Developing High Capacity, Long Life anodes
K. Amine (P.I)A. Abouimrane, D. Dambournet, and I. Belharouak,
Argonne National Laboratory
DOE merit reviewMay 09, 2011
Project ID # ES020This presentation does not contain any proprietary, confidential, or otherwise restricted information.
Overview
• Start - October 1st, 2009.• Finish – September 2014• 50% complete
• Safety of the battery.• Power density of the battery.• Cycle & calendar life span of the
battery.
• Total project funding: 900K
– FY11: 300K
– FY10: 300K
– FY09: 300K
Timeline
Budget
Barriers
• P. Chupas, K. Chapman, Y. Ren Advanced Photon Source, (APS/ANL).
• Z. Fang (University of Utah).• FMC, Northwestern University,
Partners
Develop new advanced high energy anode materials withlong life and improved Safety for PHEV and EV applications.
Objectives
Develop a low cost synthesis methods to prepare high energy anodes
Full structural and electrochemical characterizations of the prepared anode materials.
Demonstrate the applicability of these anodes in half and full cells systems.
Approaches MO-SnxCoyCz (MO=SiO, SiO2, SnO2, MoO2, GeO2) anode materials were
selected for investigation as high energy anode based on the followingcriteria:• SnxCoyCz alloys are known to provide a capacity of 400-500mAh/g for hundreds of
cycles.
• MO anodes are known to provide more than 1000 mAh/g with poor cyleability.
• The formation of SnxCoyCz and MO composite could lead to the increase in thecapacity, reduce the amount of cobalt in the material and improve the cyleablity asSnxCoyCz play the role of buffers against the volume expansion of MO.
• This anode system is more safer than the graphite and possess low potentials in therange of 0.3-0.75V (expect high voltage cells when combined with high cathodes)
• This anode system could offer higher practical capacity and higher 1st cycle chargedischarge efficiency
• This anode system offers high packing density (up to 3 g/cc), much higher than graphite(1.1g/cc) ( except higher volumetric density)
Milestones FY 10 : High capacity and Long Life Anodes
Some of the composite anode were prepared by mechanically alloyingusing metal (Co, Sn) carbon and oxides (MO). (Completed)
Comparative studies between MO-SnxCoyCz (MO=SiO, SiO2, SnO2, MoO2,GeO2) based on their electrochemical properties and their cost.(Completed)
Investigation of their structural rearrangement during the intercalationor de-intercalation of lithium. (On going)
Selection of a candidate for further electrochemical characterization:full cells study and HPPC tests. (On going)
Improvement of the 1st cycle charge discharge efficiency. (On going)
All materialswere prepared using a high energy ball milling.
Preparation of 50 wt% MO – 50 wt% Sn30Co30C40(MO= MoO3, SnO2, GeO2, SiO2, SiO) materials
10 20 30 40 50 60 70 802θ (º)
MoO2
10 20 30 40 50 60 70 802θ (º)
SnO2*
* Sample holder
10 20 30 40 50 60 70 80
* Sample holder
2θ (º)
GeO2
*
10 20 30 40 50 60 70 802
3
2θ (º)
SiO2
XRD shows that the SnO2 structure was conserved, MoO3 was reduced to MoO2 and no trace of GeO2 is present confirming the composite structure.
10 20 30 40 50 60 70 80
2θ (º)
SiO
Densities of 50 wt% MO – 50 wt% Sn30Co30C40(MO= MoO3, SnO2, GeO2, SiO2, SiO)
Material
50 wt% MO – 50 wt% Sn30Co30C40
Tap density
g/cc
True density
g/cc
MO = MoO3 2.74 6.05
MO = SnO2 3.02 7.13
MO = GeO2 2.62 5.06
MO = SiO2 1.43 3.58
MO = SiO 1.89 3.78
Materials based on tin, molybdenum and germanium have the highest tap density. Materials based silicon and tin are the cheapest.
Voltage profile and cycleability 50 wt% MO – 50 wt% Sn30Co30C40 (MO= MoO3)
0 200 400 600 800 1000 12000.0
0.5
1.0
1.5
2.0
2.5
3.0
Volta
ge
Capacity (mAh/g)
MoO3 Cycle 1 MoO3 Cycle 2 MoO3-SnCoC Cycle 1 MoO3-SnCoC Cycle 2
The laminate is prepared by using 80% active material 10% Acetylene black and 10% Polyimide binder.
