1. Property, Performance, and Life of Today's Large-format
Electrochemical Capacitors
John R. Miller a,b, Sue M. Butler a, David M. Ryan c, and Seana McNeal c
a
JME, Inc., 23500 Mercantile Road, Suite L, Beachwood, OH 44122
b
Great Lakes Energy Institute, Case Western Reserve University, Cleveland Ohio 44106
c
Air Force Research Laboratory, Wright Patterson Air Force Base, Dayton, OH USA
JME
2013 ECCAP Symposium
Slide 1
June 25, 26, 2013 Strasbourg, France

2. Evaluate today’s large electrochemical capacitors
for use in a high-power, high-rate cyclic application
Power
Objective:
TTime (s)
im
e
2
Approach: Purchase and evaluate cells
JME
•
•
•
•
•
•
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
Slide 2

3. Six Capacitor Technologies in Study
Manufacturer
Origin
Design
Electrolyte
Cell Form Factor
Maxwell
USA
symmetric C-C
acetonitrile
right cylinder
Ioxus
USA
symmetric C-C
acetonitrile
right cylinder
Nippon ChemiCon
Japan
symmetric C-C
carbonate
right cylinder
JM Energy
Japan
asymmetric (LIC)
carbonate
prismatic
Yunasko
Ukraine
symmetric C-C
acetonitrile
prismatic
BatsCap
France
symmetric C-C
acetonitrile
right cylinder
JME
Slide 3

4. Electrochemical Capacitor Cells in this Study
Maxwell—US
2.7 V 3000 F
JM Energy-Japan
3.8 V 1100 F
JME
Ioxus—US
2.7 V 3000 F
Yunasko—Ukraine
2.7 V, 1200 F
Slide 4
Nippon Chemi-Con
DXE 2.5 V 1100 F
BatsCap—France
2.7 V, 1200 F

5. Initial Properties
Manufacturer
Published Ratings
Stored
Energy*
(Wh/kg)
Measured DC
Resistance**
(µΩ
µΩ)
µΩ
Device
Response
Time*** (s)
Maxwell
3000 F, 2.7 V
4.5
229
0.7
Ioxus
3000 F, 2.7 V
4.3
231
0.7
Nippon
Chemicon
1100 F, 2.5 V
2.8
883
1.1
JM Energy
1100 F, 3.8 V
(2.2 V min)
10.1
2080
2.3
Yunasko
1200 F, 2.7 V
4.0
158
0.2
BatsCap
1200 F, 2.7 V
4.0
327
0.4
• Calculated based on rated capacitance and voltage window between rated V and
half-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
JME
Slide 5

6. Maxwell 3000 F Cells
Electrochemical Impedence Spectroscopy
NyQuist Representation- Maxwell capacitors
-0.001
- Imaginary (ohm)
-0.0008
Equivalent series resistance
(ESR ) is the intersection
with the real axis
~150 µΩ
-0.0006
-0.0004
-0.0002
(Data for 15 cells shown)
0
0
JME
0.0002
Slide 6
0.0004
0.0006
Real (ohm)
0.0008
0.001

7. Yunasko 1200 F Cells
Electrochemical Impedence Spectroscopy
NyQuist Representation - Yunasko Capacitors
-0.0005
-0.00045
- Imaginary (ohm)
-0.0004
Equivalent series resistance
(ESR ) is the intersection
with the real axis
< 100 µΩ
-0.00035
-0.0003
No porous electrode
behavior shown
-0.00025
-0.0002
-0.00015
-0.0001
-0.00005
(Data for 12 cells shown)
0
0
0.0001
0.0002
0.0003
Real (ohm)
JME
Slide 7
0.0004
0.0005

8. Initial Complex-Plane Impedance Plot
-0.003
Ioxus
- Imaginary (ohms)
-0.0025
Maxwell
-0.002
Yunasko
Batscap
-0.0015
NCC
-0.001
JM Energy
-0.0005
0
JME
0
0.0005 0.001
0.0015 0.002
Real (ohms)
Slide 8
0.0025 0.003
Gamry Reference 3000
Cell voltage at 0.75•VRated

