Name: extending the lifespan of soluble lead flow batteries with a sodium acetate additive
Uploaded: 2019-01-07T14:00:00
Description: Watch this Scientific Journal Video about Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive at JoVE.com

This work was supported by the Ministry of Science and Technology, R.O.C., under the funding number of NSC 102-2221-E-002-146-, MOST 103-2221-E-002-233-, and MOST 104-2628-E-002-016-MY3.

1. Construction of a SLFB Beaker Cell with a Sodium Acetate Additive
NOTE: This section describes the procedure to construct a SLFB beaker cell with an additive for long-term cycling experiment. The protocol includes the electrolyte preparation with and without additive, electrode pretreatment, cell assembly, and efficiency calculations.
<ol>
	<li>Preparation of lead methanesulfonate (1 L, 1 M as an example)
	<ol>
		<li>In the fume hood, add 274.6 g of methanesulfonic acid (...

<ol>
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The influence of conditions on battery performance.</a> Journal of Power Sources. 149, 96-102 (2005).</li><li>Hazza, A., Pletcher, D., Wills, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+flow+battery-a+lead+acid+battery+based+on+an+electrolyte+with+soluble+lead+(II).+IV.+The+influence+of+additives.">A novel flow battery-a lead acid battery based on an electrolyte with soluble lead (II). IV. The influence of additives.</a> Journal of Power Sources. 149, 103-111 (2005).</li><li>Pletcher, D., Zhou, H., Kear, G., Low, C. T. J., Walsh, F. C., Wills, R. G. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+flow+battery-A+lead-acid+battery+based+on+an+electrolyte+with+soluble+lead+(II).+V.+Studies+of+the+lead+negative+electrode.">A novel flow battery-A lead-acid battery based on an electrolyte with soluble lead (II). V. Studies of the lead negative electrode.</a> Journal of Power Sources. 180 (1), 621-629 (2008).</li><li>Pletcher, D., Zhou, H., Kear, G., Low, C. T. J., Walsh, F. C., Wills, R. G. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+flow+battery-A+lead-acid+battery+based+on+an+electrolyte+with+soluble+lead+(II).+Part+VI.+Studies+of+the+lead+dioxide+positive+electrode.">A novel flow battery-A lead-acid battery based on an electrolyte with soluble lead (II). Part VI. Studies of the lead dioxide positive electrode.</a> Journal of Power Sources. 180 (1), 630-634 (2008).</li><li>Li, X., Pletcher, D., Walsh, F. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+flow+battery:+a+lead+acid+battery+based+on+an+electrolyte+with+soluble+lead+(II).+Part+VII.+Further+studies+of+the+lead+dioxide+positive+electrode.">A novel flow battery: a lead acid battery based on an electrolyte with soluble lead (II). Part VII. Further studies of the lead dioxide positive electrode.</a> Electrochimica Acta. 54 (20), 4688-4695 (2009).</li><li>Krishna, M., Fraser, E. J., Wills, R. G. A., Walsh, F. 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Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stabilizing+the+electrodeposit-electrolyte+interphase+in+soluble+lead+flow+batteries+with+ethanoate+additive.">Stabilizing the electrodeposit-electrolyte interphase in soluble lead flow batteries with ethanoate additive.</a> Electrochimica Acta. 263, 60-67 (2018).</li><li>Oury, A., Kirchev, A., Bultel, Y., Chainet, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=PbO2/Pb2++cycling+in+methanesulfonic+acid+and+mechanisms+associated+for+soluble+lead-acid+flow+battery+applications.">PbO2/Pb2+ cycling in methanesulfonic acid and mechanisms associated for soluble lead-acid flow battery applications.</a> Electrochimica Acta. 71, 140-149 (2012).</li><li>Oury, A., Kirchev, A., Bultel, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Potential+response+of+lead+dioxide/Lead+(II)+galvanostatic+cycling+in+methanesulfonic+acid:+a+morphologico-kinetics+interpretation.">Potential response of lead dioxide/Lead (II) galvanostatic cycling in methanesulfonic acid: a morphologico-kinetics interpretation.</a> Journal of The Electrochemical Society. 160 (1), A148-A154 (2013).</li></ol>

This paper describes an economical method to extend the cycle life of SLFBs: by employing NaOAc agent as an electrolyte additive. A batch of fresh graphite electrodes and nickel plates are preprocessed as aforementioned in Step 1 before long-term cycling experiments. Because inconsistency among commercial carbon electrodes may cause performance deviation of the SLFBs, the physical/chemical pretreatment in Step 1.4 is critical to remove surface residues. The second part of Step 1.4 is employing electrochemical methods to ...

