High Capacitance Carbons for Electrochemical Double Layer Capacitors

Patricia H. Smith, Ph.D.

Naval Surface Warfare Center- Carderock (301) 227-4168 Patricia.H.Smith1@navy.mil

Goal: High Power, High Energy Density Energy Storage Device for Load Leveling

GOAL

Discharge Time: 10 to 100s sec. Cycle Life: 1,000,000 cycles

ED: 15-25 Wh/kg (70-130 J/cc) PD: 1000-2000 W/kg

Approach: Non-Aqueous, Asymmetric Hybrid DL Capacitor

EDL Capacitor Li Ion Battery

E = CV2
C C Li1-xMOY LixC6
4.5 4 3.5 3

Li Ion Asymmetric EDL

0 20 40 60 80 100

Voltage (V)

2.5 2 1.5

=
C Li1-xMOY

1 0.5

Asymmetric Hybrid DL Capacitor

Depth of Discharge (%)

G.G. Amatucci, F. Badway, A. Du Pasquier , and T. Zheng, J. Electrochem. Soc., 148 A930 (2001)

Lithium Titanate/Carbon
Collaboration with Glenn Amatucci, Rutgers University

Negative electrode: Li4Ti5O12

Low voltage (1.5V vs. Li Ref.) Long cycle life (0% expansion/contraction of crystal lattice) Good rate capability (high surface area nanostructured material) Undergoes faradaic reaction (battery intercalation process) Good capacity (150 mAh/g)
Li4Ti5O12 + 3Li+ + 3eLi7Ti5O12
Courtesy of Altairnano

Lithium Titanate/Carbon

Positive electrode: Activated Carbon

High Voltage (3V vs. Li Ref) Undergoes non-faradaic reaction. (Energy stored electrostatically.) Excellent rate capability and long cycle life. Low capacity (10-30 mAh/g)

Positive and negative electrodes not balanced. Energy density limited by carbon.

Investigation

Identify carbons that display high capacitance with lithium electrolytes.

Investigate:

Commercially available materials Experimental materials (SBIRs, Universities)

Minimum voltage decay Good high temperature stability

Non-Aqueous, Asymmetric EDL Capacitor Employing Li Electrolytes

Negative: Lithium Titanate Positive: Activated Carbon

G.G. Amatucci, F. Badway, A. Du Pasquier , and T. Zheng, J. Electrochem. Soc., 148 A930 (2001).

Lithium Ion Capacitor

Negative: Activated Carbon/Pitch composite Positive: Activated Carbon

A. Yoshino, T. Tsubata, M. Shimoyamads, H. Satake, Y. Okano, S. Mori, and S. Yata, J. Electrochem. Soc., 151 A2180 (2004).

Negative: Lithium Ion (graphitic carbon) Positive: Activated Carbon

O.Hatozaki, Proceedings from Advanced Capacitors World Summit 2006, San Diego.

Evaluation of Carbons
2000
TDA1

S 2p

Intensity (counts/second)

1800
TDA2

1600
TDA3

1400 1200 1000 800 600

AMS62C

Commercial & Experimental Carbons

170

168

166

164

162

160

Binding Energy (eV)

Physical & Chemical Analysis 2 x 3 Pouch Cell

5 4.5

3.5

2.5

1.5

0.005
0.5

0.004
0

Electrode Fabrication

50

100

150

200

250

300

350

400

450

500

0.003

0.002

0.001 Current (A)

0 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -0.001 0

-0.002

-0.003

Electrochemical Analysis
Potenial (V)

-0.004

-0.005

Analysis of Carbon Powders

Carbon MarkekTech International Aerogel Cloth W.L. Gore Kuraray RP-15 Kuraray YP-17D Kuraray YP-18X Kuraray NK260 MeadWestvaco Nuchar RGC Norit Supra 50 Norit SX-Ultra Pica BP-10 TDA1 TDA2 TDA3 TDA-AMS 62 C
* Supplied by manufacturer.

Precursor Resorcinol Formaldehyde Proprietary Phenolic Resin Coconut Shell Coconut Shell Pitch Mixed Hardwood Coconut Shell Peat Pine Saw Dust Sucrose Sucrose Fructose, Glucose Fructose, Glucose

BET Surface Area (m2/g) 402 2,000* 1318 1516 1479 2040 1622 1989 969 1796 2053 2114 2265 1939

