1

Ultracapacitor Technology: Present and Future Performance and Applications

Andrew Burke Marshall Miller Nathan Parker Institute of Transportation Studies University of California-Davis Davis, California 95616 afburke@ucdavis. edu

Introduction
This paper is meant to augment the materials and discussions given in a paper (Reference 1) presented in August 2003 at the 2003 Capacitor Summit. In this paper, the emphasis is on testing of small ultracapacitor cells (10 F and 120F) and a 45V module consisting of 3500 F devices and pulse charging and discharging with pulse durations much smaller than the RC time constant of the cell. Projections are also made of further progress in improving the energy density of ultracapacitors and their near-term applications in both vehicle and stationary power systems.

Present Status of Ultracapacitor Technology Cells

Carbon/carbon devices There are presently commercially available carbon/carbon ultracapacitor devices (single cells) from several companies Maxwell/Montena, Panasonic, Ness, and EPCOS. All these companies market large devices with capacitance of 1000-5000 F. These devices are suitable for high power vehicle and stationary applications. The performance of the various devices is given in Table 1. The energy densities (Wh/kg) shown correspond to the useable energy from the devices based on constant power discharge tests from V0 to V0. Peak power densities are given for both matched impedance and 95% efficiency pulses. For most applications with ultracapacitors, the high efficiency power density is the appropriate measure of the power capability of the device. For the large devices, the energy density for most of the available devices is between 3.5-4.5 Wh/kg and 95% power density is between 800-1200 W/kg. In recent years the energy density of the devices has been gradually increased for the carbon/carbon (double-layer) technology and the cell voltages have increased to 2.7V/cell using acetonitrile as the electrolyte.

2 Table 1: Summary of the Characteristics of Commercially Available Carbon/Carbon Ultracapacitors

Device V rated 2.5 2.7 2.3 2.7 2.7 2.7 2.7 C (F) 2700 10 120 1800 3640 5085 1375 R (mOhm) .32 25.0 21.0 .55 .30 .24 2.5 RC (sec) .86 .25 2.5 1.00 1.10 1.22 3.4 Wh/kg (1) 2.55 2.5 3.8 3.6 4.2 4.3 4.9 W/kg (95%) (2) 784 3040 282 975 928 958 390 W/kg Match. Imped. 6975 27000 3700 8674 8010 8532 3471 Wgt. (kg) .70 .0025 .017 .38 .65 .89 .210 (estimated) .34 Vol. lit. .62 .0015 .010 .277 .514 .712 .151

Maxwell** Ness Ness (3) Ness Ness Ness Asahi Glass (propylene carbonate) Panasonic (propylene carbonate) Panasonic Panasonic EPCOS EPCOS Montena Montena Okamura Power Sys. ESMA

2.5

1200

1.0

1.2

2.3

514

4596

.245

2.5 2.5 2.5 2.5 2.5 2.5 2.7 1.3

1791 2500 220 2790 1800 2800 1350 10000

.30 .43 3.0 .15 .50 .39 1.5 .275

.54 1.1 .66 .42 .90 1.1 2.0 2.75

3.44 3.70 2.76 3.46 2.49 3.33 4.9 1.1

1890 1035 1126 2055 879 858 650 156

16800 9200 10000 18275 7812 7632 5785 1400

.310 .395 .052 .57 .40 .525 .21 1.1

.245 .328 .042 .377 .30 .393 .151 .547

(1) Energy density at 400 W/kg constant power, Vrated - 1/2 Vrated (2) Power based on P=9/16*(1-EF)*V2/R, EF=efficiency of discharge ** Except where noted, all the devices use acetonitrile as the electrolyte (3) Psuedo-caps from Ness using carbon/metal oxide electrodes

Psuedo-capacitive cells As indicated in References (2-8), there have been considerable development of ultracapacitor devices that have at least one of the electrodes that utilize non-double-layer mechanisms for electrical charge storage. Some of these devices use carbon in one electrode (References 2-5) and psuedo-capacitive or Faradaic processes in the other electrode. The characteristics of some of these technologies are given in Table 2. Except for the Ness 120F device (Reference 8), these devices are not commercially available and are in varying stages of development and testing. In general, the energy densities of the psuedo-capacitive devices are significantly higher than the carbon/carbon devices and their power densities are lower. Also the energy densities of the psuedocapacitive devices are more discharge rate dependent than those of the carbon/carbon devices. A major concern about the psuedo-capacitive devices is cycle and calendar life even though the Ness 120F devices are claimed to have a cycle life of 100,000 deep discharge cycles. One of the most interesting ultracapacitor developments during the past year has been work on carbon/carbon devices using graphitic carbon rather than activated carbon (References 6,7) done by Okimura and at Ahasi Glass. Charge is stored in the graphitic

