Leveraging Impurities in Recycled Lead Anodes For

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Sodium-Ion Batteries

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Janna Eaves-Ratherta, Kathleen Moyer-Vanderburgh,a, b Kody Wolfe,b, Murtaza Zohairb,c, Cary L. Pinta,c *

aDepartment of Mechanical Engineering, Vanderbilt University, Nashville, TN 37235

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bInterdisciplinary Materials Science Program, Vanderbilt University, Nashville, TN 37235

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cDepartment of Mechanical Engineering, Iowa State University, Ames, IA 50011

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*Corresponding Author: [email protected], 2529 Union Dr, Ames, IA 50011-2030

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 Leveraging Impurities in Recycled Lead Anodes For

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Sodium-Ion Batteries

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Abstract

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In recent years, the supply chain shock due to the rapid rise of the lithium-ion battery has made

alternative chemistries, such as sodium-ion batteries, appealing for low-cost and large-scale energy

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storage. Meanwhile, the falling popularity of lead acid batteries has potential consequences for the

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price of scrap lead and its penetration into waste streams. In this work, we upcycle lead alloys from

a used lead acid battery into a next-generation sodium-ion system for ultra-low-cost rechargeable
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batteries. Through evaluation of sodium storage capacity and rate capability, we study the rich

interplay of Pb-Sb-Sn microstructure and properties which can be controlled through simple heat

treatment of unrefined powders to reach a maximum specific capacity of 522 mAh.g-1. When
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cycled in the presence of glyme-based electrolytes, the ternary alloys nanostructure to facilitate an
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optimal balance of power and cycle life. These findings that demonstrate how defects can be

leveraged to improve performance bring exciting implications for reducing cost and mitigating

volume expansion in other high-value commodities, like tin or silicon.

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Keywords. sodium-ion battery, alloy, anode, recycling, energy storage, grid storage
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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 1. Introduction

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In 2012, lead acid battery (LAB) production accounted for 85% of global lead demand [1].

About 80% of this demand is met with secondary lead recycled from spent batteries, exemplifying

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a largely closed-loop manufacturing cycle which keeps the toxic heavy metal out of waste streams

[2]. Through the year 2022, demand for LABs is expected to continue growing alongside motor

vehicles at an average annual rate of 3%; however, rechargeable lithium ion batteries (LIBs)

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account for increasing shares of the transportation and grid storage sectors, growing at a much

faster annual rate of 9% [3,4]. Ultimately, with the price of LIBs expected to fall below $100/kWh

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by the year 2024 [5], a surge in electric vehicle popularity could destabilize the dominance of

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LABs, leading to a decline in the price of scrap lead [6], and a potential scenario where the broken

loop of lead recycling has a detrimental environmental impact on wastewater streams and natural
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resources.

Lead-based electrodes may find new life in low-cost, rechargeable sodium ion batteries (SIBs).

As the fourth most abundant element in the world, there exist over 47 billion tons of sodium
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precursor (soda ash) reserves worldwide, compared to 62 million tons of lithium. In turn, sodium
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is a target for the extreme scaling associated with penetration of grid-scale energy storage at

residential levels [7]. Alloying anodes such as Sn [8–13], Bi [14–18], Sb [16,19–23], and Pb

[14,24–28] have garnered much attention for application in sodium ion batteries due to high
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specific capacities and low operating voltages. Since Jow et al first established reversible alloying

of sodium with lead (Pb) in 1987, the material was largely excluded from rechargeable battery
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design due to toxicity concerns. Recently, Darwiche et al studied the reversible alloying of Pb with

sodium using diglyme as the electrolyte solvent, observing capacity retention of 464 mAh/g after
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 50 cycles in half cells [24]. These findings re-established lead as a promising anode material,

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despite being relatively under-explored.