Average Pore Size (nm) 4.14

Unknown

1.94 2.03 2.38 1.92 2.99 2.05 3.49 2.95 2.04 1.90 2.35 1.99

Surface Composition of Carbons Determined by XPS

Carbon Material Aerogel Kuraray RP-15 Kuraray YP-17 Kuraray YP-18X Kuraray NK-260 Mead Westvaco Nuchar RGC Norit DLC Supra 50 Norit SX Ultra Pica BP-10 TDA-1 TDA-2 TDA-3 TDA-AMS62C HOPG At% C 92.83 88.61 93.05 91.80 92.5 95.20 94.03 95.70 93.82 94.87 92.44 94.58 93.70 99.63 At% N 0.20 0.90 0.41 0.25 0.44 0.11 0.33 0.42 0.24 0.34 1.05 0.24 0.34 0.00 At% O 5.72 10.49 6.54 7.95 5.95 4.69 5.11 3.44 5.94 4.72 5.90 5.19 5.35 0.37 At% Na or S 1.24 (Na) 0.00 0.00 0.00 0.97 (Na) 0.13 (S) 0.00 0.53 (Na) 0.44 (Na) 0.0 0.07 (S) 0.61 (S) 0.00 0.60 (Na) 0.0 Ratio (O/C) 0.0616 0.1184 0.0703 0.0866 0.0643 0.0493 0.0543 0.0359 0.0633 0.0498 0.0638 0.0549 0.0571 0.0040

Carbons as received. No heat treatment.

Experimental CarbonsElectrode Fabrication

Limited quantities of sample Fabricated at NSWC Doctor Blade Process Binder: Polyvinylidene Fluoride (Kynar ) Thickness: 12-14m 2 x 3 electrodes

Commercially Available CarbonsElectrode Fabrication

Robert Waterhouse, Amtek Research International

Sufficient quantities of carbon samples Electroflex Process Ultrahigh molecular weight polyethylene Uses extrusion, calendaring and extraction technology. Films 50-500 m thick, 21 cm wide.

Commercially Available Electrodes- Fabrication

David Zuckerbrod, W.L. Gore & Associates

GORE EDLC electrodes Activated carbon/polytetrafluoroethylene (PTFE) composite Thickness: 80 -1000m Width: 25 - 200 mm

Analysis of Carbons & Electrodes

Carbon Precursor BET Surface Area (m2/g) Powder MarkekTech International Aerogel Cloth W.L. Gore Kuraray RP-15 Kuraray YP-17D Kuraray YP-18X Kuraray NK260 MeadWestvaco Nuchar RGC Norit Supra 50 Norit SX-Ultra Pica BP-10 TDA1 TDA2 TDA3 TDA-AMS 62 C Resorcinol Formaldehyde Proprietary Phenolic Resin Coconut Shell Coconut Shell Pitch Mixed Hardwood Coconut Shell Peat Pine Saw Dust Sucrose Sucrose Fructose, Glucose Fructose, Glucose 402 2,000* 1318 1516 1479 2040 1622 1989 969 1796 2053 2114 2265 1939 Electrode 336 1845 937 916 1018 1285 1147 1198 475 1037 1588 Not avail. 1131 1598 Average Pore Size (nm) Powder 4.14
Unknown

Electrode 7.61 2.03 1.96 2.08 2.47 2.12 3.10 2.09 4.35 3.15 2.04 Not Avail. 2.33 2.04

1.94 2.03 2.38 1.92 2.99 2.05 3.49 2.95 2.04 1.90 2.35 1.99

Results of Symmetric EDLC Tests

50th discharge, 2 X 3 cells charged at 1mA/cm2 and discharged at 10mA/cm2
1M LiPF6 50%EC:50%EMC (F/g) 2M LiBF4 AN (F/g)

Carbon (% Active Carbon Material) MarkeTech Aerogel Cloth (100) W.L. Gore (83) Kuraray RP-15 (92) Kuraray YP-18X (84) Kuraray YP-17D (80) Kuraray NK-260 (80) MeadWestvaco Nuchar RGC (80) Norit Supra 50 (80) Norit SX-Ultra (80) Pica BP-10 (80) TDA-1 (81) TDA-2 (81) TDA-3 (81) TDA-AMS 62C (81)

1M TEATFB AN (F/g)

9.5 mS/cm
22 139 83 87 83 148 86 76 52 77 100 113 104 99

17.3 mS/cm
28 147 90 92 88 154 82 81 55 80 86 101 91 100

54.6 mS/cm
168 99

92

90 87 58

90 98 92 106

Three-Electrode Evaluation to Determine Limiting Electrode

5 4.5

Positive Electrode vs. Li Reference

3.5

Voltage (V)

2.5

Negative Electrode vs. Li Reference

1.5

0.5

Cell
0 50 100 150 200 250 300 350 400

Cell
450

500

50th Discharge Time (sec) (Gore Electrode, 1M LiPF6 Dissolved in 50% Ethylene Carbonate: 50% Ethylmethyl Carbonate)

Three-Electrode Evaluation to Determine Limiting Electrode

5 4 3 2 Voltage (V) 1 0 0 -1 -2 -3 -4 50th Discharge Time (sec.) 50 100 150 200 250 300 350 400 450 500

