2012-05-22 AMS Battery FC Lectures - Battery Michele P. For Hubert G. PDF

Electrochemistry Basics
- electrochemical cells & ion transport

- electrochemical potential
- half-cell reactions
Lithium Ion Batteries (LiBs)

- battery materials
- application of batteries
- post-LiBs
Fuel Cell Basics & Applications

- fuel cell types and materials
- basic electrocatalysis
- H2 reduction & O2 reduction kinetics
- transport resistances
- cell-reversal & start-stop degradation
2012-05-22 AMS Battery & FC Lectures - Battery (Michele P. for Hubert G.).ppt
p. 30
Lithium Ion Batteries (LiBs) - Solvents

use of (metallic) lithium electrodes requires aprotic organic electrolytes
Li Li e
;E(0Li / Li) 3.045 V ( -1 standardreduction potential)
H e 0.5 H2
;E(0H / H2) 0 V
Li H Li 0.5 H2
;E(0H / H2) 3.045 V
Li unstable with H+ (and H2O)
aprotic organic solvents
from: K. Xu; Chem. Rev. 104 (2004) 4303

p. 31
Lithium Ion Batteries - Solvents
requirements: - high dielectric constant (e)

- low viscosity (h)
- low melting point (Tm), high boiling point (Tb), high flash point (Tf)
propylene carbonate (PC) seems almost perfect
(1958: first Li-plating from PC)
from: K. Xu; Chem. Rev. 104 (2004) 4303

p. 32
Lithium Ion Batteries - Salts

lithium salts soluble in aprotic electrolytes aprotic organic electrolytes
from: K. Xu; Chem. Rev. 104 (2004) 4303
requirements: - complete dissociation high conductivity (s)

- oxidative/reductive stability
- thermal stability (high Tdecomposition)
- chemical stability towards all cell components (e.g., Al current collector)
p. 33
Positive Electrodes for LiBs

TiS2 : first reversible Li+ intercalation compound (Whittingham, 1973)
x Li x e TiS2 Lix TiS2
(singlephase within x 0 - 1)
- TiS2 sheets
- hexagonal close-packed S-lattice
- S stacking sequence ABABAB
from: M.S. Whittingham; Chem. Rev. 104 (2004) 4271
specific capacity theoretical capacity normalized by weight

(referenced to lithiated/de-lithiated compound for positive/negative electrode)
s
CLiTiS
specific energy:
96485 As mol
As
mAh
811
225
119 g mol
gLiTiS2
gLiTiS2
s
s
WLiTiS
[
mWh
/
g
]
C
[mWh / gLiTiS2 ] E( vs .Li / Li)
LiTiS
LiTiS
2
2
2
p. 34
Li / TiS2 Battery
Li // 2.5M LiClO4 in DL // TiS2 at 10 mA/cm2 (25C)
(M.S. Whittingham; Prog. Solid State Chem. 12 (1978) 41; 790 cits.)
E( vs .Li / Li) 2.0 V

s
WLiTiS
450mWh / gLiTiS2
2
note: dioxolane was used, since PC

co-intercalated with Li+ into TiS2
first large automotive LiB in 1977

using LiAl-alloy negative electrode
(0.2 V vs. Li/Li+; used for safety reasons)

p. 35
Li Metal Negative Electrode

highest specific capacity (3800 mAh/gLi )
but, formation of dendrites (safety!)
& shape-change (loss of active material)
from: K. Xu; Chem. Rev. 104 (2004) 4303
in addition:
continuous reduction of electrolyte
no lithium-metal electrodes in
todays rechargeable LiBs
p. 36
LiC6 Negative Electrode (Sony 1990)

Li+ insertion in between graphene planes of graphite up to 1 Li+ per 6 C
Li x e 6 C LiC6 , with CCs
ELixC vs. Li+/Li
96485 As mol
mAh
372
72 g mol
gC
no Li-plating (ELixC > ELi )

no shape-change (fixed C-cage)
but,
from: R.A. Huggins; Advanced Batteries (Springer, 2009)

p. 37
Solid Electrolyte Interface (SEI)

