1999-01-2511

Nickel-Zinc Batteries for Commercial Applications

Dwaine Coates and Allen Charkey
Evercel Corporation

Copyright 1998 Society of Automotive Engineers, Inc.

ABSTRACT
This paper discusses rechargeable nickel-zinc battery development for consumer and mobile applications such as electric bicycles, scooters and hybrid and electric vehicles. Nickel-zinc battery performance has been improved through the development of a reduced solubility zinc electrode and a patented sealed cell design. Deep cycle capability has been increased to 600 cycles while maintaining a high specific energy up to 60 Watt-hours per kilogram. Nickel-zinc provides a commercially viable alternative for lead-acid, nickelcadmium and nickel-metal hydride for many applications.

Large quantities of sealed prismatic cells have been manufactured, including a 220 V battery for a hybrid electric vehicle (HEV). Several demonstration electric vehicles have been tested with 12 kilowatt-hour batteries and additional programs are currently underway. Nickel-zinc battery cost has been reduced through the use of patented plastic-bonded nickel and zinc electrodes. The nickel-zinc battery represents the next technological plateau to replace lead-acid batteries for many applications. Nickel-zinc can also replace environmentally unacceptable nickel-cadmium and costly nickel-metal hydride batteries with a safer, more energetic and less expensive system. This patented nickel-zinc technology is currently being licensed to several commercial entities for a variety of applications.

ROLL-BONDED ELECTRODE TECHNOLOGY INTRODUCTION

The general advantages of nickel-zinc batteries are well documented. The nickel-zinc battery provides the lowest-cost, highest energy density option for alkaline rechargeable systems. The unique patented technology developed provides an even greater opportunity for large-volume manufacturing cost savings. The patented graphite-based composite nickel electrode is the lowest cost technology available and provides a substantial cost savings over conventional nickel electrodes such as pasted nickel foam and sintered nickel powder. Zinc provides the highest specific energy, the lowest material cost and the least environmental impact of any potential anode material. The patented plastic-bonded zinc electrode provides for the lowest possible manufacturing costs of any electrode technology available. The nickel-zinc system is ideal for mobile applications such as electric bicycles, electric scooters and electric and hybrid vehicles. The nickel-zinc battery, with an energy density of 60 Watt-hours per kilogram, is capable of providing a vehicle range of 200 kilometers at a total energy cost of 3 to 4 cents per kilometer for a 25 kilowatt-hour battery priced at about US$7500.00 in large production volume. Other battery systems currently under development for electric vehicles are focused on technologies that are either too expensive, too heavy or contain environmentally undesirable materials. The nickel-zinc battery will provide electric vehicles with sufficient range and economy to satisfy most vehicle requirements. A unique, patented process has been developed for the manufacture of nickel and zinc electrodes (1,2,3,4). The roll-bonding process produces an electrode structure with 40-50% less metallic content than conventional sintered or pasted nickel electrodes. This not only reduces the usage of metal, thereby reducing cost, but also yields a substantially higher specific energy by increasing the ratio of active material to inactive material in the electrode. This composite nickel electrode manufacturing process provides the lowestcost nickel electrode available. The nature of the rollbonding process is readily adaptable to high volume production and automation. The process has an inherently low material attrition rate and electrode scrap can be reprocessed back into the process feed stock further reducing cost. A report (5) released by the U.S. Naval Surface Warfare Center, Carderock Division, compared several different types of nickel electrodes, including sintered powder, nickel fiber and nickel foam. Several different manufacturers were also compared in the study. The roll-bonded nickel electrode technology received the highest overall rating in the study in terms of both electrode process cost and process speed (manufacturability). In the nickel electrode manufacturing process, the nickel-hydroxide is mixed with conductive graphite, additives, polytetrafluoroethylene (PTFE) binder, and solvent. The solvent is an environmentally benign mineral oil. The electrode materials are formed into a sheet and are then roll-calendered to achieve the finished thickness. The finished electrode active material sheet is air dried to

remove the solvent, which can be reclaimed. The plastic-bonded electrode sheet is then laminated to a current collector to produce the finished electrode. The zinc electrode is manufactured by a similar process.