3 carbons by intercalation of the electrolyte ions into space between the carbon sheets as with the Lithium ions in a Li-ion battery. The voltage of these devices are expected to be between 3 and 4V with energy densities of at least 20 Wh/kg. Their power densities should be high, but probably not as high as carbon/carbon devices using activated carbon. Table 2: Characteristics of various Psuedo-capacitor technologies Electrode Materials Carbon/ metal oxide Intercalation into graphite Intercalation into a mix of activated carbon and graphite LiTi/carbon Carbon/ NiOOH Wh/kg/ Wh/L 10/13 25/32 1200 (W/kg) 90% 1000

Device Ness Pseudocap Okamura Ashasi Glass

Electrolyte Voltage Organic Organic 1.0-2.3 0-3.8

Status Commercial Lab prototypes Lab prototypes

Organic

0-3.0

12/15

1200

Telcordia Atlantic University, Russians UC Davis, Russians

Organic Aqueous, KOH

1.0-2.8

14/24 15/30

1500 2000

Lab protoTypes Commercial and small lab devices

Carbon/PbO2

Aqueous, Sulfuric Acid

1.0-2.1 15/40 3500 Small lab cells

Modules
There are presently several 42-45V modules (see Table 3) available consisting of multiple, large ultracapacitor cells. For example, the Ness 45V module (Fig.1) consists of eighteen (18) 3500 F devices connected in series with balancing circuits across the cells. As discussed in Reference 9, the Ness module was extensively tested at UC Davis and its performance was found to be close to that expected based on the characteristics of the 3500F cells. Constant power and PSFUDS data from those tests are given in Tables 4-5. Note that the power density of the module changes only by about 10% from low power to high power (744 W/kg) and the roundtrip efficiencies on the PSFUDS cycle are 95-96%. These characteristics result from the low resistance (6.5 mOhm) of the module. As indicated in Table 3, the packaged weight and volume of the ultracapacitors in the modules can be considerably greater than that of the cells alone resulting in low packaging factors. This is especially the case if provisions for cooling (fans and cooling channels) are incorporated into the module. The density of carbon/carbon ultracapacitor cells is relatively low (1.2-1.3 gm/cm3) so unless considerable care is taken in packaging the devices into a module the ultracapacitor unit will be unattractive to incorporate into a

4 vehicle. Reasonable targets for packaging factors are .85 for weight and .7 for volume excluding cooling fans. Figure 1: Photograph of the 45V Ness Ultracapacitor Module

Table 3: Characteristics of various 42-45V ultracapacitor modules Weight Volume (kg) (liters) Voltage Power(kW) (90% effic.) Weight packaging Factor Volume packaging factor .36 (with cooling) .32 (with cooling) .50 (without cooling)

Module

Wh

Ness (1) (194 F) Maxwell (2) (135 F)

19.1

26.1

45

40

16.9

.635

16.0

22.0

42

25

8.5

.592

Asahi Glass (3) 6.1 5.4 42 15 2.2 Not avail. (80 F) (1) tested at UC Davis (Reference 9) (2) tested at the Idaho National Engineering Laboratory (3) specifications from References (7)

Table 4: Constant Power Test Data for the Ness 45V module Power density Power (W/kg)* Energy Energy density kW Cycle Wh (Wh/kg)*
2 165 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 39.4 39.3 39.2 38.0 38.0 37.9 37.0 36.8 36.8 36.0 35.8 35.8 35.3 35.3 35.3 3.26 3.25 3.24 3.14 3.14 3.13 3.06 3.04 3.04 2.98 2.96 2.96 2.92 2.92 2.92

330

495

661

744

*energy and power density based on weight of the cells in the module (weight of the cells is 12.1 kg)