In this work, we seek to establish a pathway for the recycling of Pb-based materials directly

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from used LABs. In this regard, recycled materials unlike raw pure materials contain impurities

which can be troublesome for practical rechargeable battery design. Within the growing body of

research in recycled battery cathodes[29–32] and alloying anodes[33–36], there is little

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understanding of the effect of residual impurities on electrochemical performance. In light of a

recent analysis by Ciez and Whitacre showing that direct recycling of electrode powders has

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potential to reduce greenhouse gas emissions in battery manufacturing at competitive costs[37],

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studies of impurity impact are imperative to improve recycling initiatives. Our work demonstrates

that recycled Pb alloys containing antimony (Sb) and tin (Sn) can be thermally processed to control
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the stability, rate performance, and storage capacity of sodium battery anodes. This highlights the

ample potential in defect engineering of recycled and high-value materials for next-generation

energy storage devices.

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2. Materials & Methods

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2.1. Pb Recycling. A previously used lead acid battery in fair condition was recovered from a

totaled vehicle. The battery was opened and dismantled to recover Pb materials. After draining
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the cell of sulfuric acid electrolyte, the components were neutralized by soaking in sodium

bicarbonate solution. Then, the spongy lead from anode plates was scraped off before melting

down the lead alloy in a smelting furnace above its melting point of ~330oC. Remaining lead
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oxides and sulfates floated to the surface and were removed with the dross before cooling slowly

in the furnace. Recycled Pb powder was produced by sanding the resulting ingot with a file or
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220-grit SiC-based sand paper and sifting the shavings through a 325-mesh stainless steel sieve.

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 The powder was neutralized a second time by soaking in sodium carbonate solution for ~12 hours

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before rinsing and drying under vacuum. At this point, powders undergoing heat treatment were

annealed in a tube furnace at 430oC in reducing atmosphere for 30 minutes or 280oC for 2 hours

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and cooled slowly to room temperature. Heat treated powders were immediately processed into

slurries and incorporated into coin cells within one week to avoid the recurrence of aging.

2.2. Coin Cell Assembly. Anodes were prepared via slurry casting from an aqueous solution of

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either the prepared powder or 325 mesh elemental Pb (Sigma Aldrich >99%, trace metals basis)

with 2 wt% carbon black (TIMCAL Super C45) additive, 4 wt% sodium carboxymethyl cellulose

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(CMC) binder, and 1 wt% xanthan gum as a viscosity modifier. The anode slurry was applied to

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a carbon coated aluminum current collector and dried in a vacuum oven at 80oC for 24 hours before

half cell construction. Active material loadings were between 4.5-5.5 mg/cm2. Half cells consisted
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of the Pb electrode, two CelgardTM 2325 separators, and a sodium metal reference electrode (Sigma

Aldrich 99.95%) housed in CR2032 coin cells. The electrolyte was 1M NaPF6 (99+%, Alfa Aesar)

in diethylene glycol dimethyl ether (“diglyme”, >99.5%, Sigma Aldrich). Before electrolyte
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synthesis, NaPF6 was dried at 100oC overnight on a hotplate in the glovebox and diglyme was

dried over 4 Å molecular sieves for at least 48 hours. Electrolytes were used within 48 hours of
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preparation. Electrochemical Testing: Galvanostatic charge/discharge tests were performed on an

8 Channel MTI battery Analyzer between voltages of 0.00 to 1.00 V with the sodium metal
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electrode as the reference. All cells were cycled at a low rate of C/10 during the first cycle then

brought to the testing rate. C-rates were determined based on the theoretical capacity of pure Pb:
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485 mAh.g-1.
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 2.3. X-ray Diffraction. Diffraction spectra were taken on a Rigaku SmartLab X-Ray

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Diffractometer. Background diffraction was subtracted from the sample signal and

crystallographic information was obtained through the Rigaku Data Analysis software.

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2.4. Imaging: Coin cells were de-crimped, the electrode of interest rinsed twice in dry dimethyl

ether (DME), and stored in a sealed vial for transport to SEM. Samples were exposed to air during

transfer. Imaging was conducted using a Zeiss Merlin SEM with EDS detector.