9. Bode Representation
Phase Angle Comparison
Ioxus 11d
-90
Phase Angle (degrees)
Maxwell 13
-75
Yunasko 1
-60
Batscap 1
NCC 3c
-45
-30
JM Energy 12
Response
of these three
technologies is
very similar
-15
0
0.001
JME
0.01
0.1
Frequency (Hz)
Slide 9
1
10

10. Constant-current Discharge Capacitance
3500
3000
Maxwell 3000 F
Capacitance (F)
2500
Ioxus 3000 F
Nippon Chemicon 1100 F
2000
JM Energy 1200 F
Yunasko 1200 F
1500
1000
500
0
1
JME
10
100
Discharge Time (s)
Slide 10
1000

11. EQUIVALENT CIRCUIT MODELS
(25 oC)
Technology
IOXUS
Maxwell
BatsCap
Nippon Chemi-Con
JM Energy
Yunasko
L1(µH)
µ
R1 (mΩ)
Ω
C1 (F)
R2 (mΩ )
Ω
C2 (F)
0.11
0.16
0.15
0.07
0.10
0.03
0.16
0.17
0.25
0.43
1.00
0.10
900
1000
270
190
240
1070
0.10
0.11
0.19
0.36
0.51
--
2100
2200
720
1000
680
--
Only the Yunasko technology can be accurately modeled using one time constant
JME
Slide 11

12. Reliability Study
(as June 24, 2013)
Manufacturer
Aging hours
Maxwell
5900
Ioxus
5900
4 cells at Vmax
Nippon ChemiCon
5900
and
JM Energy
5700
Yunasko
5800
BatsCap
5450
JME
CONSTANT VOLTAGE (2 levels)
5 cells at Vmax - 0.1 V
age at
maximum rated temperature
Slide 12

13. Three Groups of Capacitors Shown
Mounted in Aging Chamber
Constant T at constant voltage
(no cycling involved)
perform periodic measurements
JME
Slide 13

14. AGING RESULTS
2.7 V
2.6 V
10
0
-10
-20
-30
-40
-50
-60
300 A discharge
-70
20
Change in Capacitance (%)
Change in Capacitance (%)
Ioxus 3000 F Aging study - Change in Capacitance
Maxwell 3000 F Aging - Change in Capacitance
20
-80
10
0
-10
-20
-30
-40
2.7 V, 65 C
2.6 V, 65 C
-50
-60
300 A discharge
-70
-80
0
1000
2000
3000
4000
5000
6000
0
1000
2000
Time (hours)
Maxwell 3000 F Aging study - Change in
Resistance
2.7 V
2.6 V
700
600
5000
6000
900
300 A discharge
800
Change in Resistance (%)
Change in Resistance (%)
900
4000
Ioxus 3000 F Aging study - Change in Resistance
1000
1000
3000
Time (hours)
500
400
300
200
100
800
2.7 V, 65 C
2.6 V, 65 C
700
600
300 A discharge
500
400
300
200
100
0
0
1000
JME
2000
3000
4000
5000
6000
0
0
Time (hours)
Slide 14
1000
2000
3000
4000
Time (hours)
5000
65o C
6000

15. AGING RESULTS
65 C
10
20
2.7 VV
2.5
2.6 VV
2.4
0
Change in Capacitance (%)
Change in Capacitance (%)
Batscap 1200 F Aging study - Change in Capacitance
NCC 1200 F Aging study - Change in Capacitance
20
-10
-20
-30
-40
-50
-60
-70
150 A discharge
-80
2.7 V
2.6 V
10
0
150 A discharge
-10
-20
-30
-40
-50
lost electrolyte
due to JME error
-60
-70
-80
0
1000
2000
3000
4000
5000
6000
0
1000
2000
Time (hours)
Change in Resistance (%)
800
6000
2.7 V
2.6 V
900
150 A discharge
700
5000
1000
2.7 VV
2.5
2.4
2.6 VV
900
4000
Batscap 1200 F Aging study - Change in Resistance
NCC 1200 F Aging study - Change in Resistance
Change in Resistance (%)
1000
3000
Time (hours)
600
500
400
300
200
800
lost electrolyte
(due to JME error)
700
600
150 A discharge
500
400
300
200
100
100
0
0
0
1000
JME
2000
3000
4000
5000
6000
Time (hours)
Slide 15
0
1000
2000
3000
4000
Time (hours)
5000
65o C
6000

