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http://spacepwr.jpl.nasa.gov/battery.htm#Lithium
Lithium Batteries
Introduced by Sony in 1991.
Have been widely used to provide power for consumer
products.
Offer low safety risks, greater flexibility in battery
configuration and energy densities exceeding 120 Wh/kg.
Excellent pressure tolerance and neutral buoyancy.
Make use of intercalant solids as electrodes.
Host atoms or molecules within its lattice with very few structural
changes.
Intercalation
http://spacepwr.jpl.nasa.gov/lithumbgr.htm
Working Principles
Electrochemical chain characterized by continued transport of
lithium ions from a higher potential ( anode) to a lower potential
(cathode).
Electrical energy liberated while discharging is equal to the change
in lithium free energy due to the transfer.
Cell reactions in a Li/ Lix(cathode) system:
x Li
x Li + + x e(Li anode)
x Li + + x e- + Lix(host)
Lix + x (host cathode)
Overall reaction:
x LiLithium
+ Lix(host)
Lix + x (host)
batteries: New Materials,
Developments and
Perspectives, G. Pistoia, Elsevier 1994
Lithium MicroBattery
Miniaturized power supply needed for micro-mechanical
devices.
Lithium microbatteries built using thin film technologies.
1 Lithium metal
complex
2 Electrolyte
3 Intercalating electrode
Substrate
http://www.afrlhorizons.com/Briefs/Dec01/PR0104.html
Characteristics of a
Sony 18650 Li-ion cell
Cathode (positive
electrode) - LiCoO2.
Anode (negative
electrode) - MCMB.
Cell capacity 1.8 Ah
Characteristics of a
Sony 18650 Li-ion cell
Characteristics
Massoftheelectrode
material(g)
Geometricarea(both
sides)(cm2)
Loadingononeside
(mg/cm2)
TotalThickness
oftheElectrode(m)
SpecificCapacity
(mAh/g)
Positive
LiCoO2
Negative
Carbon
15.1
7.1
531
603
28.4
11.9
183
193
148
306
Experimental - Characterization
Batteries were cut open in a glove box after 150, 300
and800cycles.
Cylindrical disk electrodes (1.2 cm dia) were punched
fromboththeelectrodes.
Electrochemical characterization studies were done
usingathreeelectrodesetup.
Impedanceanalysis-100kHz~1mHz5mV.
Materialcharacterization-XRDstudiesandSEM,
EPMAanalysis.
Experimental - Characterization
LiCoO 2 or carbon
Lithium Foil
inert material
porous electrode
separator
reference electrode
-lithium foil
current collector
Swagelok TM Three Electrode Cell
Voltage (V)
3.76
3.32
Fresh
2.88
800-45
2.44
2.00
0.0
490-55
0.4
800-RT
0.8
1.2
Capacity (Ah)
1.6
2.0
50
100
150
300
500
800
3.8
5.11
6.09
10.29
22.5
30.63
3.8
5.46
11.75
26.46
36.21
4.3
6.4
9.4
27
70.56
fail
Capacity (Ah)
1.55
RT
1.20
45oC
0.85
0.50
55oC
100
200
300
400
500
Cycle Number
600
700
800
1.1
Current (A)
0.5
0.1
0.1
Room Temperature
50
Time (h)
300
0.9
150
0.7
0.5
0.3
0.1
55 deg C
2
Time (h)
45 degree-charge
RT-charge
0.5
0.3
300
800
0.7
0.3
150 50
0.9
1
0.7
Current (A)
Current (A)
150
50
800
0.9
1.1
2
T ime (h)
45 deg C
CC Time (h)
1.5
150
150
1.0
150
300
300
800
300
800
0.5
490
0.0
RT
Constant Current
45
55
CV Time (h)
150
2
300
300
800
800
300
150
150
1
RT
Constant Voltage
45
55
2.00