SEI: electrolyte reduction products on LixC or Li (fluorides from LiBF4 or LiPF6)
Li+-conducting, but
electronically insulating (20 )
prevents continuous electrolyte reduction
Li+ consumed for initial SEI formation
(batteries must be built with excess Li+)
but,
from: K. Xu; Chem. Rev. 104 (2004) 4303
p. 38
Graphite Electrode Defoliation

strong solvation of Li+ with PC intercalation of PC into graphite
prevents formation of stable SEI w. PC

EC, however, forms stable SEI
need to add DMC, DEC, or EMC
to increase conductivity at 25C
stable negative graphite electrode

lithium must be introduced via
the positive electrode materials
(does not work, e.g., with TiS2)
from: K. Xu; Chem. Rev. 104 (2004) 4303
p. 39
Positive Intercalation Electrode with Li

discovery of LiCoO2 (layer compound) in 1980:
reversible inter-/deintercalation of Li+

between LiCoO2 and Li0.45CoO2
0.55 Li+ + 0.55 e + Li0.45CoO2 LiCoO2
s
CLiCoO
0.55 96485 As mol

mAh
150
98 g mol
gLiCoO2
graphite // alkylcarbonates + LiPF6 // LiCoO2 developed by Sony in 1990

is the currently predominant LiB system
from: R.A. Huggins; Advanced Batteries (Springer, 2009)
p. 40
LiB Summary
from: B. Dunn, H. Kamath, J.M. Tarascon; Science 334 (2011) 928

p. 41
Electrolyte Filled Separator

porous polymer matrix: electrolyte reservoir
& electronic insulation
estimated ionic resistance:
Rareal
t separator
selectrolyte e electrolyte
1.5
from: P. Arora & . Zhang; Chem. Rev. 104 (2004) 44193

p. 42
Battery Assembly
spiral-wound cylindrical design (for high energy batteries: pouch or prismatic cells)
note: commonly the negative electrode is referred to as anode and the positive
electrode as cathode (based on the discharge reaction)
typical dimensions:
- negative current collector (Cu): 10 mm
- positive current collector (Al): 20 mm
- separator:
25 mm
- separator:
25 mm
- electrodes: - high power

- high energy
20-40 mm
60-100 mm
for high energy LiBs:

2.5 mAh/cm2 4V 10 mWh/cm2
huge area for electric vehicle batteries!
from: P. Arora & . Zhang; Chem. Rev. 104 (2004) 44193
p. 43
Ragone Plots
celates specific energy to specific power (rate)
C-rate is defined as specific power/specific energy [1/h]
from: B. Dunn, H. Kamath, J.M. Tarascon; Science 334 (2011) 928

p. 44

- battery materials
- post-LiBs

p. 45
Electromobility Challenges: BEVs

Tesla EV (2009)
battery system weight & cost:

120 Whname-plate/kgsystem (Tesla) highest Wh/kg battery pack, but very complex system
400 km range (53 kWhname-plate): 450 kg and 13000 (2030 projection*) )
charging time: hour(s)
safety:
short-term: higher Wh/kg electrode materials and/or high-cost system architecture
long-term: novel electrode and electrolyte materials
safer and higher Wh/kg batteries are required for full BEVs
*) Transitions
to Alternative Transportation Technologies Plug-In Hybrid Electric Vehicles,

National Research Council (2010); see: www.nap.edu/catalog/12826.html
p. 46
LiNiPO4
LiCoPO4
cathodes (positive)
Battery Materials/Concepts
modified from: J.-M. Tarascon & M. Armand,
Nature 414 (2001) 359
Li/air
anodes (negative)
Li/sulfur
silcon
p. 47
Battery Specific Energy [Wh/kgelectrodes ]

higher Wh/kg: - 5V cathodes (Co,Mn,Fe-phosphoolivines, Mn-spinels) 25% gain
- higher specific capacity materials
LiNiPO4
LiCoPO4
modified from: J.-M. Tarascon & M. Armand,

