miller eccap final_6-25-2013

JMEJMEJMEJME Slide 1

Property, Performance, and Life of Today's Large-formatElectrochemical Capacitors

John R. Millera,b, Sue M. Butler a, David M. Ryan c, and Seana McNeal c

aJME, Inc., 23500 Mercantile Road, Suite L, Beachwood, OH 44122bGreat Lakes Energy Institute, Case Western Reserve University, Cleveland Ohio 44106

cAir Force Research Laboratory, Wright Patterson Air Force Base, Dayton, OH USA

2013 ECCAP SymposiumJune 25, 26, 2013 Strasbourg, France


Objective: Evaluate today’s large electrochemical capacitors for use in a high-power, high-rate cyclic application

Approach: Purchase and evaluate cells• Six technologies selected, 12-cell of each type• Initial two-terminal electrical response• Property distribution characterization• Constant-voltage aging at elevated temperature • Thermal performance characterization• Response to credible abuse

Pow

er

Time

Pow

er

TimeTime (s)2


Six Capacitor Technologies in Study

prismatic

prismatic

right cylinder

right cylinder

right cylinder

Cell Form Factor

FranceBatsCap

acetonitrilesymmetric C-CUkraineYunasko

carbonateasymmetric (LIC)JapanJM Energy

carbonatesymmetric C-CJapanNippon Chemi-Con

acetonitrilesymmetric C-CUSAIoxus

acetonitrilesymmetric C-CUSAMaxwell

ElectrolyteDesignOriginManufacturer

acetonitrile right cylindersymmetric C-C


Electrochemical Capacitor Cells in this Study

JM Energy-Japan3.8 V 1100 F

Nippon Chemi-ConDXE 2.5 V 1100 F

Maxwell—US2.7 V 3000 F

Ioxus—US2.7 V 3000 F

Yunasko—Ukraine2.7 V, 1200 F

BatsCap—France2.7 V, 1200 F


Initial Properties

0.2

2.3

1.1

0.7

0.7

Device Response Time*** (s)

4.0 327 0.41200 F, 2.7 VBatsCap

1584.01200 F, 2.7 VYunasko

208010.11100 F, 3.8 V (2.2 V min)

JM Energy

8832.81100 F, 2.5 VNippon Chemicon

2314.33000 F, 2.7 VIoxus

2294.53000 F, 2.7 VMaxwell

Measured DC Resistance**

(µΩµΩµΩµΩ)

Stored Energy* (Wh/kg)

Published RatingsManufacturer

• Calculated based on rated capacitance and voltage window between rated V andhalf-rated V with JM Energy measured over full voltage window

** Measured via current-interrupt method (5 second delay)– average of all 12 cells*** Product of DC resistance and capacitance value


Electrochemical Impedence Spectroscopy NyQuist Representation- Maxwell capacitors -0.001

-0.0008

-0.0006

-0.0004

-0.0002

00 0.0002 0.0004 0.0006 0.0008 0.001

Real (ohm)

- Im

agin

ary

(ohm

)

Maxwell 3000 F Cells

Equivalent series resistance (ESR ) is the intersection

with the real axis~150 µΩµΩµΩµΩ (Data for 15 cells shown)


Electrochemical Impedence Spectroscopy NyQuist Representation - Yunasko Capacitors-0.0005

-0.00045

-0.0004

-0.00035

-0.0003

-0.00025

-0.0002

-0.00015

-0.0001

-0.00005

00 0.0001 0.0002 0.0003 0.0004 0.0005

Real (ohm)

- Im

agin

ary

(ohm

)

Yunasko 1200 F Cells

Equivalent series resistance (ESR ) is the intersection

with the real axis< 100 µΩµΩµΩµΩ

(Data for 12 cells shown)

No porous electrodebehavior shown


Initial Complex-Plane Impedance Plot

Real (ohms)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

-Im

agin

ary

(ohm

s)Ioxus

Maxwell

Yunasko

Batscap

NCC

JM Energy

Real (ohms)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

-Im

agin

ary

(ohm

s)Ioxus

Maxwell

Yunasko

Batscap

NCC

JM Energy

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

-Im

agin

ary

(ohm

s)Ioxus

Maxwell

Yunasko

Batscap

NCC

JM Energy

Cell voltage at 0.75•VRated

Gamry Reference 3000


Bode Representation-90

-75

-60

-45

-30

-15

00.001 0.01 0.1 1 10

Frequency (Hz)