Fresh
1.75
150-RT
1.50
150-45
150-55
800-45
1.25
1.00
0.0
800-RT
0.2
0.4
0.6
0.8
1.0
1.2
ZIm()-Fresh
0.08
300-RT -0 SOC
300-55-0 SOC
Fresh-RT -0 SOC
Fresh-55-0 SOC
0.06
0.04
0.02
0.00
0.30
0.35
0.40
ZRe( )
0.45
0.50
0.4
800-RT-0 SOC
800-45-0 SOC
Fresh-RT-0 SOC
Fresh-45-0 SOC
0.3
0.12
0.2
0.08
0.1
0.04
0.00
0.3
0.4
0.5
0.6
ZRe ()
0.7
0.0
0.8
ZIm()-800 cyc
ZIm()-Fresh
0.16
600
RT
45 Deg C
55 Deg C
500
400
300
200
100
0
60
120
180
Cycle Number
240
300
500
RT
45 Deg C
55 Deg C
400
300
200
100
0
60
120
180
Cycle Number
240
300
150
100
50
600
0
RT
150 Cycles
45
500
55
Resistance (ohm-cm 2 )
Resistance (ohm-cm 2 )
LiCoO2
400
300
LiCoO2
Carbon
200
100
0
RT
45
55
300 Cycles
Zim (ohm)
200
150
100
0 SOC
50 SOC
100 SOC
50
0
0
100
200
300
Zre (ohm)
400
500
600
Day
Day
Day
Day
ZIm (ohms)
200
1
2
3
4
150
100
50
0
0
100
200
300
400
ZRe (ohms)
500
600
700
800
Specificcapacity(mAh/g)
LiCoO2
Carbon
147.81
144.29 2.38%
143.12 3.17%
141.25 4.44%
139.17 5.84%
138.21 6.49%
125.10 15.36%
306.17
299.55 2.16%
296.58 3.13%
290.56 5.10%
283.95 7.26%
282.17 7.84%
246.58 19.46%
CapacityLost
(mAh)
FullCell
Capacity
Loss
LiCoO2
Carbon
(mAh)
53.061
70.744
98.996
130.390
144.885
342.846
46.947
68.046
110.773
157.719
170.379
423.046
107
125
168
182
209
481
Current (A)
Room Temperature
-1
Fresh
800 cycles
-2
2.0
2.5
3.0
3.5
Voltage (V)
4.0
4.5
Current (A)
0
Fresh-RT
Fresh-45
800-RT
800-45
-1
-2
2.0
2.5
3.0
3.5
Voltage (V)
4.0
4.5
300-55
Intensity
300-45
300-RT
150-55
150-45
150-RT
Fresh
20
30
40
2
50
60
70
Cell
c/a
Fresh
5.103
150-RT
5.077
150-45
5.066
150-55
4.995
300-RT
4.998
300-45
4.995
300-55
4.985
c/a
5.10
5.05
RT
45 deg C
55 Deg C
5.00
100
200
Cycle Number
300
CapacityFade
LossofLi
(PrimaryActiveMaterial)
DegradationofC,LiCoO2
(SecondaryActiveMaterial)
SEIFormation
ElectrolyteOxidation
SaltReduction
Overcharge
SolventReduction
CH 3CHOCO2CH 2 2e 2 Li CH 3CHCH 2 Li2CO3
Structural
Degradation
Physical Characteristics of
9.592
5.0865
436
498
22
10.2
91
70
54.5 x 4
58.5 x 4
Electrode Reactions
Atanode
Li x C Li e
charge
discharge
Li x C
Atcathode
Li (Mn 2- Li )O
4
charge
discharge
Li (Mn 2- Li )OLi
4
Non-Stoichiometric Spinel
CellReaction
Li (Mn 2- Li )O 4 Li x C
charge
discharge
Li (Mn 2- Li )O 4 Li x C
Charging Protocols
Constantcurrent-Constantvoltage
Totalchargingtimefixed
Constantvoltage
Chargingdonecompletelyatconstantvoltage
Constantcurrent-Constantvoltage
Chargingstoppedwhenthecurrentreachesavalue
of50mAduringtheCVpart
Chargingdonetodifferentcut-offpotentials
3.8
4.17
3.6
3.4
3.2
4.0
3.0
0.0
0.1
0.2
0.3
0.4
0.5
4.05
4.10
0.6
0.7
Capacity (Ah)
4.0, 4.05, 4.10, 4.17, 4.3 V Protocol
0.8
0.9
1.0
Experimental
FullCellstudiesonCellBattLi-ionCells
Galvanostaticcharge-discharge
0.25A,0.5A,0.75A,1A-(3.0-4.17V)
CyclicVoltammograms-0.05mV/s,2.5-4.2V
T-cell(halfcell)studies
GloveBox-Diskelectrodes1.2cm
Counter,ReferenceelectrodesLimetal
CyclicVoltammograms-0.05,0.1and0.2mV/s,3-4.5V
vs.Li/Li+forspineland0-1.2Vvs. Li/Li+forcarbon
ImpedanceAnalysis-100kHz~1mHz5mV.
XRDstudiesofspinelelectrodeatvariouscycles.