Table 5: Roundtrip Efficiencies for the Ness 45V Module on the PSFUDS cycle Energy in Energy out Efficiency Cycle* Wh Wh % 1 102.84 97.94 95.2 2 101.92 97.94 96.1 3 101.67 97.94 96.3 *PSFUDS power profile based on maximum power of 500 W/kg and the weight of the cells alone

Prospects for Future Improvements in Modules

Further improvements in ultracap modules are needed in the following areas: (1) cell performance, (2) packaging and cooling of the cells, (3) further development and testing of balancing circuits that both reduce cell-to-cell variability of the voltage with cycling and do not increase cell self-discharge. The performance improvements (increased energy density Wh/kg and decreased resistance and hence maximum power density) of ultracapacitor cells have been ongoing . For example, Ness (Reference 10) is projecting that by 2005 the 3500 F device will have useable energy densities of 5.9 Wh/kg and 6.8 Wh/liter and by 2009 the cell energy densities will be 8 Wh/kg and 8.4 Wh/liter. Other ultracap manufacturers can be expected to make similar improvements in the performance of carbon/carbon devices. These improvements in performance are projected with further increases in power density and no sacrifice in the cycle life that is projected to be greater than 500,000 deep discharge cycles. Cost will likely remain an

6 issue, but with increasing volume of sales, it can be expected that device costs/prices will continue to decrease as has been the case in recent years. There has been increasing research activity in hybrid ultracapacitors (References 2-7). These devices (see Table 2) have higher energy density than the carbon/carbon devices by a factor of 2-3. Presently the only hybrid device on the market is the Pseudocap from Ness (Reference 8) that utilizes carbon on the negative electrode and lithium metal oxides on the positive. The largest Pseudocap marketed at the present time has a capacitance of 120 F, but Ness plans to have 3500 F devices available by 2005 which are projected to have energy densities of 9.1 Wh/kg and 11 Wh/liter. The Pseudocaps will have lower power and shorter cycle life than the carbon/carbon devices. The projected 90% discharge power of the Pseudocaps is about 1400 W/kg and the cycle life about 100,000 cycles between 2.5 and 1V. The cost of the Pseudocaps will be less than that of the carbon/carbon devices by 15-20%. As noted in Table 3, the modules currently available for use with 42V hybrid systems have relatively low packaging factors. These modules incorporate air cooling fans which contribute significantly to their low packaging factors, especially the volume factor. In the case of the Ness 45V module, if one eliminates the volume for the fans and the air gap above the cells for cooling, the volumetric packaging factor increases from .36 to .75. The weight factor will also increase, but it is more difficult to estimate. Hence if the cooling fans are provided external to the modules, the packaging factors for the ultracapacitor modules can be expected to be reasonably high. For example, in information from Ness for a 144V system, they project weight packaging factors of .83 and volume factors of .67. These factors are considerable higher than the corresponding factors of .64 and .36 of the 45V module. Based on the result of removing the provision for the cooling fans from the 45V module, projected packaging factors of .85 and .70 seem reasonable as design targets for vehicle applications The key function of the balancing circuit is protect the cells from over-voltage when the module is charged to or maintained near its rated voltage. In principle, what is required is a balancing circuit that by-passes a small current during times of charging for those cells that have a tendency to exceed a specified maximum voltage when the module is near its rated voltage (45V in the case of the Ness module). During times of discharge and when the cell is kept well below the specified maximum voltage, the balancing circuit should not effect the operation of the cell. Discussions with Ness indicated the next generation balancing circuits will function in the manner just described and should not significantly effect the self-discharge of the module (Reference 11, 12). These improved balancing circuits should be available in the near term and improvement in the performance of balancing circuits is not expected to be an issue in hybrid vehicle applications of ultracapacitor modules. At the present time, the cost of the balancing circuits is small compared to that of the capacitors, but their cost will be more of an issue when the cost of the capacitors is significantly reduced in future years.

Recent Tests of small Capacitor devices (10F carbon/carbon and 120F psuedo-cap devices)
Constant current and constant power tests The Ness 10F and 120F ultracapacitors (see Figure 2) were tested for appropriate ranges of constant current and constant power. The data are shown in Table 6. The

7 differences between the performance of the carbon/carbon and psuedo-cap devices are evident from the table. The energy density of the carbon/carbon device is significantly less than that of the psuedo-cap at moderate powers, but the carbon-carbon device maintains its energy density to very high power densities. The data also show that the capacitance of the carbon/carbon device is essentially independent of current even at very high current densities. It can be expected that these differences between the small carbon/carbon and psuedo-cap type devices will also remain true for larger devices (1000 F). The advantages of the psuedo-cap or hybrid type devices are their higher energy density and possible lower cost.

