carlo segre - csrri.iit.edusegre/presentations/2014_iit_mmae.pdf · potential, energy density, and...
TRANSCRIPT
Making a nanoelectrofuel flow battery
Carlo Segre
Physics Department&
Center for Synchrotron Radiation Research and InstrumentationIllinois Institute of Technology
November 19, 2014
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 1 / 33
Outline
• Batteries 101
• Nanoelectrofuel concept
• Prototype design
• Electrochemical characterization
• EXAFS studies
• Conclusions
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 2 / 33
Solid state batteries
Anode - negatively chargedelectrode
Cathode - positively chargedelectrode
Separator - allows ions to passwithout short circuit
Electrolyte - medium throughwhich ions move
Consider a Li-ion battery
+
e-
Charge - Li+ ions move from cathode to anode and electrons also flow to theanode externally, anode is reduced
Discharge - Li+ ions move back to cathode and electrons flow through theexternal load, anode is oxidized
Potential, energy density, and power determined by the chemistry
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 3 / 33
Solid state batteries
Anode - negatively chargedelectrode
Cathode - positively chargedelectrode
Separator - allows ions to passwithout short circuit
Electrolyte - medium throughwhich ions move
Consider a Li-ion battery
+
e-
Charge - Li+ ions move from cathode to anode and electrons also flow to theanode externally, anode is reduced
Discharge - Li+ ions move back to cathode and electrons flow through theexternal load, anode is oxidized
Potential, energy density, and power determined by the chemistry
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 3 / 33
Solid state batteries
Anode - negatively chargedelectrode
Cathode - positively chargedelectrode
Separator - allows ions to passwithout short circuit
Electrolyte - medium throughwhich ions move
Consider a Li-ion battery
+
e-
Charge - Li+ ions move from cathode to anode and electrons also flow to theanode externally, anode is reduced
Discharge - Li+ ions move back to cathode and electrons flow through theexternal load, anode is oxidized
Potential, energy density, and power determined by the chemistry
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 3 / 33
Solid state batteries
Anode - negatively chargedelectrode
Cathode - positively chargedelectrode
Separator - allows ions to passwithout short circuit
Electrolyte - medium throughwhich ions move
Consider a Li-ion battery
+
e-
Charge - Li+ ions move from cathode to anode and electrons also flow to theanode externally, anode is reduced
Discharge - Li+ ions move back to cathode and electrons flow through theexternal load, anode is oxidized
Potential, energy density, and power determined by the chemistry
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 3 / 33
Solid state batteries
Anode - negatively chargedelectrode
Cathode - positively chargedelectrode
Separator - allows ions to passwithout short circuit
Electrolyte - medium throughwhich ions move
Consider a Li-ion battery
+
e-
Charge - Li+ ions move from cathode to anode and electrons also flow to theanode externally, anode is reduced
Discharge - Li+ ions move back to cathode and electrons flow through theexternal load, anode is oxidized
Potential, energy density, and power determined by the chemistry
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 3 / 33
Common solid state battery chemistries
Lead-acid battery: Eoc = 2.05 VCathode: PbO2 + SO4
2− + 4H+ + 2 e− ←→ Pb2SO4 + 2 H2OAnode: PbSO4 + 2 e− ←→ Pb + SO4
2−
NiMH battery: Eoc = 1.28 VCathode: NiOOH + H2O + e− ←→ Ni(OH)2 + OH−
Anode: M + H2O + e− ←→ MH + OH−
Li-ion battery: Eoc = 4.00 VCathode: CoO2 + Li+ + e− ←→ LiCoO2
Anode: Li+ + C6 + e− ←→ LiC6
Characteristics
• Medium to high energy density
• Limited cycle life (<1000)
• Large packaging overhead
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 4 / 33
Flow batteries
Characteristics
• Low packaging overhead
• Unlimited cycle life
• Low energy density
Vanadium: Eoc = 1.26 VCathode: V3+ + e− ←→ V2+
Anode: VO2+ + 2 H+ + e− ←→ VO2+ + H2O
Zinc-Bromine: Eoc = 1.67 VCathode: Br2(aq) + 2 e− ←→ 2 Br−(aq)Anode: Zn2+
(aq) + 2 e− ←→ Zn(s)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 5 / 33
Nanoelectrofuel battery
Suspended electroactive nanoparticles
Advantages of flow batteries
Energy density of solid state
Chemistry agnosticaqueous or non-aqueous
3 year funded program
Prototype: 1 kWh total energy stored40 V, C/3 discharge rate
Develop commercialization plan
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 6 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Nanoelectrofuel challenges
• What is the intrinsic performanceof active materials innanoparticle form?
• Can suspended nanoparticles beeffectively charged anddischarged during flow?