Nature 414 (2001) 359
Li/air
Li/sulfur
silcon
post-LiB: Li/air and Li/S batteries with Si-based anodes

p. 48
Battery Materials
anodes:
cathodes:
durability, safety, and cost are additional critical considerations

from: Lamm, A.; Warthmann, W.; Soczka-Guth, T.; Kaufmann, R.; Spier, B.; Friebe, P.; Stuis, H.; Mohrdieck;
Lithium-Ionen Batterie Erster Serieneinsatz im S400 Hybrid; ATZ (07-0812009) 2009, 111, 490.
p. 49
Limit of Lithium-Ion Batteries

spec. energy of C-anodes & NMC-cathodes:
LiNixMnyCozO2 / C
specific capacity of electrodes [Ah/kgelectrodes]:
110
cathode voltage (positive) [V]
4.0
anode voltage (negative) [V]
0.1
battery voltage [V]

specific energy of electrodes [Wh/kgelectrodes]:
3.9
Cs Cs
where C
(Cs Cs )
s
430
specific of cells and battery-packs:

- electrodes: 70% of cell weight
(rest: current collectors & electrolyte)
LiNixMnyCozO2 / C: 300 Wh/kgcell
long-term projection:
200 Wh/kgbattery-pack
(from F.T. Wagner et al.)
from: F.T. Wagner, B. Lakshmanan,

M.F. Mathias; J. Phys. Chem.
Lett. 1 (2010) 2204
p. 50
BEV Battery Weight & Cost

projected performance of todays LiB technology: - 200 Wh/kgbattery-pack*)
- 95% discharge efficiency

- 80% state-of-charge range
- 250 /kWhname-plate**)
energy required for small 4-passenger car:
- 100 Wh/km*)
150 km range
500 km range
15 kWhnet
50 kWhnet
20 kWhname-plate
66 kWhname-plate
battery weight:
100 kg
330 kg
battery cost:
5000
16500
required net energy:

required name-plate energy:
current cost & weight 2-fold higher

fast charging increases perceived range
*) F.T.
**)
Wagner, B. Lakshmanan, M.F. Mathias; J. Phys. Chem. Lett. 1 (2010) 2204
Transitions to Alternative Transportation Technologies Plug-In Hybrid Electric Vehicles,

National Research Council (2010); see: www.nap.edu/catalog/12826.html
p. 51
Rapid Charging
charging time vs. power: kWhelectricity / kWcharging = tcharging
from:
E.ON presentation
at the IAS Opening
by J. Eckstein
(Oct. 22, 2010)
rapid charging: impacts battery life & business case of electric utilities
long-range BEVs need advanced batteries
p. 52
Battery Targets for 500 km BEVs
battery requiriements for 500 km-range small 4-passenger cars:

- 70 kWhname-plate
< 200 kg weight > 350 Wh/kgbattery-pack
- 35 kW constant power
C-rate of 0.5 h-1 (continuous)
- 100 kW accelerating power
C-rate of 1.5 h-1 (short-term)
- 25000 km life (50% avg. charge)
> 1000 cycles
- <10000 battery cost
< 150 /kWhname-plate (15 /m2cell !)
current LiB technology will not meet the long-range Wh/kg requirements
Wh/l of concern for current car architectures:
380 kg / 500 l (ICE) 430 kg / 350 l (20kWh BEV)
alternative batteries post-LiBs ?
p. 53

- battery materials
- post-LiBs

2012-01-31 AMS Battery & FC Lectures Fuel Cell - 1 (Hubert G.).ppt
p. 54
Li-S Batteries
S + 2 Li+ + 2 e- (Li2S)solid
2 Li 2 Li+ + 2 e-
Li + eLi2S2
& Li2S
e-
e-
e-
Li2S2/Li2S
S8
Li2S8
Li+
e-
Li2S6
Li+
Li2S4
Li+
Li+
poly-sulfide redox-shuttle
Li2S4
Li-electrode
current-collector
separator
current-collector
2 Li + S (Li2S)solid ; E0 2.0 VLi
+
sulfur-electrode (e.g., porous carbon)
challenges & development needs:

- polysulfide diffusion to anode
Li+-conducting diffusion-barrier
- poor C-rate & cathode clogging cathode design
- stable anode configuration
improved Li-metal anode design or alternative
p. 55
Li-S Batteries: State-of-the-Art