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3. Results and Discussion

3.1 Recycled Alloy Characterization

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Pb-based powder was directly recycled from a used LAB. As depicted in Figure 1a, the

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used anode grid plates were neutralized, cleaned of PbO2/PbSO4 sludge, and smelted above 330oC

for 10 minutes to form a Pb-based alloy ingot. After removing the dross, the melt was furnace-
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cooled and aged at room temperature for approximately 12 months. Ageing of lead-antimony (Pb-

Sb) alloys is known to result in the precipitation of fine, Sb-rich β-phase particles within the Pb-

rich α-phase matrix and has been previously studied for its hardening effects. The aged alloy
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enables evaluation of a very fine microstructure, which can be subsequently heat-treated to restore
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the equilibrium morphology as predicted by the Pb-Sb-Sn phase diagram [38]. To establish the

alloy composition obtained from the recycled Pb electrodes, quantitative energy dispersive x-ray

spectroscopy (EDS) analysis was performed on a portion of the aged, recycled Pb ingot prepared
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by water-cooled sanding followed by polishing with 1 μm and 35 nm alumina slurry. The map

spectra of three random areas were averaged to find that the alloy contains 73.1 ± 0.7 % Pb, 21.3
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± 0.6 % Sb, and 5.55 ± 0.05 % Sn, corresponding to a hypereutectic composition (Figure 1b). An

antimony concentration of 21 at% is slightly higher than reported values for grid alloys, which
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typically range from 0.5-12% depending on the brand, application, and year of manufacture

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 [39,40], but may reflect the history of the used battery from whence it came. As antimony is a

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more noble metal than lead, it resists corrosion at positive electrodes, while lead is first to dissolve

from the current collector grids [41]. The influence of grid health on microstructural and

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electrochemical properties of the recycled alloy could be an interesting area for further study.

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Figure 1: Process for direct recycling of Pb alloy powder from a used lead acid battery. A) Anode plates are cleaned, smelted, and
aged as an ingot; B) EDS spectrum for a flat, polished section of the ingot acquired at 20kV; C) Optical microscope image of Pb
alloy filings; D) schematic phase diagram based on [42] showing the regimes of heat treatment of the Pb alloy at the measured
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composition; E-G) EDS maps of the aged and heat treated particles acquired at 20 kV, overlaid over SEM images.

Pb alloy powder with particle size <325 mesh was produced from the ingot by shaving

and sieving, resulting in oblong particles with sharp edges (Figure 1c). The powders were then
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heat treated in a tube furnace under reducing atmosphere at 430oC for 30 minutes or 280oC for 2

hours and cooled slowly to room temperature. Due to the relatively low concentration of tin, we
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approximate alloy rehomogenization in the context of the binary Pb-Sb phase diagram. [42] The

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 ternary Pb-Sb-Sn phase diagram outlines the existence of Pb, Sb, Sn, and Sb-Sn, but there is very

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little solid solubility for Sn in Pb and no ternary compounds are known [38]. A schematic phase

diagram based on [42] is included in Figure 1d, where the stars along the dotted line indicate the

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chosen heat treatment temperatures at the measured composition. Upon rehomogenization at

temperatures exceeding the liquidus line, the phase diagram would suggest that a Sb-rich β-phase

dendritic matrix is first to precipitate from the melt at hypereutectic concentrations, followed by

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formation of a lamellar eutectic structure between dendritic branches, with characteristic length

scale dictated by the cooling rate. As predicted, EDS performed on the aged particles revealed

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coarse, dendritic β-phase precipitates surrounded by a fine distribution of more Sb and Pb,

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indicating that significant ageing had occurred (Figure 1e). Upon ageing, the eutectic morphology

restructures over time, favoring spheroidal precipitates of β near dendritic boundaries [39]. After
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heating at 280oC for 2 hours and cooling slowly to room temperature (“PbR 280”), EDS maps

reveal the return of classical dendritic morphology in the form of small, branched Sb domains,

with a reduction of Sb concentration in the matrix (Figure 1f). Increasing the temperature to 430oC
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for 30 minutes (“PbR 430”) facilitated segregation of Sb into even larger β-phase dendrites (Figure

1g). Hot spots in Sn concentration appear to coincide with Sb dendrites and precipitates (Figure
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S2). Heat treated powders were immediately processed into slurries and incorporated into coin

cells within one week to avoid the recurrence of aging.

