synthesized Material
C/20
Cycling Performance by Mass Loading Future Directions
delamination and dendritic growths during cycling, improving the performance of the battery. Element Norm. At % Norm. Wt %
Lead 38.8 85.2

• Cycle long term at C/2 to determine electrode stability

From Klavetter et al. “High tap density microparticles of selenium-doped germanium as a high efficiency, stable
cycling lithium-ion battery anode material.” Journal of Materials Chemistry A, Published 2015. Oxygen 38.34 6.5
1.2mg Average 0.6mg Average
Copper 9.9 6.7 C/5
Counts

Lead Anodes in LIBs

Carbon 12.9 1.6 • Identify unknown XRD peaks to determine true
• Lead has capacity of 453 mAh/g C/2
composition of synthesized material
• 35% more than graphite 1C
1C
• Compare cycling data to electrodes of pure PbO
2C
• Lead is malleable and may be able to better handle microparticles to determine function of copper
5C
• Perform hydrothermic/carbonthermic reduction to
Energy (keV)

volume strain during lithiation X-Ray Powder Diffraction (XRD)

• Copper additive is also a better electron conductor • XRD spectrum shows peaks for PbO remove oxides from material
• Incorporating Pb0.9Cu0.1 into LIBs anodes could lead • Unidentified peaks, full composition unknown • Attempt to synthesize pure Pb0.9Cu0.1
to development of smaller, more powerful batteries • Further investigate ability for Pb, Pb0.9Cu0.1, or PbO-Cu
to be used as anodes in Li+ or Na+ batteries

Research Questions • Electrodes stable during cycles, low capacity fade

Intensity (counts)

• Lower mass electrodes exhibit better performance Acknowledgments

• Can a sub-stoichiometric lead-copper alloy be • Thicker electrodes experience worse kinetics
incorporated as an anode material in a successful • Nearly 600 mAh/g at C/20, above theo. capacity
lithium ion battery? • Very small current, likely instrument error
• Will lead anodes experience similar problems as PbO Spectrum
• Effective recovery from 5C to 1C
other group IVA anodes? 2θ (degrees)
• Electrodes can handle fast charging rates