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>
	<li>Soloveichik, G. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flow+batteries:+current+status+&amp;+trends.">Flow batteries: current status &amp; trends.</a> Chemical Reviews. 115 (20), 11533-11558 (2015).</li><li>Ravikumar, M. 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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. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Developments+in+soluble+lead+flow+batteries+and+remaining+challenges:+An+illustrated+review.">Developments in soluble lead flow batteries and remaining challenges: An illustrated review.</a> Journal of Energy Storage. 15, 69-90 (2018).</li><li>Lin, Y. -. T., Tan, H. -. L., Lee, C. -. Y., Chen, H. -. 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>

We have nothing to disclose.

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 ...

This method extends the cycle life of soluble lead flow batteries by employing sodium acetate as an electrolyte additive, which is an economical and effective approach. In addition, the beaker cell design used in this method is convenient for studying the effects of the electrolyte additive on single flow redox flow batteries. Demonstrating the procedure will be Yong-Hong Lai, Ho-Wei Chan, and Kai-Rui Pan, two grad students and an undergraduate student from my laboratory.To begin, in a fume hood, pour 274.6 grams of 70%methanesulfonic acid into a beaker, and start stirring it with a stir bar. Add 300 milliliters of deionized water, and continue stirring for one to two minutes to thoroughly mix the solution. Then, add 223.2 grams of 98%lead II oxide to the stirring solution in spatula tip-sized increments.Wait for each portion to dissolve completely before adding the next one. Filter the resulting lead methanesulfonate solution three times. Dilute it to one liter with deionized water, and stir it for two to three hours to obtain a one-molar solution.Next, combine in a beaker 20.595 grams of 70%MSA, 150 milliliters of one-molar lead methanesulfonate, and 1.23 grams of sodium acetate. Dilute the mixture to 300 milliliters with deionized water, and stir it for one to two minutes to make an electrolyte solution with sodium acetate as an additive. Next, polish a bare graphite electrode with P100-grit aluminous sandpaper until no impurities are visible.Rinse the polished electrode with deionized water. Then, add 20.83 grams of 35%hydrochloric acid to 200 milliliters of deionized water, and stir well to obtain a one-molar solution of hydrochloric acid. Soak the graphite electrode in the solution for at least eight hours.Thoroughly rinse the graphite electrode with deionized water, and dry it with a low-lint laboratory wipe. Polish a nickel electrode with P100-grit aluminous sandpaper, rinse it with deionized water, and dry it in the same way. Then, wrap polytetrafluoroethylene tape around one side of each electrode, leaving a portion exposed to be connected to the battery tester.Dissolve 3.03 grams of potassium nitrate in 300 milliliters of deionized water. Immerse the exposed sides of both electrodes in this 0.1-molar potassium nitrate solution. Also, place a reference silver-silver chloride electrode in the solution.Then, connect the electrodes to a potentiostat. The graphite working electrode will be the positive electrode, and the nickel counter electrode will be the negative electrode. Apply a potential of 1.80 volts versus silver-silver chloride to the positive electrode for five minutes.Then, apply a potential of negative one volt versus silver-silver chloride to the positive electrode for two minutes to finish the pretreatment. Rinse and dry the electrodes afterwards. Then, connect the pretreated electrodes to a custom electrode positioning board.Place the positioning board on a beaker equipped with a stir bar, and fill the beaker with electrolyte until the solution reaches the appropriate level. Place the beaker assembly on a stirring hot plate, and connect a battery tester to the electrodes. Cover the beaker cell with plastic wrap to prevent evaporation before performing the battery test.Stir the mixture at about 200 rpm during the test. To start the throwing index measurement procedure, weigh two positive electrodes and record their masses. Place a negative electrode in the center position of a Haring-Blum cell apparatus.Place one positive electrode in the assembly near the negative electrode. Place the other positive electrode at a distance several times greater than the distance between the first positive electrode and the negative electrode. Immerse the electrode in the electrolyte of interest, and connect them to a battery tester.Start the test by charging the battery assembly with a constant current density of 20 milliamperes per square centimeter for 30 minutes. After performing the desired charge-discharge cycles, rinse the positive electrodes with deionized water and allow them to dry in ambient air overnight. Then, weigh the positive electrodes, and calculate the amount of metal plated on each electrode.Repeat this process at various linear distance ratios, and generate a throwing index diagram. To prepare an electroplated graphite electrode for SEM, first rinse it with deionized water and allow it to dry at room temperature. Then, use a diamond saw to carefully slice the electrode into samples of the desired size.Cold-mount an electrode sample, fix it in a polisher, and mechanically polish it with 14-eight-and three-millimeter silicon carbide sandpaper in sequence. Rinse the sample with deionized water, and dry it with nitrogen gas after each polishing. Then, polish the sample with a one-millimeter diamond suspension, followed by a slurry of 0.05-millimeter alumina in deionized water.After that, deposit a layer of platinum on the polished sample, and attach it to the sample platform with copper tape. Acquire SEM images of the electroplated material. Adding sodium acetate to the SLFB electrode extended the charge-discharge cycle lifetime by about 50%Adding sodium acetate also improved the throwing characteristics at the positive electrodes, as indicated by the shallower slope in a throwing index diagram.Sodium acetate had no significant effect on the plating behavior at the negative electrode. SEM images of positive electrodes electroplated with lead IV oxide in electrolyte with and without sodium acetate showed that the additive corresponded to a smoother lead IV oxide surface with fewer defects. Impurities are detrimental to the performance of SLFBs.Make sure that lead oxide is completely dissolved in the MSA, and filter out all residual solids before using the electrolyte. Once the plated electrode sample is harvested, other material scalarization techniques such as EBSD, nanoindentation, or x-ray diffraction can be performed to gain insight into the additive's effect on electrodeposition. Remember to prepare the electrolyte in a fume hood because the gas released during this procedure can be hazardous.

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JoVE Journal

Chemistry

9.0K Görüntüleme.  National Taiwan University. Bu yöntem, ekonomik ve etkili bir yaklaşım olan elektrolit katkı maddesi olarak sodyum asetat çalıştırarak çözünür kurşun akış pillerinin çevrim ömrünü uzatır. Buna ek olarak, bu yöntemde kullanılan beaker hücre tasarımı tek akış redoks akış pilleri elektrolit katkı etkileri nin incelenmesi için uygundur. Prosedürü gösteren Yong-Hong Lai, Ho-Wei Chan ve Kai-Rui Pan, iki yüksek lisans öğrencisi ve benim laboratuvar bir lisans öğrencisi olacaktır.B...