Phas

e A

ngle

(deg

rees

)

Ioxus 11d

Maxwell 13

Yunasko 1

Batscap 1

NCC 3c

JM Energy 12Responseof these three

technologies isvery similar

Phase Angle Comparison


0

500

1000

1500

2000

2500

3000

3500

1 10 100 1000Discharge Time (s)

Cap

acita

nce

(F)

Maxwell 3000 F

Ioxus 3000 F

Nippon Chemicon 1100 F

JM Energy 1200 F

Yunasko 1200 F

Constant-current Discharge Capacitance


Technology L1(µµµµH) R1 (mΩΩΩΩ) C1 (F) R2 (mΩΩΩΩ ) C2 (F) IOXUS 0.11 0.16 900 0.10 2100 Maxwell 0.16 0.17 1000 0.11 2200 BatsCap 0.15 0.25 270 0.19 720 Nippon Chemi-Con 0.07 0.43 190 0.36 1000 JM Energy 0.10 1.00 240 0.51 680 Yunasko 0.03 0.10 1070 -- --

EQUIVALENT CIRCUIT MODELS(25 oC)

Only the Yunasko technology can be accurately modeled using one time constant


Reliability Study(as June 24, 2013)

5450BatsCap

5800Yunasko

5700JM Energy

5900Nippon Chemi-Con

5900Ioxus

5900Maxwell

Aging hoursManufacturer

5450BatsCap

5800Yunasko

5700JM Energy

5900Nippon Chemi-Con

5900Ioxus

5900Maxwell

Aging hoursManufacturerCONSTANT VOLTAGE (2 levels)

4 cells at Vmax

and

5 cells at Vmax - 0.1 V

age at

maximum rated temperature


Three Groups of Capacitors ShownMounted in Aging Chamber

Constant T at constant voltage(no cycling involved)

perform periodic measurements


Maxwell 3000 F Aging study - Change in Resistance

0100200300400500600700800900

1000

0 1000 2000 3000 4000 5000 6000

Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

2.7 V2.6 V

300 A discharge

Maxwell 3000 F Aging - Change in Capacitance

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

0 1000 2000 3000 4000 5000 6000

Time (hours)

Cha

nge

in C

apac

itanc

e (%

)

2.7 V2.6 V

300 A discharge

Ioxus 3000 F Aging study - Change in Resistance

0

100

200

300

400

500

600

700

800

900

1000

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

2.7 V, 65 C2.6 V, 65 C

300 A discharge

Ioxus 3000 F Aging study - Change in Capacitance

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in C

apac

itanc

e (%

)

2.7 V, 65 C2.6 V, 65 C

300 A discharge

65o C

AGING RESULTS

JMEJMEJMEJME Slide 1565o C

Batscap 1200 F Aging study - Change in Resistance

0

100

200

300

400

500

600

700

800

900

1000

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

2.7 V2.6 V

lost electrolyte(due to JME error)

150 A discharge

NCC 1200 F Aging study - Change in Resistance

0

100

200

300

400

500

600

700

800

900

1000

0 1000 2000 3000 4000 5000 6000

Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

2.7 V2.6 V

150 A discharge

2.5 V2.4 V

NCC 1200 F Aging study - Change in Capacitance

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

0 1000 2000 3000 4000 5000 6000

Time (hours)

Cha

nge

in C

apac

itanc

e (%

) 2.7 V2.6 V

65 C

150 A discharge

2.5 V2.4 V

Batscap 1200 F Aging study - Change in Capacitance

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

0 1000 2000 3000 4000 5000 6000

Time (hours)

Cha

nge

in C

apac

itanc

e (%

)

2.7 V2.6 V

lost electrolyte due to JME error

150 A discharge

AGING RESULTS


JM Energy 1200 F Aging study - Change in Resistance

-100

0

100

200

300

400

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

3.8 V3.7 V

150 A discharge

JM Energy 1100 F Aging study - Change in Capacitance

-40

-35

-30

-25

-20

-15

-10

-5

0

5

10

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in C

apac

itanc

e (%

)