REDUCED SOLUBILITY ZINC ELECTRODE

A reduced solubility zinc electrode has been developed and patented (6). The shape change that occurs in the zinc electrode during charge/discharge cycling is due to the formation of the intermediate zincate ion. The zinc active material passes through this soluble phase during oxidation and reduction in alkaline solution. The approach to zinc electrode design is to reduce the formation of the soluble zincate intermediate reaction product by proceeding directly from the metallic oxidation state to an insoluble phase. Calcium-hydroxide is used as an additive to the electrode to promote the formation of calcium zincate. Calcium-zincate is thermodynamically stable and remains substantially insoluble in the electrolyte formulation and concentration used in the cell. Zinc dissolution is mitigated by formation of a passivating layer at the electrode/electrolyte interface. A potential concern is electronic conduction through this passivating, insoluble film on the zinc electrode. This can be addressed by doping the electrode with an electronically conductive metallic oxide species such as PbO or Bi2O3 and/or by plating the current collector with metallic lead or bismuth.

specific energy and energy density. Nickel-zinc delivers 60 Watt-hours per kilogram (Wh/kg) which is intermediate between nickel-cadmium and nickel-metal hydride. Nickel-zinc delivers approximately twice the specific energy of sealed lead-acid batteries. In real terms this difference is actually greater than the numbers suggest because the nickel-zinc battery is rated at the three-hour discharge rate and the lead-acid battery is typically rated at the ten or twenty-hour rate. Volumetric energy density of the nickel-zinc battery is between that of nickel-cadmium and nickel-metal hydride and higher than that of the sealed lead-acid battery. Figure 1 indicates the capacity delivered by the battery as a function of discharge rate. Nickel-zinc rate capability is similar to that of the nickel-cadmium battery. Both are suitable for high rate applications such as power tools, trolling motors and electric vehicles. The figure also shows that the available capacity of the leadacid battery decreases significantly as the discharge rate is increased. As the discharge current is increased the battery output voltage decreases due to impedance and polarization losses. Nickel-zinc, like nickelcadmium, shows very little decrease in the discharge output voltage as the current is increased. Lead-acid batteries are typically not used in high-rate applications because the discharge voltage drops to unusable levels.

120 100 80

CELL DESIGN
Several prismatic cell designs have been developed ranging from 2 Ah to 80 Ah. The technology is scaleable to larger prismatic cells, cylindrical cells or monobloc batteries. There are several potential methods of stacking and separating the cell. In a typical cell design, the nickel electrode is wrapped with multiple layers of Celgard and the zinc electrode is wrapped with one or two layers of Pellon. In each instance, the separator material edges are heat-sealed to form a pocket enclosing the electrode. The cell is stacked with alternating nickel and zinc electrodes. A zinc half-plate terminates the electrode stack on either end. The prismatic cell case and cover is typically molded from polysulfone or Noryl depending on the application. The cover incorporates a resealable safety valve. This valve remains closed under normal operating conditions providing sealed operation. Gas recombination can be managed by means of a patented split-negative electrode stack design and/or by an auxiliary gas recombination electrode. A hydrophobic gas diffusion membrane is used to separate the back-toback zinc half-plates in the split negative design. The gas recombination electrode uses a small quantity of supported catalyst. The cell is activated with 20-25% aqueous potassium-hydroxide which contains 1% lithium-hydroxide. % Cap.

60 40 20 0
0. 1C 0. 2C 0. 3C 0. 5C 0. 7C 1C 2C 3C 6C 8C 10 C 12 C

Ni-Zn Ni-Cd SLA

Discharge Rate Figure 1. Comparison of capacity versus discharge rate for NiZn, NiMH and SLA

PERFORMANCE
Nickel-zinc compares favorably with nickel-cadmium, nickel-metal hydride and sealed lead-acid in terms of

Figure 2 is a comparison of energy and power for nickelzinc and nickel-metal hydride batteries. Three design types are compared, high energy (HE), high power (HP) and ultra high power (UHP). The nickel-metal hydride battery data is taken from the Proceedings of the 16th International Battery Conference (7). The nickel-metal hydride battery has inherently lower rate capability than the nickel-zinc system. For the nickel-metal hydride battery, a significant decrease in specific energy is required in order to sustain high power operation. The nickel-metal hydride battery can be designed for high specific energy or high power capability, but not both simultaneously. The nickel-zinc battery is capable of sustained high power operation while retaining a high specific energy. This gives the nickel-zinc battery a significant advantage for high-rate applications.

NiMH Power NiMH Energy

1200

NiZn Power NIZn Energy

90 80

NICKEL-ZINC BATTERY CHARGING

Development of a commercial nickel-zinc battery has necessitated the development of charging methods and algorithms in order to supply charging systems for commercial applications. The intention is to provide a complete power system including both battery and charger. Extensive testing has been performed to fully characterize the nickel-zinc system as a function of both charge rate and temperature. Several charging algorithms and methods of charge termination have been evaluated. Basically, the defining characteristic for the charging system is cost. The cost of the charger has to be proportional to battery cost and the cost of the system in which the battery is used. For low-cost commercial applications such as electric bicycles, a low-rate low-cost charger is being developed. This system will require 8 hours to achieve full charge of the battery. For higher cost premium applications such as trolling motors, electric scooters and electric vehicles a high-rate fast charging system has been developed using much more sophisticated charging algorithms and charge termination methods. Fast charge systems are capable of achieving a fully charged battery in less than three hours. This method works particularly well for smaller systems such as scooters and trolling motors where extremely high currents are not required. For a simple low-cost charging system a standard taper charging method can be used. This method can achieve full charge on the battery in as little as two and one half hours when used at the C/2 charge rate. Figure 4 shows a typical high-rate charging cycle in which the battery is charged at the C/2 rate up to nearly 95% state-ofcharge. A five minute rest was included at the end of the C/2 portion of the charge. When the current is re-applied the cell voltage is clamped at 2.05 volts and the current is allowed to taper. This tops off the battery to full capacity. This method greatly reduces oxygen evolution at the nickel electrode during overcharge and improves overall charge efficiency.

