Cobalt

Phosphosulphides
An Advanced Bifunctional Material for Superior
Battery Anodes
and
Electrocatalytic Oxygen Evolution

Presented by: Chia Ching Keat

Supervisor: Assoc. Prof. Alex Yan Qingyu
Mentor: Dr Dai Zhengfei
 Outline
Objectives
Lithium Ion
Water – Splitting
Batteries
Material Selection

Experimental

Results

Characterization LIB Performance OER Performance

Future Research

Conclusion
 Objectives
1. Evaluate Lithium Ion
Batteries and Clean
Hydrogen Fuel

?
 Objectives
2. Material Selection

CoP3 CoS2

3. Synthesis and Evaluation

Lithium Ion Batteries
(LIBs)

• Anode
• Cathode
• Electrolyte
Limitation of LIBs
 Water – Splitting

Hydrogen Evolution

Oxygen Evolution
Oxygen Evolution Reaction
(OER)

Equilibrium Potential of Water

= 1.23 V
Reality: >1.23 V is
needed!
 OER Performance
(Universal Descriptor)
 OER Performance
(Universal Descriptor)
Determines Catalytic
Suntivich et al. (2011) Activity
eg
dx2- dz2
dxy
t2g
3d Orbital dxy dyz dzx

Optimal Catalytic
Material
•eg-orbital filling =
1.25
 LIBs and Water -
Splitting
Lithium Ion Batteries Water - Splitting

Improve Efficiency Reduce Overpotential

Better Anode

• High Specific Capacity • Low Overpotential

• High Stability • High Catalytic Activity
• Use less lithium • Clean Hydrogen Fuel
 TMPs + TMDs
Transition Metal Transition Metal
Phosphide Dichalcogenide
Co-P-S
Cobalt Phosphide Cobalt Sulphide Cobalt Phosphosulphide

LIB Anode LIB Anode LIB Anode

• High Specific Capacity • Low Specific Capacity • High Specific Capacity

• Low Stability • Good Stability • Good Stability

OER catalyst OER catalyst OER catalyst

• Research only done for • High Catalytic Activity • High Catalytic Activity
HER

CoP3
TMPs + TMDs
(Structure)
Research by Geng et al. (2017
•Yolk – Shell Structure

Effects
•Superior Li/Na Storage
•Rapid Ion Transport
•Accommodates volume
change
Experimental (Synthesis)
Experimental (LIB)
NEWARE Multichannel Battery Test System

Assembled Coin-Type Battery

Anode Electrolyte Cathode

• 70% Co-P-S • 1M LiPF6 • Lithium

• 20%
Graphene
• 10% PVDF
 Experimental (OER)
Three – Electrode Test System

Working Counter Reference

Electrode Electrolyte
Electrode Electrode
• 5 mg Co-P-S • 1 M KOH • Platinum • Ag/AgCl (vs.
• 1 ml IPA RHE)
• 20 μL Nafion
Characterization (SEM)

1.Fairly uniform spheres (400

nm – 552nm)
 Characterization (XRD)

Co-P-S Structure = CoS Pyrite Structure

Characterization (XRD)
S

Co

P
Characterization (TEM)

1.Excessive Sonication = Damaged

Spheres
2.Co-P-S hollow spheres
3.Spheres are semi-crystalline
 Characterization
(HAADF/EDS-STEM)

Void
space

1.Yolk – shell structure confirmed

2.Uniformly distributed Co/P/S elements
throughout sphere
 Characterization (XPS)
Phosphorization Step = Co (II) decreased while
Co (III) increased

Co (II) Co (III)
decreased increased
 Characterization (XPS)

Presence of:
•Phosphorus (II)
•Sulphur (II)
•Phosphate by-
products
•Sulphate by-
products
LIB Performance
Anode Specific
Capacity(mAh/g)
Graphite 372
Co-P-S 870

Cycle Columbic
Efficiency (%)
First 56.9
Second 96.7

Sides Reactions
•By-product formation
•SEI layer formation
LIB Performance
Graphite:

Co-P-S:

Possible contribution from

yolk-shell structure: Rapid
Ion Transport
LIB Performance
Good stability due to
space in between ‘yolk’
and shell
 OER Performance

Overpotential: Co-P-S < Ir-O < Co-O <

Co-P < Co-S
Best OER
Catalyst!
 OER Performance
Kinks, ledges and unsaturated
surface defect sites
Sulphur Terminated Phosphorus Terminated
Edges Edges

Possible OER Active Sites

Square-pyramidal surface
metal centres bridged by
dichalcogenide dumbbells
 OER Performance
Co-S Phosphorization Co-P-S

