Design of Safer High-Energy Density Materials for Lithium-Ion Cells Ilias Belharouak (PI) D. Wang, G. Koenig , X. Zhang, K. Amine Argonne National Laboratory May 16, 2012 This presentation does not contain any proprietary, confidential, or otherwise restricted information Project ID es163
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Design of Safer High-Energy Density
Materials for Lithium-Ion Cells
Ilias Belharouak (PI)
D. Wang, G. Koenig , X. Zhang, K. Amine
Argonne National LaboratoryMay 16, 2012
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Project IDes163
Argonne National Laboratory, Chemical Sciences and Engineering Division
2
Overview Start – January 2011 Finish – October 2014 Percent complete – 25%
Energy density of available Li-ion battery technologies
– Weight, volume, and affordability
Abuse tolerance– Energy storage systems that must be intrinsically
tolerant of abusive conditions
Timeline
Budget
Barriers
Partners Collaboration:
– Binghamton University– Washington University in Saint Louis– Pacific Northwestern National Laboratory– Energy Systems Division, Argonne
Support: G. Koenig, D. Wang, X. Zhang, B. Polzin, W. Lu, A. Jansen, G. Krumdick, K. Takeya, K. Amine.
Project lead: Ilias Belharouak
Total project funding in FY11 and FY 12: $250K + $300K
Funding in FY12: $300K Funding in FY11: $250K
Argonne National Laboratory, Chemical Sciences and Engineering Division
3
Objectives of this StudyWe aim to correlate the electrochemical properties of
materials (ANL-composite cathodes) to their structural,
morphological, and physical properties by coordinating the
science of synthesis with the science of function, in order
to enable the use of these compounds in vehicle
technologies.
xLi2MnO3.(1-x)LiMO2 (M = Ni, Co) will be written Li1+x(NiaCobMnc)O2+d
(1+x)/(a+b+c) > 1, c>(a+b), a>b, d is for balance
In this study b = 0
Argonne National Laboratory, Chemical Sciences and Engineering Division
4
Milestones for FY12 Design of 4L-CSTR reactor to produce Ni/Co/Mn carbonate
and hydroxide, and transfer of materials scale up technologyto Energy System Division at Argonne. (completed).
Characterize and understand (correlation approach) both theprecursors and their lithiated materials using structural,physical, chemical, and electrochemical tools (75% completedfor carbonate, 50% for hydroxide, 10% for oxalate).
Investigate the origin of voltage fade observed in Li- and Mn-rich cathode materials using a material synthesis approach(initiated).
Argonne National Laboratory, Chemical Sciences and Engineering Division
5
Approach
5
Precursors Synthesis
Materials Engineering Research Facility
Morphologyproperties
Structuralproperties
Elemental properties
Thermal properties
Physicalproperties
Electrochemicalproperties
Cell Fabrication Facility
Cathodes Testing & Screening
Cathode Materials Synthesis
Battery Manufacturer
Materials Electrochemistry
Precursors Design & Engineering
Materials Characterization
Materials Scale-up
Cell Fabrication
Battery Pack
* Function means a capacity of 200-plus mAh/g @ 1C, better cycle life, and no significant voltage fade during extended cycling
Carbonate, hydroxide, oxalate precursors
Coordinating the science of synthesis with the science of function*
Argonne National Laboratory, Chemical Sciences and Engineering Division6
Technical AccomplishmentsDesign of Continuous Stirred Tank Reactor for 1Kg Precursor Production
P1 P2
Motor
pH-meter
4L Reactor
(M = Ni, Co, Mn)sulfate Solution
Collection tank
NaOH, or Na2CO3
NH4OH
Pump
M(OH)2
MCO3
4L-tank
4L-tank
4L-tank
Control parameters• Concentration• pH of solution • Feed flow rate• Fluid motion• Temperature• Time
Nucleation/growth
Collection timeSeeds
Particlesgrowth
Precursor
Production ~ 250g/hour
Motor
Controls
4L-reactor
Shear
Table
We developed 4L-CSTR reactor to produce Ni/Co/Mncarbonate, hydroxide, oxalate precursors. Basic design wastransferred to ES division at Argonne for scale up.
Argonne National Laboratory, Chemical Sciences and Engineering Division7
Technical AccomplishmentsNucleation and growth mechanism of precursor particles were investigated during CSTR co-precipitation of Ni0.3Mn0.7CO3 precursor
10 20 30 40 50 60 70 80
t = 15min
t = 10min
t = 4min
MnCO3
2θ/degree
DLH or NiOOH
t = 2min
10 nm
The following observations could be made: Seed particles were rich in nickel during the nucleation stage. Spherical carbonate particles were obtained after few hours of co-precipitation. Packing density was in the range of 1.6-1.8 g/cm3
Particles growth was continuous.