3.8 V3.7 V

150 A discharge

60o C65o C

Yunasko 1200 F Aging - Change in Capacitance

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in C

apac

itanc

e (%

)

2.7 V2.6 V

150 A discharge Electrolyte leakage at seal

Yunasko 1200 F Aging - Change in Resistance

-1000

0

1000

2000

3000

4000

5000

0 1000 2000 3000 4000 5000 6000Time (hours)

Cha

nge

in R

esis

tanc

e (%

)

2.7 V2.6 V

150 A discharge

Electrolyte leakage at seal

AGING RESULTS


Maxwell 3000 F Cells

Mean,Std. dev.163.5,6.061404.8,581315.2,15.9

Normal Distribution

x

dens

ity

0 500 1000 15002000 25000

0.01

0.02

0.03

0.04 Mean,Std. dev.163.5,6.061404.8,581315.2,15.9

Normal Distribution

x

dens

ity

0 500 1000 15002000 25000

0.01

0.02

0.03

0.04

ESR (microOhm)

Rel

ativ

e N

umbe

r

Normal Probability Distribution

Initial2.6 V, 5670 hours2.7 V, 5670 hours

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

Initial

5670 hours 2.6 V, 65oC

5670 hours 2.7 V, 652.7 V


Ioxus 3000 F Cells

Normal Distribution

xde

nsity

0 200 400 600 800 1000 12000

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber



Normal Distribution

xde

nsity

0 200 400 600 800 1000 12000

4

8

12

16

20

24(X 0.001)

Normal Distribution

xde

nsity

0 200 400 600 800 1000 12000

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber




-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

Initial2.6 V, 65o C2.7 V, 65o C


-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)

-0.003

-0.0025

-0.002

-0.0015

-0.001

-0.0005

00 0.0005 0.001 0.0015 0.002 0.0025 0.003

Real (ohm)

- Im

agin

ary

(ohm

)



Initial and after 5742 hours of aging


Nippon Chemi-Con 1100F Capacitor

-0.002

-0.0018

-0.0016

-0.0014

-0.0012

-0.001

-0.0008

-0.0006

-0.0004

-0.0002

00 0.0005 0.001 0.0015 0.002

Real (ohm)

- Im

agin

ary

(ohm

)


580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

2.4 V, 5612 hours2.5 V, 5612 hours

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

2.4 V, 5612 hours2.5 V, 5612 hours

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

580 630 680 730 780 8300

4

8

12

16

20

24(X 0.001)

ESR (microOhm)R

elat

ive

Num

ber

2.4 V, 5612 hours2.5 V, 5612 hours


Electrochemical Impedence Spectroscopy NyQuist Representation - Yunasko Capacitors

-0.0008

-0.0007

-0.0006

-0.0005

-0.0004

-0.0003

-0.0002

-0.0001

00 0.0002 0.0004 0.0006 0.0008

Real (ohm)

- Im

agin

ary

(ohm

)

Initial2.6 V 5720 hours2.7 V, 5720 hours

Yunasko 1200F Capacitor


7 8 9 10 11 12 13(X 0.0001)

0

1

2

3

4

5(X 10000)


Rel

ativ

e N

umbe

r

Normal Probability Distribution – JM Energy ESR

ESR (10-4 Ohm)

JM Energy 1100F Capacitor


Summary Results

• All capacitors demonstrate extremely high power performance

• JM Energy technology has highest energy density but withlargest characteristic response time

• Yunasko technology is by far the most powerful (smallest τ)

• Nippon Chemi-Con technology (with PC electrolyte) has identical phase angle behavior to ACN electrolyte cells

• Capacitors show long life--no catastrophic failures after 5500 hr at maximum rated voltage and maximum rated temperature—aging study continues

• Thermal performance and abuse testing is scheduled


“Power System Efficiency Improvements Achieved by Adding Energy Storage”John R. Miller, David M. Ryan, and Seana McNeal,

Proceedings of the 45th Power Sources Conference, paper 15.1, pp 235-238 (June 2012).

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miller eccap final_6-25-2013

Technology

f aging change

f yunasko

f slide

f aging study change

smaxwell3000 f

3yunasko1200 f

7ioxus3000 f

2batscap1200 f