Renewable energy sources including solar and wind have been developed for decades, but their intermittent nature poses great challenges. For a future power grid with renewable energy sources incorporated, grid stabilization and load leveling are critical and can be achieved by integrating energy storage. Redox flow batteries (RFBs) are one of the promising options for grid-scale energy storage. Traditional RFBs contain ion-selective membranes separating anolyte and catholyte; for example, the all-vanadium RFB has shown to operate with high efficiency and a long cycle life1,2. However, their market share as energy storage is very limited in part due to the expensive comprising materials and ineffective ion-selective membranes. On the other hand, a single-flow soluble lead flow battery (SLFB) is presented by Plectcher et al.1,2,3,4,5. The SLFB is membrane-less because it has only one active species, Pb(II) ions. Pb(II) ions are electroplated at the positive electrode as PbO2 and the negative electrode as Pb simultaneously during charging, and convert back to Pb(II) during discharging. A SLFB thus needs one circulation pump and one electrolyte storage tank only, which in turn can potentially lead to reduced capital and operational cost compared to conventional RFBs. The published cycle life of SLFBs, however, is so far limited to less than 200 cycles under normal flow conditions6,7,8,9,10.
Factors leading to a short SLFB cycle life is preliminarily associated with deposition/dissolution of PbO2 at the positive electrode. During charge/discharge processes, the electrolyte acidity is found to increase over deep or repeated cycles11, and protons are suggested to induce the generation of a passivation layer of non-stoichiometric PbOx12,13. The shedding of PbO2 is another phenomenon related to SLFB degradation. Shed PbO2 particles are irreversible and can no longer be utilized. The coulombic efficiency (CE) of SLFBs consequentially declines because of imbalanced electrochemical reactions as well as accumulated electrodeposits at both electrodes. To extend cycle life of SLFBs, stabilizing the pH fluctuation and electrodeposit structure are critical. A recent paper demonstrates an enhanced performance and extended cycle life of SLFBs with addition of sodium acetate (NaOAc) in methanesulfonic electrolyte11.
Here, a detailed protocol for employing NaOAc as an additive to the methanesulfonic electrolyte in SLFBs is described. The SLFB performance is shown to be enhanced and the lifespan can be extended by over 50% in comparison to SLFBs without NaOAc additives. In addition, procedures for throwing index (TI) measurement are illustrated for the purpose of quantitative comparison of additive effects on electrodeposition. Finally, a scanning electron microscopy (SEM) sample preparation method for electrodeposit on SLFB electrodes is described and the additive impact on electrodeposit is manifested in acquired images.

<table>
	<tbody>
		<tr>
			<td>70 mm cellulose filter paper</td>
			<td>Advance</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Autolab</td>
			<td>Metrohm</td>
			<td>PGSTA302N</td>
			<td></td>
		</tr>
		<tr>
			<td>BT-Lab</td>
			<td>BioLogic</td>
			<td>BCS-810</td>
			<td></td>
		</tr>
		<tr>
			<td>commercial carbon composite electrode</td>
			<td>Homy Tech,Taiwan</td>
			<td></td>
			<td>Density 1.75 g cm-3, and electrical conductivity 330 S cm-1</td>
		</tr>
		<tr>
			<td>Diamond saw</td>
			<td>Buehler</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrochloric Acid</td>
			<td>SHOWA</td>
			<td>0812-0150-000-69SW</td>
			<td>35%</td>
		</tr>
		<tr>
			<td>Lead (II) Oxide</td>
			<td>SHOWA</td>
			<td>1209-0250-000-23SW</td>
			<td>98%</td>
		</tr>
		<tr>
			<td>Lutropur MSA</td>
			<td>BASF</td>
			<td>50707525</td>
			<td>70%</td>
		</tr>
		<tr>
			<td>nickel plate</td>
			<td>Lien Hung Alloy Trading Co., LTD., Taiwan,&#160;</td>
			<td></td>
			<td>99%</td>
		</tr>
		<tr>
			<td>Potassium Nitrate</td>
			<td>Scharlab</td>
			<td>28703-95</td>
			<td>99%</td>
		</tr>
		<tr>
			<td>Scanning electron microscopy</td>
			<td>JEOL</td>
			<td>JSM-7800F</td>
			<td>at accelerating voltage of 15 kV</td>
		</tr>
		<tr>
			<td>Sodium Acetate</td>
			<td>SHOWA</td>
			<td>1922-5250-000-23SW</td>
			<td>98%</td>
		</tr>
		<tr>
			<td>water purification system</td>
			<td>Barnstead MicroPure</td>
			<td></td>
			<td>&#160;18.2 M&#937;&#160;&#8226; cm</td>
		</tr>
	</tbody>
</table>

extending the lifespan of soluble lead flow batteries with a sodium acetate additive

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate amount of sodium acetate (NaOAc) to the electrolyte, a cycle life extension of over 50% is demonstrated for SLFBs via long-term galvanostatic charge/discharge experiments. A higher quality of the PbO2 electrodeposit at the positive electrode is quantitatively validated for NaOAc-added electrolyte by throwing index (TI) measurements. Images acquired by scanning electron microscopy (SEM) also exhibit more integrated PbO2 surface morphology when the SLFB is operated with the NaOAc-added electrolyte. This work indicates that electrolyte modification can be a plausible route to economically enable SLFBs for large-scale energy storage.

To extend cycle life of SLFBs, NaOAc is supplied as an electrolyte additive. Cycling performance of SLFBs with and without NaOAc additive are examined in parallel, and results are shown in Figure 3. For easier quantitative comparison of cycle life, we define the &#34;death&#34; of a SLFB as when its CE is lower than 80% under continuous galvanostatic charge/discharge. Figure 3a and 3b show that approximately 50% ...

Watch this Scientific Journal Video about Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive at JoVE.com

Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive

A protocol for the construction of a soluble lead flow battery with an extended lifespan, in which sodium acetate is supplied in the methanesulfonic electrolyte as an additive, is presented.

In this report, we present a method for the construction of a soluble lead flow battery (SLFB) with an extended cycle life. By supplying an adequate ...

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