TEM of Ni-rich nuclei
TEM of Ni-rich nuclei
Nucleation stage
Argonne National Laboratory, Chemical Sciences and Engineering Division
8
Technical Accomplishments
Solution: particle Selection- Particles below 20µm- Particles between 20 and 38µm- Particles above 38µm
Ni0.3Mn0.7CO3 Particle size distribution and growth during CSTR co-precipitation
0 100 200 300 400 500 6000
5
10
15
20
25
30
35
40
D50/
µm
Time/min
3.5 µm/hrNi0.3Mn0.7CO3
Individual particles grew in mass and volume during the co-precipitation
Continuous growth
Continuous growth of particles for the carbonate process will have an impact on:
- results consistency.- lithium diffusion.- engineering of electrodes.- issue shared with ES materials scale
up staff.
Argonne National Laboratory, Chemical Sciences and Engineering Division9
Sample Mn(atomic %)
Ni(atomic%)
Mn/Ni(atomic)
Li/(Mn+Ni) (atomic)
<20um 75.620 24.380 3.1017 1.49
20-38um 75.889 24.111 3.1475 1.52
>38um 75.935 24.065 3.1554 1.51
Sample a (Å) b (Å) c (Å) V(Å3) c/a
Pristine 2.862 2.862 14.267 101.260 4.98
>38um 2.862 2.862 14.266 101.250 4.98
20-38um 2.862 2.862 14.268 101.27 4.98
<20um 2.862 2.862 14.268 101.27 4.98
Technical AccomplishmentsNo noticeable structural or compositional differences between the size selected particles
ICP analysisStructural refinement
Particle cross section and EDXS analysis
Particles < 20µm 20µm <P< 38µm P>38µm
X-ray diffraction analysis
Argonne National Laboratory, Chemical Sciences and Engineering Division10
Technical AccomplishmentsThe capacity and rate performance of the material depends upon the size of particles
Solid Core
Concentricshells
Gaps
This morphology could make the particle fragileduring electrode calendaring
The gaps could make lithium diffusion difficult
Argonne National Laboratory, Chemical Sciences and Engineering Division
11
Technical AccomplishmentsContinuous growth of particles has been observed for different compositions NixMnyCO3
Mn/Ni
3
4
5
3
4
5
0 50 100 150 200 250 300 3502
3
4
5
Li1.4 Li1.5 Li1.6
Volta
ge(V
)
Specific capacity(mAh/g)
2.33
3.0
4.0
Li/(Mn+Ni) 1.4 1.5 1.6
NixMnyCO3 (y/x = 2.33, 3, and 4) particles were selected below 20 µm
The capacity is higher for Mn/Ni = 3.0 and Li/(Ni+Mn) = 1.4
Mn/Ni = 2.33
Mn/Ni = 3.0
Mn/Ni = 4.0
Argonne National Laboratory, Chemical Sciences and Engineering Division
12
0 5 10 15 200
50
100
150
200
250
300
5C2C1CC/2
C/4
Ca
paci
ty, m
Ah/g
Cycle number
C/10
0 10 20 30 40 50 60 70 80100
125
150
175
200
225
250
275
300
Cap
aict
y, m
Ah/
g
Cycle number
Technical AccomplishmentsSynthesis of Li1.2Ni0.2Mn0.6O2 using Ni0.25Mn0.75(OH)2 nano-plates
Charge @ C/10Discharge @ 1C
TEM of a Nano-plate
Primary particleNano-plates
Secondary particles
Lattice fringe
0.47 nm
Nano-plates morphology improved the rate capability of the material
50 nm
Packing density <1 g/cm3
Argonne National Laboratory, Chemical Siences and Engineering Division
13
10 20 30 40 50 60 70 80
2 θ, degree
20 30 40 50 60 70 80
2 θ, degree
Technical AccomplishmentsLi1+x(Ni0.25Mn0.75)O2+d made of Ni0.25Mn0.75(OH)2: effect of primary particles
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 50 100 150 200 250 300 3502.0
2.5
3.0
3.5
4.0
4.5
5.0
E v
s Li
/ V 1st cycle
C/10, 2-4.8V
4th-15th cyclesC/3, 2-4.6V
E v
s Li
/ V
Specific Capacity, mAh/g0 5 10 15 20
100
150
200
250
300
350ChargeDischarge
Cap
acity
/ m
Ahg
-1
Cycle Number
C/3 cycling
0 10 20 30 40 50100
150
200
250
300
350
C/3 cycling
Charge Discharge
Cap
acity
/ m
Ahg
-1
Cycle Number
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 50 100 150 200 250 300 3502.0
2.5
3.0
3.5
4.0
4.5
5.0
E v
s Li
/ V 1st cycle
C/10, 2-4.8V
E v
s Li
/ V
Specific Capacity, mAh/g
4th-48th cyclesC/3, 2-4.6V
5 µm
5 µm
Small Primary Particles
Large Primary Particles
Packing density ~ 1 g/cm3
Packing density ~ 1 g/cm3
215 mAh/g @ C/3cycling
200 mAh/g @ C/3cycling
Li2MnO3signature
Li2MnO3signature
Noticeable voltage fade
Less voltage fade
R-3m + C2/mStructural components
R-3m + C2/mStructural components
Argonne National Laboratory, Chemical Sciences and Engineering Division
14
Technical AccomplishmentsRecent development on materials made from hydroxide process
5 µm 5 µm
5 µm 5 µm
Packing density = 1 g/cm3
Packing density = 1.6 g/cm3
Ni0.25Mn0.75(OH)2 Precursor Lithiated cathode material
Ni0.25Mn0.75(OH)2 Precursor
Li2CO3
Li2CO3
Tuning of both experimental and engineering conditions during CTRS co-precipitation have led to obtaining spherical particles and higher packing density Ni0.25Mn0.75(OH)2
Lithiated cathode material
Argonne National Laboratory, Chemical Sciences and Engineering Division
15
Collaborations
Binghamton UniversityPh.D. work is being performed at Argonne on the synthesis, structural, and electrochemical characterizations of high capacity materials.