• Co2+

• Co3+

Co3+

Increased number of P/S Modified ∆G2

Modulated eg-orbital
active sites

Increased OER activity

 OER Performance
Co-S Phosphorization Co-P-S

Electronegative P atoms restrict electron delocalization = less conductive

However,

Appropriate metal-phosphorus ratios = excellent conductivity

Anode Overpotential (mV / decade)

Co-S 109
Co-P 111
Co3O4 61
IrO2/C 82
Co-S0.32-P0.68 72
Co-S0.72-P0.28 53
Co-S0.46-P0.54 48
 OER Performance

Build-up of catalytically inactive phosphate/sulphate side products

Lower stability over time

 Future Research
1. LIB capacity and OER activity may be improved
by adding nanoflower or urchin-like features to
Rui et al. (2013) the yolk – shell spheres
Tang et al. (2013)
 Future Research

2. LIB capacity and OER activity may be improved

by decreasing Co-P-S spheres to nano-sized

Size (nm) Specific Capacity OER Overpotential

(mAh/g) (mV/decade)
400 – 552 870 48
<100 >870? <48?
 Future Research

3. OER activity may be improved by doping

additional transition metals

Anode OER Overpotential at 10mA/cm2

Co-P-S Yolk-Shell Spheres 250 mV
NiCoPS nanowire/carbon cloth 230 mV
Li et al. (2017)

Is OER activity improved by Nickel doping OR carbon cloth OR nanowire shape?

 Future Research

4. Feasibility studies: Using Co-P-S in Sodium Ion

Batteries.
Can SIBs be commercialized?
Lithium Ion Batteries Sodium Ion Batteries

High Capacity Low Capacity due to larger sodium

ions

Fairly Stable Large sodium ions tend to pulverize

anodes quickly
 Conclusion
TMPs Synergy TMDs

LIB Anode
• High Specific Capacity
• Good Stability

OER catalyst
• High Catalytic Activity
• Good Stability
 Conclusion
Superior Li+ Yolk – Shell
LIB Performance
Storage Structure

Various OER Active Sites

Modulated
OER Performance Modified ∆G2
eg-orbital

Electrical Conductivity Yolk – Shell Structure

Thank you for your
attention!
Q&A
 References
(in addition to the ones used in FYP
Report)
• http://www.emc2.cornell.edu/content/view/battery-anodes.html
• http://pubs.acs.org.ezlibproxy1.ntu.edu.sg/doi/pdf/10.1021/jacs.6b00036
• Y. Shi and B. Zhang. “Recent advances in transition metal phosphide
nanomaterials: synthesis and applications in hydrogen evolution reaction”,
Royal Society of Chemistry, 2016, Volume 45, Pages 1529-1541. http://
dx.doi.org/10.1039/C5CS00434A
• W. Liu, E. Hu, H. Jiang, Y. Xiang, Z. Weng1, M. Li, Qi Fan, X. Yu, E. I.
Altman and H. Wang. “A highly active and stable hydrogen evolution
catalyst based on pyrite-structured cobalt phosphosulfides”, Nature
Communications Volume, 2016, 7. http://dx.doi.org/10.1038/ncomms10771
Appendix (LIB Types)
Lithium Cobalt Oxide
•High Capacity
•Low Specific Power
•Short Lifespan

Lithium Manganese Oxide

•Higher Thermal Stability
•Enhanced Safety
•Short Lifespan

Lithium Iron Phosphate

•High Specific Power
•Long Cycle Life
•Lower Capacity
 Appendix (LIB Anodes)
Anode
Carbonaceous (Most Commonly Used)
Lithium
Tin
Metal-Metal Alloys
Metalloids
Transition Metal Phosphides (TMPs) Large Irreversible Volume Changes
Transition Metal Dichalcogenides
(TMDs)
TMPs + TMDs Compound/Mixture
Limitation
Irreversible Capacity Loss
Dendrite Growth
Inclusion of Solid Electrolyte Phase
Large Volume Changes
Moisture Sensitive
Low Capacity
?
Appendix (Catalyst Selection)
(Cathode and Anode)
Butler – Volmer Equations:
 Appendix
(HER)

H+

Electrolyte H+
1
1 H2

2 or 3
H(ad) H(ad)

Electrode Surface

HER Mechanism: 1+2

or 1+3
Appendix
(HER)

Sabatier Principle
“Volcano Plot”

=0
Appendix
(OER)
 Appendix
(OER Performance)

Overpotential = Operational Potential – 1.23V