Figure 2: Photograph of the Ness 10 F carbon/carbon and 120F psuedoCap devices

120F

10F

Ness Pseudocapacitors

8 Table 6: Summary of the constant current and constant power data for the small Ness ultracapacitors

Ness 10F carbon/carbon

Current (A) .5 1.0 2.0 3.0 Capacitance (F) 10.6 10.5 10.2 10.1

Ness 120F Psuedo-cap

Current (A) .5 1.0 2.0 3.0 4.0 5.0 V0 =2.3 Resistance=21 mOhm Capacitance (F) 133 128 126 125 123 121

V0 = 2.7 Resistance = 25 mOhm (from pulse tests) 10 F Power (W) .5 1.0 1.5 2.0 2.5 3.0 W/kg 200 400 600 800 1000 1200 Wh/kg 3.1 3.05 2.92 2.92 2.90 2.86

120 F Power (W) 1 2 3 4 6 8 10 W/kg Wh/kg 59 4.29 118 4.16 176 4.03 235 3.9 353 3.26 470 3.02 588 2.79 Voltage: 2.3-1.0 Weight = 17 grams Volume = 10 cm3

Voltage: 2.7-1.35 Weight =2.5 grams Volume = 1.5 cm3

Pulse charging and discharging tests The 10 F and 120 F devices were also tested using pulse currents rather than steady currents. The time durations of the current pulses were short compared to the RC time constants of the devices. In the case of the 10 F device having a RC time constant of .25 seconds, the pulse duration was .01 seconds with a repeat time of .05 seconds (duty cycle of 20%). For the 120 F device having a RC time constant of 2.5 seconds, the pulse duration was .05 seconds with a repeat time of .25 seconds (duty cycle of 20%). The ratio of time constant to pulse duration time was 25 for the 10 F device and 50 for the 120 F device. The pulse charge/discharge profiles (voltage vs. time) for the two devices are shown in Figures 3 and 4. In both cases, the capacitance and resistance of the devices determined

1.5

2.5

1 2 0.5 1.5 Current 0 0 -0.5 0.5 -1 100 200 300 400 500 600 1 Voltage

-1.5

-2 Test_Time

-0.5

Figure 3: Voltage vs. time trace for pulse charge/discharge of the Ness 10 F carbon/carbon device

2.5

4 2

2 1.5 Current Voltage

0 0 100 200 300 400 500 600 700 800 1 -2

0.5 -4

-6 Test_Time

Figure 4: Voltage vs. time trace for pulse charging/discharging of 120 F Ness psuedo-cap device

10 from the pulse tests (see Table 7) were close to those determined from the steady DC current tests even though the pulse durations were much smaller than the RC time constants. These tests indicate that ultracapacitors can be used in applications in which the duration of the charge and discharge pulses are very short compared to the RC time constant of the devices without a loss of energy storage capacity. Table 7: Pulse charging/discharging results for short duration pulses Device 10 F 120 F Pulse duration .01 sec .05 sec RC/pulse 25 50 Capacitance 10.6 110 Resistance 25 mOhm 20 mOhm