• How much loading can bestabilized in suspension?
• Will these nanoelectrofuels bepumpable and not destroy theenclosure materials?
• Can physics graduate studentson the project get a Ph.D. doingthis very applied project?
40 V aqueous chemistry stack
25 kWh using 4.5 L of nanoelectrofuel
26 kg stack, 10 kg 50% loaded fluid
70 Wh/kg (compare to 40 Wh/kg forPb-acid)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 7 / 33
Charging & discharging nanoelectrofuel
Charging and discharging in a flow can be achieved byproper design of the electrode but all these ideas haveto be validated through computation and experiment.
• Porous electrodefor high contactprobability
• Turbulent flowto maximizeelectrodecontact
• Moderatepressure dropacross the cell
• Must haveelectron transferwith transientcontact
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 8 / 33
Charging & discharging nanoelectrofuel
Charging and discharging in a flow can be achieved byproper design of the electrode but all these ideas haveto be validated through computation and experiment.
• Porous electrodefor high contactprobability
• Turbulent flowto maximizeelectrodecontact
• Moderatepressure dropacross the cell
• Must haveelectron transferwith transientcontact
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 8 / 33
Charging & discharging nanoelectrofuel
Charging and discharging in a flow can be achieved byproper design of the electrode but all these ideas haveto be validated through computation and experiment.
• Porous electrodefor high contactprobability
• Turbulent flowto maximizeelectrodecontact
• Moderatepressure dropacross the cell
• Must haveelectron transferwith transientcontact
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 8 / 33
Charging & discharging nanoelectrofuel
Charging and discharging in a flow can be achieved byproper design of the electrode but all these ideas haveto be validated through computation and experiment.
• Porous electrodefor high contactprobability
• Turbulent flowto maximizeelectrodecontact
• Moderatepressure dropacross the cell
• Must haveelectron transferwith transientcontact
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 8 / 33
Charging & discharging nanoelectrofuel
Charging and discharging in a flow can be achieved byproper design of the electrode but all these ideas haveto be validated through computation and experiment.
• Porous electrodefor high contactprobability
• Turbulent flowto maximizeelectrodecontact
• Moderatepressure dropacross the cell
• Must haveelectron transferwith transientcontact
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 8 / 33
First charging results
December 2012 data comparing x-ray absorption spectroscopy results on Cu6Sn5
anode material in a coin cell and flowing through a metal frit.
0 2 4
R (Ao
)
0
0.2
0.4
0.6
0.8
χ(R
) [A
o-3
]
lithiated @ 0.5V
unlithiated
lithiated @ 0.0V
lithiation
coin cell
0 2 4
R (Ao
)
0
0.1
0.2
0.3
0.4
0.5
0.6
χ(R
) [A
o-3
]
1 hr @ 0.01V vs. Li/Li+
unlithiated
1 hr @ 0.23V vs. Li/Li+
lithiation
flow cell
Similar trends indicate that nanoparticles in the flow cell are charging, albeitslowly and inefficiently.
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 9 / 33
Initial prototype cell
Made from metal with machined postsfor increased contact area
Future designs manufactured with 3Dprinting & metal electrode inserts
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 10 / 33
CFD modeling
Inject 5000 particles and evolve for 15 s
Extend to repeated injections of 5000 particles and add electrochemical modelingIllinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 11 / 33
Initial CFD results
Pressure field −→
Velocity field ↑Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 12 / 33
Nanofluid settling
TiO2 pristine (left & center) and sulfonated (right) in 0.4M KOH/LiOH (left) and0.04M KOH/LiOH (center & right)
0 hours
45 hours
18 hours
1 month
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 13 / 33
Nanoparticle electrochemical performance
LiNixMnyCozO2 non-aqueous cathode material
As received micron-sized particles (MTI Inc.)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 14 / 33
Nanoparticle electrochemical performance
LiNixMnyCozO2 non-aqueous cathode material
Ball milled ∼400 nm particles (MTI Inc.)
