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Capacity Studies of Li-ion Battery

With some cathodes

General Principle and Classification


Principle
Electrons released at the
negative electrode.
These flow through the load
and are accepted by the positive
electrode.
A voltage is measured due to
the potential difference between
the two electrodes of the cell.

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.

Lithium batteries: New Materials, Developments and Perspectives,


G. Pistoia, Elsevier 1994

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

Typical lithium microgenerator

Hundreds of microcells on a four-inch


diameter silicon wafer.

http://www.afrlhorizons.com/Briefs/Dec01/PR0104.html

Perform rate capability studies on cells cycled


to different charge-discharge cycles.
Perform half-cell studies to analyze causes for
capacity decrease
Use impedance spectroscopy to analyze the
change in cathode and anode resistance with
SOC.
Study structural and phase changes at both
electrodes using XRD.

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 Cycling Studies


CellscycledusingConstantCurrent-ConstantPotential
(CC-CV)protocol.
Cellsweredischargedataconstantcurrentof1A.
Batteries were cycled at 3 different temperatures
25oC,45oCand55oC.
Experimentsdoneonthreecellsforeachtemperature.
Rate capability studies done after 150, 300 and 800
cycles-Cellschargedat1Aanddischargedatcurrents
of0.2,0.4,0.6,0.8and1.0A.

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

Discharge Curve Comparison of Sony


18650 Cells after 800 Cycles
4.20
300-55 300-45
300-RT

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

Capacity Fade as a Function of Cycle Life

Percentage Capacity Fade


Temperature
RT
45
55

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 Fade as a Function of Cycle Life


1.90

Capacity (Ah)

1.55
RT

1.20

45oC

0.85

0.50

55oC

100

200

300

400

500

Cycle Number

600

700

800

Charge Curves at Various Cycles


300

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

Change in Charging Times with Cycling

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

Rate Capability after 150 and 800 Cycles

Discharge Capacity (Ah)

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

Applied Current (A)


Rate Capability comparison after 150 and 800 cycles

Nyquist Plots of Sony Cell at RT and 55oC


0.10

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

Nyquist Plots of Sony Cell at RT and 45oC


0.20

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

Negative Electrode Resistance


(Fully Lithiated)
Resistance (cm2 )

600
RT
45 Deg C
55 Deg C

500
400
300
200
100
0

60

120

180

Cycle Number

240

300

Positive Electrode Resistance


(Fully Lithiated)
Resistance (cm2 )

500
RT
45 Deg C
55 Deg C

400
300
200
100
0

60

120

180

Cycle Number

240

300

Comparison of Electrode Resistances


200
Carbon

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

Possible Reasons for Rapid Capacity Fade


at Elevated Temperatures
The SEI layer formed on a graphite electrode changes in both
morphology and chemical composition during cycling at
elevated temperature.
The R-OCO2Li phase is not stable on the surface and
decomposes readily when cycled at elevated temperatures
(55oC).
This creates a more porous SEI layer and also partially exposes
the graphite surface, causing loss of charge on continued
cycling.
The LiF content on the surface increases with increasing storage
temperature mainly due to decomposition of the electrolyte salt.
SEI and electrolyte (both solvents and salt) decomposition have
a more significant influence than redox reactions on the
electrochemical performance of graphite electrodes at elevated
temperatures.

Nyquist Plot of Fresh LiCoO2


as a function of SOC at RT
250

Zim (ohm)

200
150
100
0 SOC
50 SOC
100 SOC

50
0
0

100

200

300
Zre (ohm)

400

500

600

Nyquist Plot of Fully Delithiated LiCoO2 as


a function of Storage Time at RT

Nyquist Plot of Fully Lithiated LiCoO2 as


a function of Storage Time at RT
250

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

Specific Capacity of Positive and Negative


Electrodes at Various Cycles and Temperature
Cell
(CycleNo.
Temperature)
Fresh
150-RT
150-45
150-55
300-RT
300-45
300-55

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%

Comparison of Capacity Fade of Individual


Electrodes with Full Cell Loss
Cell
(CycleNo.
Temperature)
150-RT
150-45
150-55
300-RT
300-45
300-55

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

CVs of Sony Cell


2
Scan rate: 0.1 mV/sec

Current (A)

Room Temperature

-1
Fresh
800 cycles
-2
2.0

2.5

3.0

3.5

Voltage (V)

CV-fullcell-fresh and 800 cycles-RT

4.0

4.5

CVs of Sony Cell


2
Scan rate: 0.1 mV/sec

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

XRD Patterns of LiCoO2 after Different


Charge-Discharge Cycles

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

Variation of Lattice Constants with


Cycling and Temperature
Decrease in c/a ratio leads to
decrease in Li stoichiometry*

c/a

5.10

5.05

RT
45 deg C
55 Deg C

5.00

100
200
Cycle Number

300

G. Ting-Kuo Fey et al., Electrochemistry Comm. 3 (2001) 234

CapacityFade
LossofLi
(PrimaryActiveMaterial)

DegradationofC,LiCoO2
(SecondaryActiveMaterial)

SEIFormation
ElectrolyteOxidation
SaltReduction

PF6 2e 3Li 3LiF PF3

Overcharge

SolventReduction
CH 3CHOCO2CH 2 2e 2 Li CH 3CHCH 2 Li2CO3

Structural
Degradation

Physical Characteristics of

Cellbatt Lithium Ion Battery


Electrodes
Characteristics

Positive Spinel Negative Carbon

Mass of the electrode material (g)

9.592

5.0865

Geometric area (both sides) (cm 2)

436

498

Loading on one side (mg/cm 2)

22

10.2

Thickness of the Electrode ( m)

91

70

54.5 x 4

58.5 x 4

Dimensions of the electrode (cm x cm)

Cellbatt is a Prismatic type cell

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

Change in discharge capacity for Li-ion


cells charged to different potentials
4.0
4.3

Cell Voltage (V)

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.

