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Title: The Refuelable Zinc-air Battery: Alternative Techniques for Zinc and Electrolyte Regeneration

Abstract

An investigation was conducted into alternative techniques for zinc and electrolyte regeneration and reuse in the refuelable zinc/air battery that was developed by LLNL and previously tested on a moving electric bus using cut wire. Mossy zinc was electrodeposited onto a bipolar array of inclined Ni plates with an energy consumption of 1.8 kWh/kg. Using a H{sub 2}-depolarized anode, zinc was deposited at 0.6 V (0.8 kA/m{sup 2}); the open circuit voltage was 0.45 V. Three types of fuel pellets were tested and compared with results for 0.75 mm cut wire: spheres produced in a spouted bed (UCB); coarse powder produced by gas-atomization (Noranda); and irregular pellets produced by chopping 1-mm plates of compacted zinc fines (Eagle-Picher, Inc.). All three types transported within the cell. The coarse powder fed continuously from hopper to cell, as did the compacted pellets (< 0.83 mm). Large particles (> 0.83 mm; Eagle-Picher and UCB) failed to feed from hopper into cell, being held up in the 2.5 mm wide channel connecting hopper to cell. Increasing channel width to {approx}3.5 mm should allow all three types to be used. Energy losses were determined for shorting of cells during refueling. The shorting currents between adjacent hoppersmore » through zinc particle bridges were determined using both coarse powder and chopped compressed zinc plates. A physical model was developed allowing scaling our results for electrode polarization and bed resistance Shorting was found to consume < 0.02% of the capacity of the cell and to dissipate {approx}0.2 W/cell of heat. Corrosion rates were determined for cut wire in contact with current collector materials and battery-produced ZnO-saturated electrolyte. The rates were 1.7% of cell capacity per month at ambient temperatures; and 0.08% of capacity for 12 hours at 57 C. The total energy conversion efficiency for zinc recovery using the hydrogen was estimated at 34% (natural gas to battery terminals)--comparable to fuel cells. Producing zinc shot was quoted at 1.5-3 cents/lb above base price (52 cents/lb, ASM) for super purity ingot. Both the spouted-bed and the Eagle-Picher processes might conceivably be configured for fleet operation in user-owned and operated equipment located a the fleet's home base. This would eliminate the need for green-field industrial plants and fuels distribution systems. Scaleup of the spouted bed process and detailed examination of the Eagle-Picher process are recommended.« less

Authors:
;
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
898511
Report Number(s):
UCRL-TR-218414
TRN: US200708%%118
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 30 DIRECT ENERGY CONVERSION; AMBIENT TEMPERATURE; ELECTRIC POTENTIAL; ELECTRODES; ELECTROLYTES; ENERGY CONSUMPTION; ENERGY CONVERSION; ENERGY LOSSES; FUEL CELLS; FUEL PELLETS; HYDROGEN; INDUSTRIAL PLANTS; POLARIZATION; REGENERATION; UNINTERRUPTIBLE POWER SUPPLIES; ZINC

Citation Formats

Cooper, J F, and Krueger, R. The Refuelable Zinc-air Battery: Alternative Techniques for Zinc and Electrolyte Regeneration. United States: N. p., 2006. Web. doi:10.2172/898511.
Cooper, J F, & Krueger, R. The Refuelable Zinc-air Battery: Alternative Techniques for Zinc and Electrolyte Regeneration. United States. doi:10.2172/898511.
Cooper, J F, and Krueger, R. Thu . "The Refuelable Zinc-air Battery: Alternative Techniques for Zinc and Electrolyte Regeneration". United States. doi:10.2172/898511. https://www.osti.gov/servlets/purl/898511.
@article{osti_898511,
title = {The Refuelable Zinc-air Battery: Alternative Techniques for Zinc and Electrolyte Regeneration},
author = {Cooper, J F and Krueger, R},
abstractNote = {An investigation was conducted into alternative techniques for zinc and electrolyte regeneration and reuse in the refuelable zinc/air battery that was developed by LLNL and previously tested on a moving electric bus using cut wire. Mossy zinc was electrodeposited onto a bipolar array of inclined Ni plates with an energy consumption of 1.8 kWh/kg. Using a H{sub 2}-depolarized anode, zinc was deposited at 0.6 V (0.8 kA/m{sup 2}); the open circuit voltage was 0.45 V. Three types of fuel pellets were tested and compared with results for 0.75 mm cut wire: spheres produced in a spouted bed (UCB); coarse powder produced by gas-atomization (Noranda); and irregular pellets produced by chopping 1-mm plates of compacted zinc fines (Eagle-Picher, Inc.). All three types transported within the cell. The coarse powder fed continuously from hopper to cell, as did the compacted pellets (< 0.83 mm). Large particles (> 0.83 mm; Eagle-Picher and UCB) failed to feed from hopper into cell, being held up in the 2.5 mm wide channel connecting hopper to cell. Increasing channel width to {approx}3.5 mm should allow all three types to be used. Energy losses were determined for shorting of cells during refueling. The shorting currents between adjacent hoppers through zinc particle bridges were determined using both coarse powder and chopped compressed zinc plates. A physical model was developed allowing scaling our results for electrode polarization and bed resistance Shorting was found to consume < 0.02% of the capacity of the cell and to dissipate {approx}0.2 W/cell of heat. Corrosion rates were determined for cut wire in contact with current collector materials and battery-produced ZnO-saturated electrolyte. The rates were 1.7% of cell capacity per month at ambient temperatures; and 0.08% of capacity for 12 hours at 57 C. The total energy conversion efficiency for zinc recovery using the hydrogen was estimated at 34% (natural gas to battery terminals)--comparable to fuel cells. Producing zinc shot was quoted at 1.5-3 cents/lb above base price (52 cents/lb, ASM) for super purity ingot. Both the spouted-bed and the Eagle-Picher processes might conceivably be configured for fleet operation in user-owned and operated equipment located a the fleet's home base. This would eliminate the need for green-field industrial plants and fuels distribution systems. Scaleup of the spouted bed process and detailed examination of the Eagle-Picher process are recommended.},
doi = {10.2172/898511},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Jan 19 00:00:00 EST 2006},
month = {Thu Jan 19 00:00:00 EST 2006}
}