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The crystal structure of the aged, recycled Pb alloy (“PbR”) was compared to >99%

elemental Pb from Sigma Aldrich (“PbS”) using x-ray diffraction (XRD). Spectra were acquired
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before and after one full discharge at C/10 in a coin cell versus a sodium metal counter electrode

(Figure 2a). The numbered positions on the discharge curves in Figure 2a correspond to the
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numbered XRD patterns in Figure 2b. The results for micrometric lead purchased from Sigma

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 Aldrich confirm that the composition is mostly metallic Pb with some contamination by α-PbO,

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which is common in Pb manufacturing processes [1]. After sodiation, weak peaks corresponding

to Na15Pb4 emerge at 2θ = 37.8o and 63o, indicated by blue stars. The pattern for recycled Pb proves

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successful processing of metallic Pb with elimination of most α-PbO and other oxides or sulfates.

Additional peaks match most closely with Pb0.1Sb0.9, consistent with expectations for a Sb-rich α-

phase cooled at a finite rate. As with the commercial sample, alloying with sodium results in a

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peak at 37.8o, corresponding to Na15Pb4.

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Figure 2: XRD analysis of commercial, 325 mesh elemental Pb (Sigma Aldrich >99%, trace metals basis) compared with recycled
alloy powders in pristine and fully sodiated states. A) Galvanostatic discharge of Pb and Pb alloy at a rate of C/10 in coin cells
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versus sodium metal, with numbered circles to indicate charge state at time of B) ex-situ XRD measurements.

3.2. Electrochemical Comparisons of Recycled vs Refined Pb

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Recycled and purchased lead anodes were electrochemically characterized in half cells

versus sodium metal. In galvanostatic testing, the first cycle was measured at a current density of

C/10, while subsequent cycles were driven at C/2 (242.5 mA/gactive). For the purchased, refined
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lead, the first discharge capacity was 522 mAh.g-1 and the first charge capacity was 477 mAh.g-1.

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 While the first discharge includes contributions from irreversible SEI formation and intercalation

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in PbO, the charge capacity matches closely with the theoretical capacity of 485 mAh.g-1 for

Na15Pb4 [14]. In contrast, the aged, recycled alloy had a high first charge capacity of 497 mAh.g-

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1, suggesting that Sb and/or Sn are also active within the voltage window. Analyzing the

differential charge with respect to voltage for the second cycle provides further evidence for the

electrochemical activity of Sb. The major peaks, which represent nucleation of a new crystalline

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phase, are in good agreement with known voltages for NaPb3, NaPb, Na9Pb4, and Na15Pb4,

[14,24,25]; however, the recycled Pb also produces a broad discharge peak around 0.55 V,

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accompanied by two sharper charge peaks at 0.74 and 0.84 V. Such behavior is characteristic of

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Sb sodiation, in which an amorphous intermediate phase is formed during discharge while

desodiation proceeds through the definite evolution of Na3Sb to NaSb to Sb [23,43]. Analysis of
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the galvanostatic transients reveal that approximately 81 mAh/galloy is stored in these two charge

plateaus during the first cycle. With a concentration of 21 at%, or ~14 wt%, antimony in the alloy

and a theoretical capacity of 660 mAh/gSb, this result agrees well with the theoretical maximum
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contribution from Sb of 90 mAh/galloy.

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Figure 3: Comparison of first cycle behavior of commercial and recycled Pb-based anodes in half cells versus sodium metal. A)

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First galvanostatic cycle of off-the-shelf elemental Pb powder and B) recycled Pb powder at a rate of C/10; C-D) differential
charge plots corresponding to (A) and (B), respectively; E) results of galvanostatic intermittent titration to enable comparison of
solid state diffusion coefficient, which is proportional to the slope of voltage with respect to the square root of time (inset).