Pacific Northwestern National LaboratoryCollaboration on the characterization of high capacity composite materials at atomic scale using aberration corrected STEM imaging and atomic level EELS analysis.
Washington University in Saint Louis & X-Tend EnergyCollaboration to characterize and evaluate the electrochemistry of advanced cathode materials produced by aerosol synthesis process.
Energy Systems Division, ArgonneCollaboration to assist the scale up of high capacity cathode materials via the transfer of the carbonate co-precipatiation technology.
Argonne National Laboratory, Chemical Sciences and Engineering Division16
10 20 30 40 50 60 70 80
2 Theta, degree
CollaborationCollaboration to characterize and evaluate the electrochemistry advanced cathode materials produced by aerosol synthesis process.
0 10 20 30 40 500
50
100
150
200
250
300
350
400
Charge Discharge
Spec
ific
Cap
acity
/ m
Ahg-1
Cycle Number
C/10
C/3, 2-4.6V
Aerosol Synthesis setup
0 100 200 300 4001.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
C/3C/10
1st 2nd 4th
E vs
. Li /
V
Specific Capacity / mAhg-1
C/10
Layered-layered composite structure
Advantages:One step processConsistency in resultsLow cost processScalable process
2hours calcinationWashington University in Saint Louis & X-Tend Energy
Argonne National Laboratory, Chemical Sciences and Engineering Division
17
Future Work Continue the work on synthesis of high capacity and stable materials via the carbonate co-
precipitation method with the focus on: (1) preventing growth of the precursor particles above 20 µmduring co-precipitation; (2) optimizing the Li/transition metal ratio because the particles have Ni-hydroxide enriched cores and are sensitive to moisture; and (3) determining the proper balancebetween porosity and surface area of particles because the former is suited for improving the capacityand rate capability and the latter is unsuited for long life due to parasitic side reactions withelectrolytes.
Continue the work on synthesis of hydroxide and oxalate precursors using the same approach ofcoordinating the science of synthesis with the science of function. In the case of hydroxide co-precipitation method, the focus will be on further tuning the experimental and engineering conditionin order to prepare spherical and high packing density precursors that will serve to prepare variety ofcathode including the 5V-spinel and high capacity composite materials.
Assist the synthesis combinatory (robot assisted) effort recently adopted for ABR program in order toinvestigate the landscape of cathode materials . Compositions selected by this method will be scaledup using CSTR reactor for electrochemical screening.
Investigate the origin of voltage fade observed in Li- and Mn-rich cathode materials by benefiting fromthe accelerated combinatory synthesis approach.
Argonne National Laboratory, Chemical Sciences and Engineering Division
18
SummaryCarbonate process: Systematic investigations including morphological, structural, compositional, and electrochemical
characterizations were conducted on cathode materials prepared using co-precipitated carbonateprecursors in a CSTR reactor.
Continuous particle growth has been observed for carbonate precursors regardless of chemicalcompositions.
The cathode samples were found to contain secondary particles composed of highly crystallinepolyhedral primary particles whose sizes depend upon lithium contents.
The particles larger than 20 µm developed concentric ring layers within their cores, whichcompromised the overall electrochemical performance in terms of capacity and rate capability dueto the sequential void that separates the inner layers.
Ball milling improved the electrochemical performance; however, it also accelerated side reactionsbetween the electrode and electrolyte at high operating voltage, leading to gradual capacity losswith cycling.
Hydroxide process: Variety of morphologies were obtained using CSTR-hydroxide process. Secondary particles (10 µm size) comprising nano-plate primary particles were found to deliver
over 200 mAh/g capacity at the 1C rate. However, the packing density was below 1 g/cm3. Ni0.25Mn0.75(OH)2 precursor having spherical particles (15 µm) and high packing density (1.6 g/cm3)
has been obtained by tuning the experimental and engineering conditions during CTRS co-precipitation.