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 14 / 33
Nanoparticle electrochemical performance
0 10 20 30 40 50 60Cycle #
0
50
100
150
200
250
Specific
Capacity [m
Ah/g
]
C/10
C/3
C/3
C/4
MTI as-received (2.5V - 4.3V)
MTI ball milled (2.5V-4.6V)
MTI ball milled (2.5V-4.3V)
Nanoparticle-sizedLiNixMnyCozO2 haslower capacity and morefading
Cycling to 4.6 V yieldsslightly higher initial ca-pacity but faster fading
Solid electrolyte inter-face (SEI) layer is asignificant problem athigh potentials and fornanoparticles
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 15 / 33
Initial nanofluid charging tests
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 16 / 33
Fe2O3 coin cell
Hydrogen evolution atpotentials below -1.0V
Fe2O3 cyclic voltam-metry shows Li interca-lation
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 17 / 33
Fe2O3 coin cell
Theoretical capacity forFe+3 →Fe+2 is ∼335mAh/g
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 18 / 33
Fe2O3 nanofluid
5% wt suspension ofFe2O3 nanoparticles inKOH/LiOH solution
Performance ofnanofluid equivalent orto solid nanoparticleelectrode
Capacity increase withcycles indicates that itis limited by suboptimalcurrent collector
Need to move to flow-through current collec-tor design
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 19 / 33
Fe2O3 nanofluid – overcharged
5% wt suspension ofFe2O3 nanoparticles inKOH/LiOH solution
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 20 / 33
The EXAFS equation
The EXAFS oscillations can be modelled and interpreted using a conceptuallysimple equation (the details are more subtle!)
χ(k) =∑j
NjS20 fj(k)
kR2j
e−2k2σ2j e−2Rj/λ(k) sin [2Rj + δj(k)]
The sum could be over shells of atoms (Pt-Pt, Pt-Ni) or over scattering paths forthe photo-electron.
fj(k): scattering factor for the pathλ(k): photoelectron mean free pathδj(k): phase shift for the jth path
Nj : number of paths of type jRj : half path lengthσj : path “disorder”
Ni
Pt
Pt
Ni Pt
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 21 / 33
EXAFS analysis
11500 12000 12500
E(eV)
-2
-1.5
-1
-0.5
0
0.5
ln(I
o/I
)
remove background
andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background
andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background
andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background
andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transform
and fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell
ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transformand fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
EXAFS analysis
11500 12000 12500
E(eV)
0
0.5
1
ln(I
o/I
)
remove background andapply k-weighting
0 5 10 15
k(Å-1
)
-0.2
-0.1
0
0.1
0.2
χ
extract structural pa-rameters for first shell ormore distant atoms asappropriate
0 2 4 6
R(Å)
0
5
10
15
20
25
30
χ(R
)
take Fourier Transformand fit with a structuralmodel
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 22 / 33
Synthesis of Sn-graphite nanocomposites
One-pot synthesis pro-duces evenly distributedSn3O2(OH)2 nanoparticleson graphite nanoplatelets
XRD shows a small amountof Sn metal in addition toSn3O2(OH)2
10 20 30 40 50 60 70
0
100
200
300
Inte
nsity
Scattering Angle (2 )
GnP
Sn3O2(OH)2
Sn3O2(OH)2/GnP
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 23 / 33
In situ XAS studies of lithiation
1 2 3 4 50.0
0.3
0.6
0.9
1.2Sn-O
|x
(R)|
(Å-3
)
R (Å)
OCV 1st Charge 1st Discharge
Sn-Sn
1 2 3 4 50.0
0.1
0.2
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 24 / 33
In situ battery box
Pouch cell clamped against front window in helium environment
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 25 / 33
In situ battery box
Suitable for both transmission and fluorescence measurements
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 25 / 33
In situ XAS studies of lithiation
0 5 10 15 20 25 300
100
200
300
400
500
600
700
2100
2800
In situ
C
apac
ity (m
Ah/
g)
Cycle Number
Charge Discharge
Ex situ
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 26 / 33
In situ XAS studies of lithiation
-0.5
0.0
0.5
1.0
0 2 4 6 8 10 12
-0.5
0.0
0.5
1.0
0 1 2 3 4 50.0
0.5
1.0
k (Å-1)
k 2
(k) (Å-2
)
Re[
(R)]
(Å-3
)
|x(R
)| (Å
-3)
R (Å)
Fresh electrode can be fitwith Sn3O2(OH)2 structurewhich is dominated by thenear neighbor Sn-O dis-tances
Only a small amount ofmetallic Sn-Sn distances canbe seen
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 27 / 33
In situ XAS studies of lithiation
-0.5
0.0
0.5
1.0
0 2 4 6 8 10 12
-0.5
0.0
0.5
1.0
0 1 2 3 4 50.0
0.5
1.0
k (Å-1)
k 2
(k) (Å-2
)
Re[
(R)]
(Å-3
)
|x(R
)| (Å
-3)
R (Å)
Fresh electrode can be fitwith Sn3O2(OH)2 structurewhich is dominated by thenear neighbor Sn-O dis-tances
Only a small amount ofmetallic Sn-Sn distances canbe seen
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 27 / 33
In situ XAS studies of lithiation
-0.5
0.0
0.5
1.0
0 2 4 6 8 10 12
-0.5
0.0
0.5
1.0
0 1 2 3 4 50.0
0.5
1.0
k (Å-1)
k 2
(k) (Å-2
)
Re[
(R)]
(Å-3
)
|x(R
)| (Å
-3)
R (Å)
Fresh electrode can be fitwith Sn3O2(OH)2 structurewhich is dominated by thenear neighbor Sn-O dis-tances
Only a small amount ofmetallic Sn-Sn distances canbe seen
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 27 / 33
In situ XAS studies of lithiation
-0.2
0.0
0.2
0 2 4 6 8 10 12
-0.1
0.0
0.1
0 1 2 3 4 50.0
0.1
0.2
k (Å-1)
k 2
(k) (Å-2
)
Re[
(R)]
(Å-3
)
|(R
)| (Å
-3)
R (Å)
Reduction of number of Sn-O near neighbors and 3 Sn-Li paths characteristic of theLi22Sn5 structure
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 28 / 33
In situ XAS studies of lithiation
-0.2
0.0
0.2
0 2 4 6 8 10 12
-0.2
-0.1
0.0
0.1
0.2
0 1 2 3 4 50.0
0.1
0.2
k (Å-1)
k 2
(k) (Å-2
)
Re[
(R)]
(Å-3
)
|(R
)| (Å
-3)
R (Å)
Metallic Sn-Sn distances ap-pear but Sn-Li paths are stillpresent, further reduction inSn-O near neighbors.