Technical Report:

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  • We are developing a refuelable zinc/air battery (6-cells) for evaluation under the five USABC `core` test protocols. In the first half of the two year project ($1OOK, FY1997), an advanced refuelable design was developed, fabricated and tested at power levels up to 415 W. Performance matched or exceeded that of earlier multicell systems. A computer program was developed for automated data acquisition and drive cycle simulation. Small mockup cells (80 cm 2) were constructed for rapid testing of components. In the follow-on effort (FY1998, $1OOK) we will make minor advances in system design and fabrication efficiency, and seek to improvemore » cathode performance and life, before delivery of two final units for test at DOE laboratory.« less
  • The Electric Fuel Limited (EFL) refuelable zinc-air battery system is currently being tested in a number of electric vehicle demonstration projects, the largest of which is a field test of zinc-air postal vans sponsored chiefly by Deutsche Post AG (the German Post Office). The zinc-air battery is not recharged electrically, but rather is refueled through a series of mechanical and electrochemical steps that will require a special infrastructure in commercial application. As part of the German Post Office field test program, Electric Fuel designed and constructed a pilot zinc anode regeneration plant in Bremen, Germany. This plant is capable ofmore » servicing up to 100 commercial vans per week, which is adequate for the field test vehicle fleet. This paper will describe the design and operation of each of the areas and devices within the plant.« less
  • Multicell zinc/air batteries have been tested previously in the laboratory and as part of the propulsion system of an electric bus; cut zinc wire was used as the anode material. This battery is refueled by a hydraulic transport of 0.5-1 mm zinc particles into hoppers above each cell. We report an investigation concerning alternative zinc fuel morphologies, and energy losses associated with refueling and with overnight or prolonged standby. Three types of fuel pellets were fabricated, tested and compared with results for cut wire: spheres produced in a fluidized bed electrolysis cell; elongated particles produced by gas-atomization; and pellets producedmore » by chopping 1 mm porous plates made of compacted zinc fines. Relative sizes of the particles and cell gap dimensions are critical. All three types transported within the cell 1553 and showed acceptable discharge characteristics, but a fluidized bed approach appears especially attractive for owner/user recovery operations.« less
  • This project has the broad objectives of developing materials and assessing costs of the sodium-sulfur battery. During this phase of the project costs of two cell design alternatives were compared, a new electrolyte was investigated, and electrolyte tubes were fabicated and delivered to EPRI. The fabicating of electrolyte tubes is not covered in the report. The first major objective of this study was to evaluate performance and cost of sodium-sulfur cells. These cells use a beta alumina electrolyte tube to separate the active materials, sodium and sulfur. In one design approach sulfur is contained inside the electrolyte tube and sodiummore » surrounds the tube, in the other approach the location of sulfur and sodium are reversed. The study evaluates the former approach and compares the results with an earlier study (RP726-1) in which the latter approach is evaluated. Cells, modules, and units for a 100 MWh load-leveling battery were designed and costs were estimated on the basis of production of 25 units/year. Particular attention was paid to reliability, safety, and heat transfer and recovery. Efficiency will be a minimum of 75.2%. Installed cost will be $53 (1976)/kWh, as compared with $41 (1976)/kWh the sulfur outside configuration case. The second major objective was to evaluate the fabrication process and properties of the new solid electrolyte Na/sub 3/Zr/sub 2/Si/sub 2/PO/sub 12/ (NASICON). Helium leak-tight tubes with a resistivity of about 5 ..cap omega.. cm at 300/sup 0/C were made. Sintering occurs at 1280/sup 0/C, without any buffering atmosphere. A phase transformation, at 280/sup 0/C, did not allow the manufacturing of an electrochemical cell that could stand thermal shocks. The high cost of raw materials seemed to cancel the benefit of low-cost sintering. 47 figures, 17 tables.« less
  • We report the development and on-vehicle testing of an engineering prototype zinc/air battery. The battery is refueled by periodic exchange of spent electrolyte for zinc particles entrained in fresh electrolyte. The technology is intended to provide a capability for nearly continuous vehicle operation, using the fleet s home base for 10 minute refuelings and zinc recycling instead of commercial infrastructure. In the battery, the zinc fuel particles are stored in hoppers, from which they are gravity fed into individual cells and completely consumed during discharge. A six-celled (7V) engineering prototype battery was combined with a 6 V lead/acid battery tomore » form a parallel hybrid unit, which was tested in series with the 216 V battery of an electric shuttle bus over a 75 mile circuit. The battery has an energy density of 140 Wh/kg and a mass density of 1.5 kg/L. Cost, energy efficiency, and alternative hybrid configurations are discussed.« less