Battery are cycled between 5mV and 2.5V.
A Voltage ~ 0.6V higher than the graphite was observed. High Voltage means less Li- plating and better safety.
The composite material cycles far much better than the MoO3 oxide alone.
0 20 40 60 80 100
200
400
600
800
1000
1200
1400
MoO3
50wt%MoO3-50wt%Sn30Co30C40
Capa
city
(mAh
/g)
Cycle number
Cycles 1 & 2 at 50mA/g (5mV-2.5V)From cycles 3 at 300mA/g
0 20 40 60 80 100 120 140 160 180 2000
200
400
600
800
1000
1200
Capa
city
(mAh
/g)
Cycle number
Charge Capacity Discharge Capacity
MoO3-Sn30Co30C40 PIVS (300mA/g)
~ 0.625/cm2
0 50 100 150 2000
200
400
600
800
1000
1200
MoO3-Sn30Co30C40 PIVS (300mA/g)
Active material ~ 1.35/cm2
Charge Discharge
Capa
city
(mAh
/g)
Cycle number
580
A capacity near 580 mAh/g is delivered after 200 cycles under 300 mA/g current rate (over C/2 rate).
1st cycle effeciecy~70%.
The capacity changes with the active material loading.
With low active loading, a capacity of 800 mAh/g can be reached.
Cycleability and effect of loading on 50 wt% MO – 50 wt% Sn30Co30C40 (MO= MoO3)
Good cycling with high coulombic efficiency after the first cycle.
50 wt% MoO3 – 50 wt% Sn30Co30C40 anode showed superior rate capability, i.e. 325 mAh/g capacity under a 7~8C rate.
0 5 10 15 20 25 300
200
400
600
800
1000
1200
1400
50
100
200400
8001200
16002000
Capa
city
(mAh
/g)
Number Of Cycles
Charge Discharge
2400
Current
(mA/g)
Capacity
(mAh/g)
100 610
200 565
400 515
800 460
1200 415
1600 375
2000 335
2400 325
Rate capability of 50 wt% MO – 50 wt% Sn30Co30C40(MO= MoO3)
Voltage profile and cycleability of 50 wt% MO – 50 wt% Sn30Co30C40 (MO= SnO2)
0 50 100 150 2000
400
800
1200
1600
2000
SnO2
Charge Discharge Charge Discharge
Capa
city
(mAh
/g)
Cycle number
50wt%SnO2-50wt%Sn30Co30C40
A Voltage ~ 0.75V, higher than the graphite that provide better safety and no lithium plating
The composite shows a capacity of 400 mAh/g for more than 150 cycles with moderate capacity fade under 300mA/g current rate.
1st cycle effeciecy~65%.
The composite material cycles better than the SnO2 oxide alone.
0 500 1000 1500 20000.0
0.5
1.0
1.5
2.0
2.5
Volta
ge
Capacity (mAh/g)
SnO2 Cycle 1 SnO2 Cycle 2 SnO2-SnCoC Cycle 1 SnO2-SnCoC Cycle 2
0 5 10 15 20 25 300
200
400
600
800
1000
1200
1400
50
100200
400600
8001000
Capa
city
(mAh
/g)
Cycle number
Charge Discharge
1200
Current
(mA/g)
Capacity
(mAh/g)
100 510
200 455
400 410
600 371
800 342
1000 332
1200 316
Rate capability of 50 wt% MO – 50 wt% Sn30Co30C40(MO= SnO2)
Good cycling with high coulombic efficiency (1st cycle irreversibility is about 65% due to the formation of Li2O which is not active in the case of SnO2-Sn30Co30C40 composite).
50 wt% SnO2 – 50 wt% Sn30Co30C40 anode showed superior rate capability, i.e. 316 mAh/g capacity under a 4C rate.
0 500 1000 1500 20000.0
0.5
1.0
1.5
2.0
2.5
Volta
ge
Capacity (mAh/g)
GeO Cycle 1 GeO Cycle 2 GeO-SnCoC Cycle 1 GeO-SnCoC Cycle 2
0 20 40 60 80 100 120
0
500
1000
1500
2000
2500
GeO2
Charge Discharge Charge Discharge
Capa
city
(mAh
/g)
Cycle number
50wt%GeO2-50wt%Sn30Co30C40
A Voltage ~ 0.5V higher than the graphite was observed
The composite shows a capacity of 800-1000 mAh/g for 100 cycles with moderate capacity fade under 300 mA/g current rate.