Early cycling behavior was further probed using galvanostatic intermittent titration
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technique (GITT) to minimize the role of mass transport through the interphase. By applying the

appropriate parameters for current density and rest time, the concentration gradient of Na+ across
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the cell is expected to approach quasi-steady-state, such that the system becomes reaction-rate

limited. More information regarding GITT is provided in the Supplementary Material. A C/10
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current (48.5 mA.g-1) was applied for 10 seconds, followed by a rest period of 300 seconds,

yielding the envelope patterns in Figure 2e. To first discuss the commercial Pb, a short plateau
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emerges early in sodiation, beginning at approximately 0.48 V, which corresponds to the formation

of NaPb3. In this regime, the width of the envelope is related to polarization, which continuously

narrows through the formation of NaPb at 0.37 V, and is suddenly reduced with the formation of
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Na9Pb4 at 0.19 V. These findings are consistent with polarization calculations performed by

Darwiche et al, who hypothesized that electrochemical gridding during the first cycle facilitated
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future sodiation [24]. In the case of aged, recycled Pb alloy, sodiation begins with a solid solution

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 regime at potentials between 1 V and 0.6 V vs Na/Na+. This cannot be attributed to the carbon

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additive, since both the recycled and commercial samples contained 2 wt% carbon black and this

feature does not appear in both sets of data, but may represent limited activity in the minority

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alloying element, Sn. In accordance with the binary Na-Sb phase diagram, it is unlikely that the

solid solubility of Na in Sb would be greater than 1 at%.[44] The first plateau beginning at 0.60

V corresponds to the sodiation of Sb through an amorphous intermediate phase, as previously

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described. This does not seem to be a result of mass transport limitation, since pulses along this

plateau still obey the linear relationship between potential and the square root of time defined by

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the Sand Equation for times much less than the characteristic diffusion time, and has been

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explained as a stress-balancing mechanism [23]. The following NaPb3 plateau is substantially

longer than that observed for the commercial counterpart, and the narrow envelope of the NaPb
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plateau beginning at 0.32 V implies less polarization than the formation of this phase in pure Pb.

For times much less than the characteristic diffusion time (t << r2/D) and small

concentration changes, there should be a linear relationship between potential, E, and the square
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root of time, t, which obeys Equation 1 [45]:

𝑅𝑇 |𝑖|
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𝐸𝑡 = ‒ 𝑡 + 𝐸𝑛
𝐹 0.5𝐹𝑐𝑛 𝜋𝐷

Equation 1
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where n designates the state before application of a current pulse, cn is the concentration of sodium

in the alloy, and En is the potential before the pulse [45]. This formula was applied to the two
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alloys at the same voltage, 0.33 V, which coincides with growth of NaPb. As shown in the inset

of Figure 2e, the plots obey a linear relationship, with an R-squared value of 0.994 for commercial

Pb and 0.992 for recycled. Although the exact diffusion constant cannot be determined explicitly,
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we assume similar electrode surface area and current density to calculate an effective diffusion

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 coefficient 3.62 times greater in recycled Pb. Details regarding this calculation are available in the

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Supplementary Material. From this result, we hypothesize that the increased interfacial surface

area between alloy phases in the recycled Pb intrinsically enhances solid state diffusion.

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3.3. Thermal Processing of Alloys to Control Electrochemical Properties

To support this argument of improved solid state diffusion, we evaluated the relationship

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between electrochemical performance and interfacial surface area between phases in the thermally

processed powders. Heat treatment of the Pb-Sb-Sn alloys enabled significant tuning of power and

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cycle life properties through manipulation of phase boundaries and microstructural stability.

Figure 4a compares the power performance of PbS with the recycled alloys at rates ranging from

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C/10 to 2C. Full galvanostatic traces at each rate are available in Figure S3 of the Supplementary
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Materials. The ranking of samples in order of discharge capacity retention is as follows: PbR 430

< PbS < PbR 280 < PbR. In cycle life tests over 50 cycles (Figure 4b), the order of capacity

retention is nearly reversed: PbR 280 < PbR < PbS < PbR 430. Although PbS tracks closely with
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PbR 280 in early cycles, it ultimately undergoes a recovery, reaching a local maximum in specific

capacity around cycle 45.