16. AGING RESULTS
Yunasko 1200 F Aging - Change in Capacitance
JM Energy 1100 F Aging study - Change in Capacitance
20
5
10
Change in Capacitance (%)
Change in Capacitance (%)
10
0
-5
-10
-15
3.8 V
3.7 V
-20
-25
150 A discharge
-30
-35
0
-10
-20
-30
-40
2.7 V
2.6 V
-50
150 A discharge
-60
-40
0
1000
2000
3000
4000
Time (hours)
5000
-80
6000
0
1000
JM Energy 1200 F Aging study - Change in Resistance
Change in Resistance (%)
300
150 A discharge
200
100
0
-100
0
1000
JME
2000
3000
4000
Time (hours)
65o C
5000
6000
3000
4000
5000
6000
Yunasko 1200 F Aging - Change in Resistance
5000
3.8 V
3.7 V
2000
Time (hours)
400
Change in Resistance (%)
Electrolyte leakage at seal
-70
2.7 V
2.6 V
4000
Electrolyte leakage at seal
150 A discharge
3000
2000
1000
0
-1000
Slide 16
0
1000
2000
3000
4000
Time (hours)
5000
60o C
6000

17. Maxwell 3000 F Cells
Normal Distribution
Normal Probability Distribution
-0.003
0.04
Mean,S
163.5
1404.
315.2
-0.002
-0.0015
-0.001
2.7 V
Initial
0.03
Relative Number
density
- Imaginary (ohm)
-0.0025
Initial
2.6 V, 5670 hours
2.7 V, 5670 hours
0.02
0.01
5670 hours 2.7 V, 65
-0.0005
0
0
0
0.0005
o
5670 hours 2.6 V, 65 C
JME
0.001
0.0015
0.002
0.0025 0.003
Real (ohm)
0
500 1000 1500 2000 2500
x
ESR (microOhm)
Slide 17

18. Ioxus 3000 F Cells
Initial and after 5742 hours of aging
NormalNormal Distribution
Probability Distribution
(X 0.001)
Initial
o C
24
2.6 V, 65
-0.003
-0.0025
Relative Number
-0.002
density
- Imaginary (ohm)
2.7 V, 65o C
-0.0015
-0.001
20
Initial
2.6 V, 5742 hours
2.7 V, 5742 hours
16
12
8
4
-0.0005
0
0
0
0.0005
JME
0.001
0.0015
Real (ohm)
0.002
0.0025
0.003
Slide 18
0
200
400
600
800 1000 1200
ESR (microOhm)
x

19. Nippon Chemi-Con 1100F Capacitor
(X 0.001)
24
-0.002
Initial
2.4 V, 65o C
2.5 V, 65o C
-0.0018
-0.0014
16
Relative Number
- Imaginary (ohm)
-0.0016
2.4 V, 5612 hours
2.5 V, 5612 hours
20
-0.0012
12
-0.001
-0.0008
-0.0006
-0.0004
8
4
-0.0002
0
0
0.0005
0.001
Real (ohm)
0.0015
0.002
0
580
630
680
730
ESR (microOhm)
JME
Slide 19
780
830

20. Yunasko 1200F Capacitor
Electrochemical Impedence Spectroscopy
NyQuist Representation - Yunasko Capacitors
-0.0008
Initial
2.6 V 5720 hours
2.7 V, 5720 hours
-0.0007
- Imaginary (ohm)
-0.0006
-0.0005
-0.0004
-0.0003
-0.0002
-0.0001
0
0
JME
0.0002
0.0004
Real (ohm)
Slide 20
0.0006
0.0008

21. JM Energy 1100F Capacitor
Normal Probability Distribution – JM Energy ESR
(X 10000)
5
Initial
3.7 V, 5595 hours
3.8 V, 5595 hours
Relative Number
4
3
2
1
0
7
8
9
10
ESR (10-4 Ohm)
JME
Slide 21
11
12
13
(X 0.0001)

22. Summary Results
• All capacitors demonstrate extremely high power performance
• JM Energy technology has highest energy density but with
largest 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
JME
Slide 22

23. “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).
JME
Slide 23