Vehicle and Stationary Applications

Vehicle applications During the last several years there has been an increasing recognition that ultracapacitors can be utilized as the energy storage component in electric and hybrid vehicles. In a number of cases, demonstration programs involving the use of ultracapacitors have been undertaken with good results. In this section of the paper, vehicle applications of ultracapacitors will be identified and demonstration programs using them briefly described. One of the most near-term applications of ultracaps is to use them in combination with lead-acid batteries to start the diesel engines in large (Class 8) tractor-trailer trucks (see reference 22). The ultracaps are especially advantageous in very cold, sub-zero temperatures. Several companies are presently field testing ultracap/battery units before offering them for sale. Programs involving the use of ultracaps in electric vehicles are discussed in References 13, 14. In these programs, ultracaps are used to provide the power during acceleration of the vehicles and to recover energy during braking. The ultracaps are then recharged from the batteries during periods of reduced electrical power demand. In these vehicles, the power split between the ultracaps and the batteries was controlled with interface electronics. The electrical drivelines functioned well as designed with the ultracaps protecting the batteries from the high power surges in both discharge and charge. There are a number of examples in which ultracaps have been utilized in hybrid vehicles. In these applications, ultracaps are used alone and in combination with batteries. Most of the vehicle demonstrations using ultracaps have been in heavy duty vehicles (buses and trucks) designed as series hybrids (References 15-17). In these vehicles, the ultracaps are used to load level an engine/generator permitting it to operate with much reduced transients and resultant lower emissions and higher fuel economy. The ultracaps also permit the recovery of significant energy during braking in stop-go city driving. These programs have been quite successful with the ultracaps functioning as envisioned by the system designers. In recent meetings there has been much discussion of the use of ultracaps in hybrid passenger cars (References 18-22). The application most discussed is the 42V

11 stop/go hybrid utilizing a relatively low power electric drive (5-8 kW). In this case, the ultracap could be combined with a lead-acid battery that would recharge the ultracap as needed. The lead-acid battery would be recharged from the engine using either the alternator or the traction motor as a generator. Systems utilizing this approach in hybrid passenger cars have been built and tested showing fuel economy gains of 10-15% (References 18-19). Ultracaps can also be used in high voltage, power assist mild hybrids replacing the nickel metal hybrid batteries. These designs utilize only slightly down sized engines so that if/when the ultracaps become depleted the vehicles still has good performance. Recent simulation results for such systems are shown in Table 8 taken from Reference 9. Using this approach, fuel economy increases of 30-40% are possible with good vehicle acceleration performance. Table 8: Fuel Economy Simulation (Advisor) Results using Batteries and Ultracapacitors in Mild Hybrid Passenger Cars Compact Car Fuel economy Driving cycle FUDS Fed. HW US 06 EC-EUDC Mid-size Car Fuel economy Driving cycle FUDS Fed. HW US 06 EC-EUDC Full-size Car Fuel economy Driving cycle FUDS Fed. HW US 06 EC-EUDC Small cap (210 Wh) 33.6 37.4 24.9 30.9 mpg Ni mt.hydride Battery 31.4 34.1 23.7 28.4 Small cap (150 Wh) 37.7 43.3 29.7 35.4 mpg Ni mt.hydride Battery 33.8 37.3 26.1 30.7 Small cap (94Wh) 44.1 50.2 32.6 39.6 mpg Ni mt.hydride Battery 40.2 43.8 30.1 36.6

Large cap (180 Wh) 44.4 50.4 33.1 40.6

Large cap (293 Wh) 37.9 43.5 29.8 35.4

Large cap (405 Wh) 33.9 37.6 25.0 31.2

12 It has recently been recognized that ultracaps are especially well suited for use with fuel cells (References 23-24) for the following reasons. First, unlike a battery, the rest voltage of the ultracap is variable and not fixed by its chemistry resulting in easy matching the fuel cell and ultracap voltages at rest (zero or minimum power draw). Second, the ultracap/fuel cell system is almost self-regulating without interface electronics in that the fuel cell can only provide low power at high voltage when the ultracap is nearly fully charged and will automatically provide high power at lower voltage when the ultracap becomes depleted and needs to be recharged. Honda has used ultracaps in their fuel cell vehicles with great success (Reference 24) for a number of years and Hydrogenics (Toronto, Canada) is presently assembling and testing a fuel cell powered neighborhood EV (GEM) and a fork-lift truck using ultracaps to provide the power during periods of high power demand. The use of ultracaps with fuel cells tends to stabilize the fuel cell operation even during periods of rapidly changing electrical loads and transients in hydrogen flow or purging. Stationary applications Many markets have been developing for ultracaps for non-vehicle or stationary applications. Most of these markets are related to consumer electronics, but some are for industrial applications. In most cases, the applications utilize relatively small devices with capacitances less than 100 F. The markets are in the areas of cell phones, pagers, toys, audio boom boxes, lighting fixtures, wind turbine blade actuators, etc. One of the markets that could use large ultracap devices that has been widely discussed is distributed UPS systems with engine/generators or fuel cells. Most of the UPS systems currently in use or being planned use lead-acid or nickel cadmium batteries for energy storage. These systems are designed for long outages of at least several hours. However, with the recent power blackouts, there is much present interest in UPS systems to cope with short periods (30 seconds or less) of high power demand or poor power quality (Reference 25). These systems will require high power for short periods and relatively small energy storage. Ultracaps should be ideal for use in such systems. For example, using the present technology for carbon/carbon devices, a 1000 kg, 750 liter unit of capacitors could provide 3-4 MW of power for 6 seconds (5 kWh of energy). It would be impractical to use batteries for such short time UPS applications. Ultracaps can also used with fuel cells in UPS systems to meet the starting transient when the system is activated during a power outage.