1000 70 800 60 50 600 40 400 30 20 200 10 0 HE HP UHP 0

Design Type

Figure 2. Comparison of NiZn and NiMH A comparison of cycle life for nickel-zinc and nickelmetal-hydride batteries is shown in Figure 3. The nickelzinc data is for current production cells and the nickelmetal hydride data is from the Proceedings of the 16th International Battery Conference (8). In both sets of data the cells were cycled at 100% depth-of-discharge (DOD). The nickel-metal hydride cell was charged and discharged at the C/2 rate. The nickel-zinc cell was charged at the C/2 rate and discharged at the C/3 rate to a 1.2 volt cutoff each cycle. The nickel-metal hydride data is for an advanced cell design. A standard nickel-metal hydride cell included in the data for comparison yielded only about 300 cycles to 80% of its original capacity.

Watt Hours/Kg

Watts/Kg

2.5

18 16

1.2
CELL VOLTAGE (volts)
2

1 "C" Capacity 0.8 0.6

NiMH

12 10 8 6

1.5

0.4 0.2 0

NiZn

V LA E OT G CRET URN

0.5

4 2

50 100 150 200 250 300 350 400 450 500 550 600 Cycle Number

0 0.00

0.50

1.00

1.50

2.00

2.50

0 3.00

E A S DT (hours) L P E IME

Figure 3. Cycle life comparison of NiZn and NiMH

Figure 4. NiZn taper charge method

CURRENT (Amperes)

14

For a 30 Ampere-hour battery, only about 4 amperehours of charge is input during the taper charge step. The battery could also be unplugged and used at the end of the C/2 charge with a minimal sacrifice in device run time. The taper charge is included to insure an extra boost in capacity when the battery is left on the charger. A time limit is also included as a safety precaution. This limits the total amount of overcharge possible to a maximum value. Charge termination voltage is a function of both temperature and charge rate as shown in Figure 5. At higher charge rates the end-of-charge voltage increases as a function of cell impedance and polarization. The charge termination voltage also increases at colder temperatures, primarily due to the decreased conductivity of the electrolyte (20% aqueous potassiumhydroxide). Because of this strong temperature dependence the battery charger must be temperature compensated which requires the use of a thermistor to detect battery temperature. This slightly increases the cost of the charging system but provides much more efficient charging of the battery.
2.4 2.3
END-OF-CHARGE VOLTAGE

CONTACT
Allen Charkey, Executive Vice-President/Chief Operating Officer Evercel Corporation 2 Lee Mac Avenue Danbury, CT 06810 Phone: 203-825-3900 www.evercel.com

REFERENCES
1. U. S. Patent 5,023,155 (1991). 2. U. S. Patent 4,976,904 (1990). 3. U. S. Patent 4,758,473 (1988). 4. U. S. Patent 4,546,058 (1985). 5. NSWCCD-TR-96/001 Carderock Division, Naval Surface Warfare Center, Silver Spring, MD February 1995. 6. U. S. Patent 5,460,899 (1995). 7. Varta AG, Proceedings of the 16th International Seminar and Exhibit on Primary and Secondary Batteries, Ft. Lauderdale, FL March 1-4, 1999. 8. Ovonic Battery Company, Proceedings of the 16th International Seminar and Exhibit on Primary and Secondary Batteries, Ft. Lauderdale, FL March 1-4, 1999.

2.2 2.1 2.0 1.9 1.8 1.7 1.6 0 5 10 15 20 25 30 35 40 C/10 C/5 C/3 C/2

TEMPERATURE (C)

Figure 5. NiZn charge termination voltage as a function of temperature

CONCLUSION
After years of development and several patent awards, the nickel-zinc battery system has achieved commercial viability. The performance obtained from the battery makes it competitive with the nickel-cadmium and nickel-metal hydride systems. The low material and manufacturing costs make it competitive with lead-acid batteries. The technology has been licensed to several commercial entities for a variety of applications. A small scale manufacturing facility in the U.S. is currently producing commercial grade cells and a full-scale manufacturing joint-venture is coming online in China in the near-term.