Positive Electrode vs. Li Reference Cell

- (Negative Electrode vs. Li Reference)

(Gore, 1M LiPF6 Dissolved in 50% Ethylene Carbonate: 50% Ethylmethyl Carbonate)

 Cell CV Experiments
Negative NEt4+: 93 F/g
1M NEt4 BF4 in AN (1/2 cell Anode Exp)
0.005 0.004 0.006 0.003 0.002 0.001 Current (A) 0 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -0.001 -0.002 -0.003 -0.004 -0.006 -0.005 -0.006 Potential (V) -0.008 Potential (V) 0 Current (I) 0.004 0.008

Positive BF4-: 109 F/g

1M NEt4 BF4 in AN 1/2 Cell Cathode Exp

1M NEt4 BF4 in AN

0.002

0 0 -0.002 0.2 0.4 0.6 0.8 1 1.2

-0.004

Negative Li+: 70 F/g

2M Li BF4 in AN
0.005 0.01 0.004 0.008 0.003 0.006

Positive BF4-: 94 F/g

2M LiBF4 in AN

Current (A)

Current (A)

2M Li BF4 in AN

0.002 0.004 0.001

0 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -0.001 0

0.002

0 0 -0.002 -0.002 -0.003 -0.004 -0.004 0.2 0.4 0.6 0.8 1 1.2

-0.005 Potenial (V)

-0.006 Potential (V)

Mead Westvaco Nuchar RGC

Results Suggests

Cell is limited by negative electrode.

Ionic Radius (no solvation):

Power Supply

NEt4+ : 3.4 - 3.7 Li+: 0.8 - 1.2 BF4-: 2.3 - 2.4

+ +

Li+ solvation sphere radius must be larger than NEt4+ solvation sphere.

Cotton and Wilkinson

For same charge species: As radius decreases hydration (solvation) energy increases.

+ + + + + +

+ +
Solvated Anion Solvated Cation Li+
+

NEt4+

Results of Symmetric EDLC Tests

50th discharge, 2 X 3 cells charged at 1mA/cm2 and discharged at 10mA/cm2
1M LiPF6 50%EC:50%EMC (F/g) 2M LiBF4 AN (F/g)

Carbon (% Active Carbon Material) MarkeTech Aerogel Cloth (100) W.L. Gore (83) Kuraray RP-15 (92) Kuraray YP-18X (84) Kuraray YP-17D (80) Kuraray NK-260 (80) MeadWestvaco Nuchar RGC (80) Norit Supra 50 (80) Norit SX-Ultra (80) Pica BP-10 (80) TDA-1 (81) TDA-2 (81) TDA-3 (81) TDA-AMS 62C (81)

1M TEATFB AN (F/g)

9.5 mS/cm
22 139 83 87 83 148 86 76 52 77 100 113 104 99

17.3 mS/cm
28 147 90 92 88 154 82 81 55 80

54.6 mS/cm
168 99

92

90 87 58

86 101 91 100

90 98 92 106

Intensity (counts/second)

TDA Carbons Analysis

XPS Results
Sample TDA1 TDA2 TDA3 TDA AMS 62C HOPG At% C At% O 94.87 92.44 94.58 93.70 99.63 4.72 5.90 5.19 5.35 0.37 At% N 0.34 1.05 0.24 0.34 0.00 At% S (Na) 0.07 0.61 0.00 0.00 (0.60) 0.00 O/C Ratio 0.050

2000
TDA1

S 2p

1800
TDA2

Sulfur 2p
TDA3

1600 1400 1200 1000 800 600 170 168 166 164 162 160
AMS62C

x105

Binding Energy (eV)

C
HOPG TDA1

0.064
Intensity (counts/second)

Na C(KVV)
1

TDA2 TDA3 AMS62C

0.055 0.057 .0004

O(KLL)

O N S Si

5 nanometer XPS penetration

1000

800

600

400

200

Binding Energy (eV)

Effect of C Powder Surface Area on Specific Capacitance

180 160 Capacitance (F/g of Active C) 140 120 100 80 60 40 20 1M LiPF6 in 50%EC, 50%EMC 0 0 500 1000 1500
2

(50th Discharge, D:10mA/cm2, C:1mA/cm2)

2M LiBF4 in AN 2000 2500

Carbon Powder Surface Area (m /g)

Effect of Electrode Surface Area on Specific Capacitance

180 160 140 Capacitance (F/g Active C) 120 100 80 60 40 20 0 0 200 400 600 800 1000 1200
2

(50th Discharge, D:10mA/cm2, C:1mA/cm2)