Cathode / Electrolyte / Anode
C+S / liquid electrolyte / Li
C+S / liquid+solid-electrolyte/ Li
C+S / polymer electrolyte / Li
C+Li2S / liquid electrolyte / Si
C+Li2S / polymer electrolyte / Sn
S-Utilization
70%
70%
70-50%
40%
40%
C-Rate
0.10 h-1
0.20 h-1
0.20 h-1
0.13 h-1
0.20 h-1
Cycles
20
150
200
20
100
Ref.
[1]
[2]
[3]
[4]
[5]
[1] X. Ji, K.T. Lee, L.F. Nazar; Nature Materials 8 (2009) 500.
[2] SION Power presentation; ORNL Symposium on Scalable Energy Storage Beyond Li-Ion:
Materials Perspective (Oct. .2010)
https://www.ornl.gov/ccsd_registrations/battery/presentations/Session7-1020-Affinito.pdf.
[3] G. Ivanov (Oxis Energy Ltd.); (Jan. 2010); Oxis web site:
http://www.oxisenergy.com/downloads/Recent%20progress%20Polymer%20Li-S_2010.pdf;
[4] J. Li, R.B. Lewis, J.R. Dahn; Electrochem. & Solid-State Lett. 10 (2007) A17.
[5] H.S. Ryu, Z. Guo, H.J. Ahn, G.B. Cho, H. Liu; J. Power Sources 189 (2009) 1179.
increased cycle-life with poly-sulfide diffusion barriers

still insufficient performance: - S-utilization 70% vs. 90% target
- C-rate 0.2 h-1 vs. 0.5 h-1 target
- cycle-life 200 cycles vs. 2000 cycle target
further advances needed, also wrt. Li-metal safety

p. 56
Li-S Batteries: Metallic Li-Anodes
supression of Li dendrite formation / shape-change is challenging

alternative anode concepts ?
p. 57
spec. capacity of electrodes [Ah/kg]
Anode Effect on Wh/kg

900
800
C C
C electrodes
(C C )
700
600
500
Si-anode
400
Li-anode
300
C-anode
200
100
0
0
500
1000
1500
2000
2500
3000
3500
specific capacity of negative electrode [Ah/kg]
high capacity anodes essential for Li-S & Li-air batteries

Si-anodes (Li15Si4): volumetric expansion (4x) is challenging
p. 58
Wh/kg of LiB vs. Li/S

Li/air
Li/sulfur
spec. capacity & energy projections:
J.-M. Tarascon & M. Armand,

Nature 414 (2001) 359
silcon
LiNixMnyCozO2 / C
Li2S / Si
110
630
4.0
2.0
0.1
0.5
battery voltage [V]

specific energy of electrodes [Wh/kgelectrodes]
3.9
1.5
430
950
gain vs. current batteries
2-fold
2x Wh/kgbattery-pack gains projected for Li-S

p. 59
Li-Air Batteries: Thermodynamics

O2
O2 + 2 Li+ + 2 e- (Li2O2)solid
2 Li 2 Li+ + 2 e2 Li + O2 (Li2O2)solid ; E0 = 2.96 VLi1)
Li2O2 observed by ex-situ Raman2,3)

O2 + 4 Li+ + 4 e- (Li2O)solid
Limetal
4 Li 4 Li+ + 4 e-
O2
4 Li + O2 (Li2O)solid ; E0 = 2.91
VLi1)
partial Li2O formation via O2 balance4)
evidence for Li2O2 & Li2O in organic electrolytes

bulk-LiO2 only stable at 15 K5), but [LiO2]solvated in organic electrolytes
1) M.W.
Chase; NIST-JANAF Thermochemical Tables 4th Ed. (1998)

2) K.M. Abraham, Z. Jiang; J. Electrochem. Soc. 143 (1996) 1
3) A. Dbart, A.J. Paterson, J. Bao, P.G. Bruce; Angew. Chem. Int. Ed. 47 (2008) 4521
4) J. Read; J. Electrochem. Soc. 149 (2002) A1190
5) L. Andrews, R. Smardzew; J. Chem. Phys. 58 (1973) 2258
p. 60
separator
current-collector
Li-Air Batteries: Processes
ec
c
Li2O2 / Li2O
Li+
Li
O2 (air)
LixO2
( H2O, CO2 )
Li2CO3
LiOH
Li-electrode
[ LiO2 ]solv. c
e-
porous air-electrode
challenges:
- solid Li2O2/Li2O can clog electrodes and limit O2 & Li+ mass-transport
- O2, H2O, & CO2 can react on the lithium anode
p. 61
engineering
fundamentals
Challenges for Li/Air Batteries