1.2
1A
0.75 A
0.5 A
0.25 A
Current (A)
1.0
0.8
0.6
0.4
0.2
4.2
0.2
0.4
0.6
Capacity (Ah)
0.8
1.0
3.9
Potential (V)
0.0
0.0
3.6
1A
0.75 A
0.5 A
0.25 A
3.3
3.0
0.00
0.25
0.50
Capacity (Ah)
0.75
1.00
4.1
0.4
3.9
0.3
1 Cycle
0.2
3.5
0.1
0.0
3.7
800
500
0.00
0.18
C/2 Rate
0.36
0.54
0.72
200
0.90
3.3
1.08
Capacity (Ah)
0.5 C Protocol
3.8
Cell Voltage (V)
Current (A)
0.5
Voltage (V)
4.17 V
0.5 A
3.6
3.4
1 cycle
3.2
800
500 200
3.0
0.0
C/2 Rate
0.1
0.2
0.3
0.4
0.5
0.6
Capacity (Ah)
0.7
0.8
0.9
1.0
4.2
1A
Current (A)
0.8
0.5 A
0.23 Ah
3.8
0.25 Ah
0.6
3.6
0.56 Ah
0.4
0.52 Ah
200 cycles
0.2
3.4
3.2
500 cycles
0.0
0.0
4.0
0.2
0.4
0.6
Capacity (Ah)
0.8
3.0
1.0
Voltage (V)
1.0
4.17 V
0.03
0.02
100 (Charged)
35
20
10
0
0.01
0.00
0.25
0.26
0.27
0.28
0.29
Real Z ( )
0.30
0.31
0.32
ZIm ()
0.02
Fresh-0-SOC
200-0-SOC
600-0-SOC
Fresh-100-SOC
200-100-SOC
600-100-SOC
0.01
0.00
0.24
0.25
0.26
0.27
ZRe ( )
0.28
0.29
0.30
ZIm (cm2 )
40
30
20
10
100
200 cycles
600 cycles
800 cycles
90
0
Spinel
30
60
ZRe
90
2
( cm )
120
80
150
70
ZIm (cm2 )
60
50
40
30
20
10
0
Carbon
20
40
60
Spinel
Carbon
400
311
222
511 440
531
331
Intensity
800 cycles
400 cycles
Cycle
0
400
800
Fre sh
"a" (Ao )
8.17162
8.14257
8.12964
10
25
40
2
55
70
Conclusions
Varyingthechargingrateaffectstheoverallcapacityof
thecell.
Impedance studies reveal no significant increase in
resistanceatbothelectrodesafter800cycles.
XRDstudiesofSpinelelectroderevealtheformationof
anadditionalphasewithcycling.
Capacity fade in the case of Cellbatt
summarized as
cells can be
Mn Dissolution
from Spinel
HF formation
E. Wang et al.
Structural Degradation
of LiMn2O4
J.C.Hunter et al.
Salt Hydrolysis
PF6 H 2O POF 2HF
Electrolyte Oxidation
(starts from 3.7 V)
Intercalation Electrodes
Lithiated metal oxides VOx, LiCoO2, LixMn2O4, LixNiO2, LixSn
Thin film deposition- CVD, RF Sputtering, Pulsed
Laser Deposition.
Sides, C.R.; Li, N.; Patrissi, C.J.; Scrosati, B.; Martin, C.R.
Nanoscale Materials for Li-ion Batteries, MRS Bulletin, 2002,
27, 604-607.
Limitations
Critical area for improvement rate capability
Rate capability- ability to deliver large capacity when
discharged at high C rates. ( rate of C/1 corresponds to the
current required to completely discharge an electrode in 1
hour)
Future applications require high-discharge-rate periods.
Sides, C.R.; Li, N.; Patrissi, C.J.; Scrosati, B.; Martin, C.R.
Nanoscale Materials for Li-ion Batteries, MRS Bulletin, 2002,
27, 604-607.
Fabrication Technique
Template method General method to synthesize nanomaterials.
Synthesis entails deposition of material of interest/
precursor, within cylindrical and monodisperse pores of
a microporous template membrane.
Cylindrical
nanostructures
with
monodisperse
diameters and lengths obtained.
May be solid nanofibers or hollow nanotubes
depending on membrane used.
C.R.Martin, Science, 266, 1961 (1994)
Electrode Fabrication
Precursor deposition
Gel formation
50 nm pores filled with
triisopropoxyvanadium oxide.
Gel formation after 12 hrs.
Template
removal
Thermal
processing
SEM micrographs
Sn-based anodes
Can store twice as much lithium compared to carbon
anodes.
4Li+ + 4e- + SnO2
2Li2O + Sn
xLi + + xe - + Sn
LixSn
Can store upto 4.4 Li atoms per atom of Sn.
Volume changes during alloying/dealloying cause internal
damage to electrode lower cyclability.
Nanostructure based designs can better accommodate for
volume changes
Li, Naichao; Martin, C.R. J. Electrochem. Soc. 2001, 148, A164-A170.