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 29 / 33
In situ XAS studies of lithiation
OCV1s
t Cha
rge1s
t Disc
harge
2nd C
harge
2nd D
ischa
rge3rd
Cha
rge3rd
Disc
harge
4th C
harge
0
2
4
6
8
10
12
14
Med. Li
Long Li
Short Li
C/7.5C/2.5
Num
ber o
f Nei
ghbo
rs
Total Li
Number of Li nearneighbors oscil-lates with thecharge/dischargecycles but neverreturns to zero
In situ cell promotesaccelerated aging be-cause of Sn swellingand the reducedpressure of the thinPEEK pouch cellassembly
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 30 / 33
In situ XAS studies of lithiation
OCV1s
t Cha
rge1s
t Disc
harge
2nd C
harge
2nd D
ischa
rge3rd
Cha
rge3rd
Disc
harge
4th C
harge
0
2
4
6
8
10
12
14
Med. Li
Long Li
Short Li
C/7.5C/2.5
Num
ber o
f Nei
ghbo
rs
Total Li
Number of Li nearneighbors oscil-lates with thecharge/dischargecycles but neverreturns to zero
In situ cell promotesaccelerated aging be-cause of Sn swellingand the reducedpressure of the thinPEEK pouch cellassembly
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 30 / 33
In situ XAS studies of lithiation
OCV1s
t Cha
rge1s
t Disc
harge
2nd C
harge
2nd D
ischa
rge3rd
Cha
rge3rd
Disc
harge
4th C
harge
0
2
4
6
8
10
12
14
Med. Li
Long Li
Short Li
C/7.5C/2.5
Num
ber o
f Nei
ghbo
rs
Total Li
Number of Li nearneighbors oscil-lates with thecharge/dischargecycles but neverreturns to zero
In situ cell promotesaccelerated aging be-cause of Sn swellingand the reducedpressure of the thinPEEK pouch cellassembly
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 30 / 33
In situ XAS studies of lithiation
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 31 / 33
Acknowledgements
Illinois Institute of Technology• John Katsoudas – MRCAT staff
• Vijay Ramani - Chemical Engineering
Argonne National Laboratory• Elena Timofeeva – Energy Systems Division
• Dileep Singh – Energy Systems Division
• John Zhang – Chemical Sciences & Engineering Division
Graduate Students• Chris Pelliccione – Ph.D. Physics
• Yujia Ding – Ph.D. Physics
• Yue Li – Ph.D. Chemical Engineering
• Nathaniel Beaver – Ph.D. Physics
• Shankar Aryal – Ph.D. Physics
Supported by the DOE ARPA-e programIllinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 32 / 33
Abstract
We are currently in the first year of an ARPA-e project to pro-duce a prototype nanoelectrofuel flow battery. This new bat-tery concept marries the traditional solid state battery with aflow battery to obtain higher energy densities and reduction inpackaging weight. Successful development of this new batteryformat requires the ability to charge and discharge nanoparti-cle suspensions by transient contact with the current collectors.While the basic effect has been demonstrated, many challengeslie ahead. Notably the ability to make efficient and high capac-ity battery materials in nanoparticle form. In order to under-stand the differences between battery materials in macroscopic(micron-sized) and nanoparticle form, we are using x-ray ab-sorption spectroscopy to probe the structure of materials asthey are electrochemically cycled. I will present some initial re-sults on our in-situ studies of anode lithiation and discuss ourfuture plans.
Illinois Institute of Technology IIT – MMAE/Chemistry Colloquium November 19, 2014 33 / 33