Economic and Cycle life Considerations

With the heightened recognition of the value of ultracaps in many applications, the cost of the devices is the primary deterrent to their use or at least serious consideration in many advanced systems requiring electrical energy storage. The cost of ultracaps has been decreasing markedly over the last few years, but remains higher than can be justified in many applications especially in vehicles. Present prices for large devices appears to be 2-3 cents per farad. For a rated voltage of 2.7 V/cell, one cent per Farad corresponds to $15/Wh of useable energy. If the capacitor being considered has an energy density of 5 Wh/kg and a power density of 1500 W/kg, $15/Wh corresponds to a power cost of $50/kW. If a target device cost for vehicles is $20/kW, this requires a device cost of about .4 cents per Farad or about one-fifth (1/5) the present cost. This

13 corresponds to $6/Wh. A key issue in reducing the cost of carbon/carbon ultracaps is the unit cost of activated carbon, which at the present time can be $50/kg or higher. As discussed in Reference 1, a 5000 F device (3.25 Wh) would use about 250 gm of carbon. At .4 cents/Farad, the 5000 F device would cost $20. If the cost of the carbon were to be about 20% the total cost of the device, the price of carbon would have to be $20/kg or less. To reduce the device price to .2 cents/Farad, the price of the carbon would have to be less than $10/kg. Hence it appears that $10/kg is a reasonable target for the cost of carbon for low cost ultracaps. This would result in device costs of about $3.5/Wh rather than the present cost of about $15/Wh. Cycle and calendar life are much less issues than cost for carbon/carbon ultracaps. Tests of carbon/carbon devices have shown that a cycle life of 500,000 cycles seems to be achievable at temperatures less than 40deg C. If a cycle life of several million cycles is needed as in a hybrid transit bus, this may be difficult to achieve even with ultracaps. For non-vehicle applications where daily or less cycling is required, the cycle life of even psuedo-capacitors having a cycle life of about 100,000 cycles may be more than sufficient leading to a device life of decades. In these cases, calendar life becomes the main issue.

Summary and Conclusions

The discussions and data presented in this paper indicate that continuing progress is being made in improving the performance of ultracapacitor devices and reducing their cost. As a result there are strong indications that the interest of both the auto companies and electric utilities in using ultracapacitors to meet energy storage requirements in advanced systems being evaluated has increased markedly in the last year or two. The present relatively high cost of ultracaps compared to batteries seems to be the over-riding factor in preventing their inclusion in the advanced systems. Ultracap markets have grown significantly in recent years with most applications being in the consumer electronics and industrial areas. Both analysis and vehicle demonstration/test projects indicate that ultracaps are well suited for use in mild hybrid vehicles in the idle stop/go and power assist configurations. One particularly attractive option is to combine ultracaps with lead-acid batteries in a stop/go 42V system with regenerative braking energy recovery. Demonstration/testing of ultracaps with fuel cells has shown that ultracaps are well suited for this application and several companies are actively pursuing this option. Most of the ultracapacitors currently on the market utilize activated carbon in both electrodes. These devices are true double-layer capacitors. R&D is presently underway to develop ultracaps that utilize psuedo-capacitive energy storage processes, such as intercalation as in a Lithium battery or Faradaic chemical reaction as in a lead-acid or nickel metal hydride battery, in at least one of the electrodes. Either activated carbon or graphitic carbon is used in the other electrode(s). Present results indicate that energy densities of 10-20 Wh/kg can be achieved with these advanced ultracap technologies while maintaining their present advantage in power density and cycle life compared to batteries.

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References
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