slow reaction rates at the air-cathode
low round-trip efficiency ( 70%)
low rate capability (C-rate 0.1 h-1)
insufficient cycle-life (<50 cycles)
reaction of O2 with carbonate-based electrolytes
Li-metal electrode (dendrites, shape-change, corrosion)
(electro)catalysis,
electrode design
open-system due to air-feed

contamination/degradation from H2O-vapor & CO2
electrolyte evaporation
low volumetric energy density (air-feed channels)
improved catalysts, electrodes, electrolytes, & Li+-ion selective separators

high-risk / high-gain technology
p. 62
Wh/kg of LiB, Li/S, & Li/Air Electrodes

Li/air
Li/sulfur
spec. capacity & energy projections:
J.-M. Tarascon & M. Armand,

Nature 414 (2001) 359
silcon
LiNixMnyCozO2 / C
Li2S / Si
Li2O / Si
110
630
800
4.0
2.0
2.7
0.1
0.5
0.5
battery voltage [V]

specific energy of electrodes [Wh/kgelectrodes]
3.9
1.5
2.2
430
950
1,700
2-fold
4-fold
gain vs. current batteries
large Wh/kgbattery-pack gains projected for Li-S (2x) and Li-air (3x)
p. 63

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Electrochemistry Basics

- electrochemical cells & ion transport

Lithium Ion Batteries (LiBs)

Fuel Cell Basics & Applications

Lithium Ion Batteries (LiBs) - Solvents

;E(0Li / Li) 3.045 V ( -1 standardreduction potential)

;E(0H / H2) 3.045 V

Li unstable with H+ (and H2O)

aprotic organic solvents

from: K. Xu; Chem. Rev. 104 (2004) 4303

Lithium Ion Batteries - Solvents

requirements: - high dielectric constant (e)

from: K. Xu; Chem. Rev. 104 (2004) 4303

Lithium Ion Batteries - Salts

from: K. Xu; Chem. Rev. 104 (2004) 4303

requirements: - complete dissociation high conductivity (s)

Positive Electrodes for LiBs

from: M.S. Whittingham; Chem. Rev. 104 (2004) 4271

specific capacity theoretical capacity normalized by weight

E( vs .Li / Li) 2.0 V

note: dioxolane was used, since PC

first large automotive LiB in 1977

from: M.S. Whittingham; Chem. Rev. 104 (2004) 4271

Li Metal Negative Electrode

from: K. Xu; Chem. Rev. 104 (2004) 4303

LiC6 Negative Electrode (Sony 1990)

Li x e 6 C LiC6 , with CCs

ELixC vs. Li+/Li

no Li-plating (ELixC > ELi )

from: R.A. Huggins; Advanced Batteries (Springer, 2009)

Solid Electrolyte Interface (SEI)

Graphite Electrode Defoliation

prevents formation of stable SEI w. PC

stable negative graphite electrode

Positive Intercalation Electrode with Li

reversible inter-/deintercalation of Li+

0.55 96485 As mol

graphite // alkylcarbonates + LiPF6 // LiCoO2 developed by Sony in 1990

from: B. Dunn, H. Kamath, J.M. Tarascon; Science 334 (2011) 928

Electrolyte Filled Separator

estimated ionic resistance:

from: P. Arora & . Zhang; Chem. Rev. 104 (2004) 44193

- electrodes: - high power

for high energy LiBs:

from: B. Dunn, H. Kamath, J.M. Tarascon; Science 334 (2011) 928

Lithium Ion Batteries (LiBs)

Fuel Cell Basics & Applications

Electromobility Challenges: BEVs

battery system weight & cost:

to Alternative Transportation Technologies Plug-In Hybrid Electric Vehicles,

Battery Specific Energy [Wh/kgelectrodes ]

modified from: J.-M. Tarascon & M. Armand,

post-LiB: Li/air and Li/S batteries with Si-based anodes

durability, safety, and cost are additional critical considerations

Limit of Lithium-Ion Batteries

cathode voltage (positive) [V]

anode voltage (negative) [V]

battery voltage [V]

specific of cells and battery-packs:

from: F.T. Wagner, B. Lakshmanan,

BEV Battery Weight & Cost

- 95% discharge efficiency

required net energy: