A protocol is presented to study multi-electron metal/air battery systems by using previous technology developed for the zinc/air cell. Electrochemical testing is then performed on fabricated batteries to evaluate performance.
A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for synthesizing nanoscopic VB2 is presented as well as step-by-step procedure for applying a zirconium oxide coating to the VB2 particles for stabilization upon discharge. The process for disassembling existing zinc/air cells is shown, in addition construction of the new working electrode to replace the conventional zinc/air cell anode with a the nanoscopic VB2 anode. Finally, discharge of the completed VB2/air battery is reported. We show that using the zinc/air cell as a test bed is useful to provide a consistent configuration to study the performance of the high-energy high capacity nanoscopic VB2 anode.
Vanadium diboride as an anode has among the highest volumetric charge capacity of any anode material. This protocol introduces a method for studying this fascinating material. Metallic zinc has been the predominant anode material in aqueous primary systems due to zinc metal’s high two-electron volumetric and gravimetric charge storage capacities of 5.8 kAh L-1 and 820 Ah kg-1, respectively.* The zinc-carbon battery, known as the Leclanché cell, was first introduced in the 19th century, combining a zinc anode with a manganese dioxide (carbon current collector) cathode in a chloride electrolyte1. The common alkaline battery utilizes the same couple, but replaces the chloride electrolyte with an aqueous alkali hydroxide electrolyte. Together zinc-carbon and alkaline batteries comprise the majority of primary batteries sold 1. When the manganese dioxide cathode in the alkaline cell is replaced by an air cathode, substantially higher energy storage capacities are achieved. This zinc-air battery utilizes oxygen from the air, and is commonly found in hearing-aid batteries 1-3.
Our search for higher capacity battery storage has focused on materials that can transfer multiple electrons per molecule 4-11. Among the wide variety of redox couples we have explored, VB2 stands out as an extraordinary alkaline anode capable of releasing 11 electrons per VB2, with volumetric and gravimetric capacities of 20.7 kAh L-1 and 4060 Ah kg-1 respectively.* In 2004, Yang and co-workers reported the discharge of VB2, but also documented the extended domain in which VB2 is susceptible to corrosion in alkali media 12. In 2007, we reported that a coating on the VB2 particles prevents this corrosion13, leading to demonstration of the VB2/air battery in 2008 14.
In this paper, we present a protocol used to investigate new metal/air systems employing the technology previously developed for the zinc/air cell as applied to the VB2/air cell. A nanoscopicVB2 anode is presented as a high-energy high-power density anode capable of exhibiting an eleven-electron oxidation reaction approaching the theoretical intrinsic capacity of 4060 Ah kg-1 at increased battery voltage and battery load capability. The VB2/air couple uses an alkaline electrolyte of KOH/NaOH, employing the same oxygen air cathode extracted from the zinc/air cell 1. The carbon electrocatalyst cathode is not consumed during discharge.
There exists a need for a greater understanding the VB2 /air system in order to further improve cell performance. The properties and performance of nanoscopic VB2 materials can be explored using the cell configuration of the zinc/air cell 15,16. Electrochemical testing can be performed for nanoscopic VB2 to compare performance through percent efficiency at various rates.
1. Preparation Nano-VB2
Nanoscopic VB2 is directly synthesized from elemental vanadium and boron via ball-milling in a 1:2 mole ration.
2. Preparation of Electrolyte
3. Disassembling Zinc/Air Batteries
See the table of regents and materials for details about battery manufacturer and model number.
4. Preparation of a 5 mAh Working Electrode with a 70/30 dry mixture
5. VB2-Air Cell Assembly – Dry Method
6. Nano-VB2/Air Cell Testing
Electrochemical testing is performed to determine the performance of VB2/air batteries. The results obtained for multiple cells provide evidence for reproducibility of the cell performance. Figure 1 compares the VB2/air batteries during a 3,000 ohm (left) and 1,000 ohm (right) discharge. Note that the discharge voltage, as well as the fraction of the 4,060 Ah kg-1 intrinsic capacity is higher with the nanoscopic VB2 anode compared to the macroscopic VB2 anode cell, and that this cell also retains higher efficiency at higher rate (comparing the 1,000 to 3,000 ohm loads) with this anode. The labeling of cells is as follows, for example I-FC000, where I is an arbitrary constant, FC stands for a full cell, and 000 is the test number. Figure 2 validates that blank, Zn or Zn/VB2 cells discharge is as expected. Figure 3 shows the zirconia overlayer present on the VB2 nanoparticles. Figure 4 photographs consecutive stages of the Zinc/air battery disassembly, and Figure 5 stages of the replacement anode fabrication. Finally, Figure 6 presents correct gluing of the cell to ensure good connections on both the anode and cathode to establish a good cell seal. The working electrode may also be fabricated using alternative processes to the dry method. For example, the VB2 may be mixed as an aqueous dispersion (slurry), and then evenly distributed over the stainless current collector, or as seen in Figure 7, cast as a solid VB2 disc with a Kynar binder on a stainless steel shim.
Figure 1. Data obtained for relatively slow discharge times (3,000 Ω and 1,000 Ω). Cells are typically discharged at 3,000 Ω to provide comparisons between experiments and cell performance.
Figure 2. Validation that cleaned Panasonic 675 Zinc/Air batteries provide a useful test bed for the nano-VB2 anode; compared to the macro-VB2 anode are an empty anode cell (top left), anode containing only packing carbon- no VB2 (bottom left), anode with Zn- no VB2 (top right), and anode with a composite of Zn and VB2 (bottom right). Top Left shows the discharge of a fully gutted and closed Zinc/Air cell without any anode material (empty blank cell, no carbon and without VB2) present with a typical nano-VB2 discharge for comparison. Top Right shows the discharge of cell containing 20mAh of the zinc anode material. The zinc cell is used to validate the VB2 cell configuration and uses the original zinc as reintroduced back into the cell. Bottom Left provides an example of a discharge containing only the appropriate amount of graphitic carbon black for a typical VB2 discharge with a typical nano-VB2 discharge for comparison. Bottom Right shows a nano-VB2 cell with the presence of purposely added zinc in the anode, and the observed distinct voltage discharge plateaus are evidence that the VB2-alone anode does not contain a significant zinc contaminant. The left figure validates that the blank cell exhibits an upper limit of less than 4% of the measured VB2 containing anode capacity.
Figure 3. High resolution SEM image of the zirconia coated VB2.
Figure 4. Correct way to disassemble a Zinc/Air battery for VB2-Air Cell Assembly. Figures 4a and 4b show a factory cells prior to opening. Figure 4c and 4d demonstrate the initial cut and opening of the battery. Figure 4e (also labeled Top) and Figure 4f (Bottom) provides a view of the opened cell prior to removing the Zinc anode material. Upon removal the membrane is cleaned and wiped out as shown in Figure 4g. Figure 4h displays the area where the VB2 anode is fabricated.
Figure 5. Fabrication of the working electrode. Figure 4a provides an example of how this is prepared. When constructing the electrodes it is important that no cracks or clumps are visible; the electrode surface should appear smooth as shown in Figure 4b.
Figure 6. Correct gluing of cells to ensure good connections on both the anode and cathode and a good seal on the cell.
Figure 7. The working electrode may also be fabricated using alternative processes to the dry method. Above is an example of cast nano-VB2 anode preparation on a stainless steel shim.
*Intrinsic volumetric specific capacity is calculated as ndF/MW, from the molecular weight, MW (such as for Zn or VB2 respectively MW = 0.0654 kg or .0726 kg mol-1), the number of electrons transferred, (such as for Zn or VB2 n = 2 or 11), the density, d (such as for Zn or VB2 d = 7.1 kg liter-1 or 5.1 kg liter-1), and Faraday’s constant of 28.8 Ah mol-1.
Construction of the VB2/air battery in this way provides the ability to study and probe the eleven electrons per molecule charge transfer that occurs, allowing the possibility for a new high capacity battery. If obtained results do not demonstrate reproducible results, ensure that all of the zinc anode material was removed from the battery, that there is an even dispersion of active material on the cap, and that the cells are properly glued without any leaks. If a problem continues to occur, ensure that the batteries are Panasonic 675 Zinc/Air cells made in Japan not Germany. The gasket of a Japanese cell should appear opaque and attached to the separator as one entity. If the gasket is separate and blue the cells are German. Limitations to this technique include not having the ability to control the humidity of cell, although previously there have been no issues observed. When constructing a VB2/air battery, there are several critical steps outlined in the Protocol section: opening of the cell, removing the zinc material, preparation of the anode material and insertion in the cell, closing the cell carefully, and proper gluing to ensure that there are no leaks and a good electrical connection.
X-ray powder diffraction is a convenient technique to confirm 15,16 that the starting reactants (elemental vanadium and boron) are not present in the synthesized nano-VB2. Transmission electron microscope (TEM) images establish that the zirconium oxide coating is evenly covering the VB2 particles. While disassembling and assembling the Zinc/Air batteries it is important to make sure that the casing remains intact and that the membrane and separator are not cut or damaged in anyway. During discharge, relatively small differences in the voltages and capacities observed for repeated cells may result from small mass differences, as well as from using a cell configuration that did not result in uniform pressure applied for each cell.
The authors have nothing to disclose.
The authors would like to acknowledge the National Science Foundation Award 1006568 for funding this project.
MATERIALS | |||
Boron | Alfa Aesar | 11337 | |
Diethyl Ether | J.T. Baker | 9244-06 | 4L |
Epoxy | Loctite | Heavy Duty 5 min setting time | |
Isopropyl Alcohol | |||
Panasonic 675 Zinc/Air cell | Panasonic | PR675H | Made in Japan (not German) |
C-NERGY Super C65 | Timcal | Graphitic carbon black | |
Vanadium | Aldrich | 262935 | |
Vanadium Diboride | American Elements | 12007-37-3 | |
Zirconium Chloride | Spectrum | Z20001 | |
EQUIPTMENT | |||
50-mL round bottom flask | Fisher Scientific Co LLC | CG151001 | |
Diagonal cutting pliers | Hardware store | ||
Hot/stir plate | IKA | C-MAG HS 7 | |
Glove box | Labconco | Precision Basic | |
Ten 10-mm tungsten carbide balls | Lab Synergy | 55.0100.08 | |
Tungsten carbide milling jar | Lab Synergy | 50.8600.00 | |
Razor blade | Hardware store | ||
Retsch PM 100 planetary ball mill | Retsch | 205400003 | |
Stir bar | VWR International | 58947-140 |