Charge curves for CC-CV


Protocol

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)

Charge Curve com parison 100 cycles

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

Charge and Discharge curves for Liion Cell at various Cycles


0.6

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

Capacity Fade 15.4% for C/2 rate

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

Capacity Fade 19% for 1 C rate

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

Change in CC-CV Profiles with Cycling


1.2

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

Nyquist plots for Cellbatt cell


charged at 0.5 A at different states of
charge
Imaginary Z ()

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

Nyquist plots for Cellbatt cell


charged at 0.5 A during different
cycles
0.03

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

Nyquist Plots for Spinel and Carbon Electrodes


at Discharged state at Various Cycles
50
200 cycles
600 cycles
800 cycles

ZIm (cm2 )

40
30
20
10

100
200 cycles
600 cycles
800 cycles

90
0

Spinel

30

Discharge Impedance LiMn2O4

60
ZRe

90
2
( cm )

120

80

150

70
ZIm (cm2 )

60
50
40
30
20
10
0

Carbon

20

40

60

80 100 120 140 160 180 200


2
ZRe ( cm )

Cyclic Voltammograms of Spinel Electrode


after 800 Cycles at various Scan rates

Cyclic Voltammograms of Carbon Electrode


after 800 Cycles at various Scan rates

Cyclic Voltammograms of Spinel and Carbon


Electrodes at Different Cycles

Spinel

Carbon

XRD Patterns of Spinel after Different


Charge-Discharge Cycles
111

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

P. G.. Bruce et al., J. Electrochem. Soc., 146, 3649 (1999).

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

Capacity Fade in Cellbatt


Li-ion cells

Secondary Active Material


Degradation(C6 & LiMn2O4)

Mn Dissolution
from Spinel

SEI layer attack on


Negative Electrode

HF formation
E. Wang et al.

Structural Degradation
of LiMn2O4

Accumulation of -MnO2 with Cycling

2LiMn 2O 4 3 - MnO 2 (solid) + MnO(solution) + Li 2O(solution)

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.

Lithium batteries: New Materials, Developments and


Perspectives, G. Pistoia, Elsevier 1994

Advantages of Lithium Ion


Batteries
Store 2-3 times more energy per unit weight and volume
than lead-acid or Ni-Cd batteries.
Long cycle lives (>1000 cycles)
Low self-discharge and long shelf life.
Widespread use in electronic devices.
Potential applications promise in the areas of
communications and remote sensing devices too!!!

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.

Motivation for use of Nano


technology
Limitations in rate capabilities slow diffusion process
Shorter diffusion distance for Li+ ion
Increased surface area
Promise better rate capabilities.
Smaller effective current density during discharge.
Better cyclability due to smaller particles.
Need for energy sources to power nano devices
Martin, C.R.; Li, N.; Scrosati, B. Nanomaterial-Based Li-Ion
Battery Electrodes, J. Power Sources, 2001, 97-98, 240-243.

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

Template removed with oxygen


plasma(100mTorr O2, 2hrs)
Processed at 400C for 10hrs in
150psi O2
Patrissi, C.J.; Martin, C.R. J. Electrochem. Soc. 1999, 146,
3176-3180.

Thermal
processing

SEM micrographs

SEM images of the componenents of a


nanostructured electrode: (A) low-magnification
image of the V2O5 nanofibrils, (B) highmagnification image of the nanofibrils, and (C)
the underlying V2O5 surface layer.
Patrissi, C.J.; Martin, C.R. J. Electrochem. Soc., 2001, 148,
A1247-A1253.

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.

Sn- based anodes


Fabricated using template
synthesis with a SnCl2 based
precursor.
Nanofibers heated at 440C to
convert them to crystalline
SnO2.
Fiber dia. 110nm
Thin film electrode fabricated
without template membrane.
(550nm)
Li, Naichao; Martin, C.R. J. Electrochem.
Soc. 2001, 148, A164-A170.

Template based electrodes


Observed improved rate capabilities
Loss of volumetric energy density due to extremely low
porosity of polycarbonate membranes(1.2%)
Low number density of nanofibers protruding from current collector
surface.

Problem addressed by using alumina membranes (highly


porous)
Dissolution of membrane in aqueous acid or base; but this
also dissolves the electrode materials.
Chemical etching used to increase porosity of polycarbonate
membranes.
Sides, C.R.; Li, N.; Patrissi, C.J.; Scrosati, B.; Martin, C.R. MRS
Bulletin, 2002, 27, 604-607.

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