1st cycle charge discharge effeciecy~80%.
The composite material cycles better than the GeO2 oxide alone with much higher 1st
cycle charge-discharge efficiency.
Voltage profile and cycleability of 50 wt% MO – 50 wt% Sn30Co30C40 (MO= GeO2)
0 20 40 60 80 1000
200
400
600
800
1000
SiO2
50wt%SiO2-50wt%Sn30Co30C40
Capa
city
(mAh
/g)
Cycle number
DischargeChargeDischargeCharge
Cycles 1 & 2 at 50mA/g (5mV-2.5V)From cycles 1 (5mV-1.5V)
0 200 400 600 8000.0
0.5
1.0
1.5
2.0
2.5
3.0
Volta
ge
Capacity (mAh/g)
SiO2-SnCoC Cycle 1 SiO2-SnCoC Cycle 2 SiO2 Cycle 1 SiO2 Cycle 2
Voltage profile and cycleability of 50 wt% MO – 50 wt% Sn30Co30C40 (MO= SiO2)
A Voltage ~ 0.5V higher than the graphite with MO=SiO2
SiO2 alone is not electrochemically active.
The composite shows a capacity of 432 mAh/g for 100 cycles with outstanding charge discharge efficiency when it cycled between 5mV and 1.5V under 100 mA/g current using only a PVDF binder.
1st cycle effeciency~64%.
0 500 1000 1500 2000 25000.0
0.5
1.0
1.5
2.0
2.5
3.0
Volta
ge
Capacity (mAh/g)
SiO Cycle 1 SiO Cycle 2 SiO-SnCoC Cycle 1 SiO-SnCoC Cycle 2
0 50 100 150 2000
500
1000
1500
2000
2500
SiO
Charge Discharge Charge Discharge
Capa
city
(mAh
/g)
Cycle number
50wt%SiO-50wt%Sn30Co30C40
Voltage profile and cycleability of 50 wt% MO – 50 wt% Sn30Co30C40 (MO= SiO)
A voltage ~0.5V higher than that of graphite.
A capacity near 580 mAh/g is delivered after 130 cycles under 300 mA/g current rate between 5mv and 1.5V
1st cycle charge-discharge effeciecy~79% is better than SiO alone (only 67%).
Summary
MO-SnxCoyCz (MO = SiO, SiO2, SnO2, MoO2, GeO2) system was prepared bymechanically alloying using a high energy ball milling.
MO-SnxCoyCz system where (MO = SiO, SiO2, SnO2) are the most competitivesystem in term of cost.
50wt% SnO2 - 50wt% Sn30Co30C40 system provides the higher tap density butsuffers from the first cycle irreversibility ( near 65% ).
50wt% SiO - 50wt% Sn30Co30C40 system shows promising properties in termsof cost, tap density, capacity, cycleability and 1st cycle charge discharge efficiency.
Future Works Investigate of MO-SnxCoyCz (MO = SiO, SiO2, SnO2, MoO2, GeO2) system in fullcell configuration.
In-situ structural characterizations of MO-SnxCoyCz (MO = SiO, SiO2, SnO2,MoO2, GeO2) system with APS (Dr. Ren ).
Ex-situ PDF characterizations with APS (Dr. Chupas).
Surface characterization of lithiated anode materials by XPS with UtahUniversity (Dr. Fang).
Investigate the pulse-discharge and charge performance of designed cell basedon MO-SnxCoyCz (MO = SiO, SiO2, SnO2, MoO2, GeO2) system anode throughhybrid pulse power characterization (HPPC test).
Understand the causes of the first cycle charge discharge irreversibility and tryto reduce it.
Collaborations
A. Tressaud & A. Demourgues (ICMCB, Bordeaux, France)
FMC corporation
PJ. Chupas, and Y. Ren Advanced Photon Sources, Argonne
Z. Fang University of Utah.
Provisional application- New Silicon-based anode material, A. Abouimrane, K. Amine, (IN-10-013).
Patents
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