1M LiPF6 50% EC/50%EMC 1400

2M LiBF4 in AN 1600 1800 2000

Electrode Surface Area (m /g)

Results of Symmetric EDLC Tests

50th discharge, 2 X 3 cells charged at 1mA/cm2 and discharged at 10mA/cm2
1M LiPF6 50%EC:50%EMC (F/cc) 2M LiBF4 AN (F/cc)

Carbon (% Active Material) MarkeTech Aerogel Cloth (100) W.L. Gore (83) Kuraray RP-15 (92) Kuraray YP-18X (84) Kuraray YP-17D (80) Kuraray NK-260 (80) MeadWestvaco Nuchar RGC (80) Norit Supra 50 (80) Norit SX-Ultra (80) Pica BP-10 (80) TDA-1 Doctor Blade (81) TDA-2 Doctor Blade (81) TDA-3 Doctor Blade (81) TDA-AMS 62C Doctor Blade (81)

F/g 139 87 148

1M TEATFB AN (F/cc)

11 55 51 42 26 38 20 25 17 27 36 32 32 35

17 58 56 47 29 43 19 27 21 26 29 31 33 25 37 29 22 30 66 59

113

33 22 35

Effect of Electrode Surface Area on Volumetric Capacitance

70

(50th Discharge, D:10mA/cm2, C:1mA/cm2)

60

AMTEK (92%)
Capacitance (F/cc Electrode) 50

W.L. Gore (83%)

AMTEK (84%)

40

30

20

AMTEK, Doctor Blade (80-81%)

10

MarkeTech (100%)
0 0 200 400 600 800

1M LiPF6 in 50%EC/50%EMC 1000 1200

2

2M LiBF4 in AN 1600 1800 2000

1400

Electrode Surface Area (m /g)

Electrode Processing is Important!

Voltage Decay
2.6

2.4

2.2 Voltage (volts)

1.8

1.6

1.4 0 5 10 Rest Time (Hours) Mead Westvaco Pica BP10 (10mil) Norit DLC Supra 50 Kuraray RP-15 Kuraray YP-17 Gore Electrode Kuraray YP-18X 15 20

Causes of Voltage Decay

Mechanical short (e.g. fibrils piercing separator) Metal impurities (e.g. Fe+3, Fe+2) and adsorbed O2 that can be reduced and re-oxidized. Oxygen functional groups, commonly residing on the edges of graphitic particles undergoing redox reactions. Amount and type depend on manufacturing conditions:
- Basic Groups: formed after heating C in a vacuum or inert air then exposing to O2 on cooling. - Acid Groups: formed when C treated with O2 at high temperatures (400 to 500oC)

1. carboxyl, 2. phenolic, 3. quinone, 4. lactone, 5. carboxyl anhydride, 6. peroxide C-H Kim and S-I Pyun, J Korean Ceramic Soc., 40, 819 (2003)

Groups Can React with Electrolyte Increasing Cell Impedance

4.50

Impedance of Li4Ti5O12/C Cells Using Different Carbons 2M LiBF4 in AN, 2.5V constant storage, 60oC
MK 231 NK 331 NK 260 MK261

4.00

3.50

impedance (mohm/cm2)

3.00

2.50

2.00

1.50

1.00

0.50

0.00 1 week rt +1 wk 60C 2wks 60C 3wks 60C 4 wks 60C 5 wks 60C cycling conditions

Impedance of Li4Ti5O12/C Cells Using Different Carbons

Impedance of hybrid cells comparing different carbons
6.00

2M LiBF4 in AN, 2.5V constant storage, 60oC

MK 231 NK 331 MK 261 NK 260

5.00

ASupra Commercial

impedance (mohm/cm2)

4.00

3.00

2.00

1.00

0.00 1 w eek rt +1 w k 60C cycling conditions 4 w ks 60C

Summary

NSWC-Carderock collaborating with Rutgers University in developing non-aqueous asymmetric hybrid DLCs for load leveling applications. Capacitance of thirteen carbons using two lithium based electrolytes determined. Greatest capacitance achieved with W.L. Gore Carbon and Kuraray NK-260. Electrode processing is important. Cells containing 2M LiBF4 in AN electrolyte generally: Gave 5% higher capacitance (F/g) than cells containing 1M LiPF6 in EC/EMC. Exception: TDA-1, TDA-2, TDA-3 displayed highest capacitance with 1M LiPF6 EC/EMC. Efforts underway to determine: Why TDA carbons utilizing carbonate electrolytes yielded higher capacitance than NEt4BF4 in AN Role of Cs surface functional groups on self-discharge.

Acknowledgements

My colleagues, Mrs. Michelle Cervenak, Dr. Azzam Mansour, & Dr. Glenn Zoski Dr. Glenn Amatucci, Rutgers University Dr. Michele Anderson, ONR