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In order to elucidate the performance trends summarized in Figure 4c, we performed post-

mortem analysis on the electrodes after undergoing power tests. We found that all of the electrodes
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had gradually self-assembled into a highly porous network supported by ligaments which increase

in average thickness as PbR280 < PbR < PbR 430 < PbS. Glymes are also known to cause gradual
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evolution of microstructure [26]. Wang et al concluded that ether solvent wets the electrode surface

well enough to penetrate pinholes left behind during desodiation, which eventually grow and force

rearrangement of the surrounding material [15]. In the case of PbR, nanoscale domains, high
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interfacial surface area, and expansion mismatch of the elemental components[43,46–48] may lead

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 to the development of many pinholes for diglyme ingress, creating a multitude of small pores. The

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thin ligaments greatly enhance solid state diffusion and power performance, but ultimately form a

fragile structure with reduced capacity retention. An additional mechanism for loss is suggested

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by the gradual disappearance of defined plateaus between 0.6 - 1.0 V in Figure S4, in combination

with the fragmentation of Sb precipitates observed in Figure S5; as Sb and Sn domains are stressed,

broken, and dispersed, the small size creates a larger barrier to nucleation of a second phase [43].

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The intermediate sample, PbR 280, evolved average strut thickness on par with the aged sample,

PbR, but exhibited rapid capacity loss. It was treated in a regime of the Sb-Pb binary phase diagram

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very near the liquidus line, which was expected to ripen existing precipitates without melting,

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forming blocky structures. The early failure could be related to domain size and shape effects

which maximize interfacial stress. In contrast, the fully rehomogenized PbR 430 demonstrated the
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best cycle life, but performed poorly at high discharge rates. The lower interfacial surface area and

extensive phase segregation resulted in behavior very similar to pure Pb, although contributions

from Sb and Sn secure a higher final specific capacity. Altogether, we demonstrate that battery
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performance is sensitive to elemental distribution in ternary alloys, and conventional metallurgical

heat treatment can be applied to balance power and cycle life. This work provides the basis for us
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to facilitate self-assembly of porous nanostructures with differing electrochemical characteristics

influenced by the original alloy microstructure, capable of both extending cycle life through
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accommodation of swelling and enhancing rate capability by reducing diffusion lengths.

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Figure 4: Summary of a) rate capability and b) cycle life at a rate of C/2 for pure lead compared to recycled, heat treated powders;
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c) relationship with average strut thickness measured from d) SEM images acquired during post-mortem analysis. Scale bar = 10
µm.

Conclusion

In this work we demonstrate that the recovery of Pb-based materials from LABs results in
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impurity phases that facilitate a rich interplay of alloy properties that can be tuned to manipulate
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final electrode and cell characteristics. The ternary Pb-Sb-Sn system is unique because the large

differences in assumed crystal structure and atomic radius of the elemental materials lead to very

limited solid solubility, except for the existence of a SbSn intermetallic compound. Thus, the
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constituents retain their independent electrochemical properties, but are modified by the size and

shape of domains, differential stresses, and interfacial surface area. In the presence of glyme-
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based electrolytes, the result is a tunable self-assembled nanostructured alloy phase with a high

specific capacity of 522 mAh.g-1. Although the final nanostructure enhances rate kinetics, GITT
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was used to show the enhancement of solid state diffusion in the early stages of cycling via

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 transport along interfaces. We show that, despite very high impurity levels in the recycled alloy,

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extra temporal and energy inputs for refinement were not only unnecessary, but would be

detrimental to cell performance. Heat treatment was utilized to modify alloy structure, and our

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findings indicate the time/temperature design space is extensive to produce optimal electrode

architectures. We envision this work to be applicable not only to Pb anodes, but other alloying

electrodes used in rechargeable batteries, such as tin or silicon. The approaches described in this

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work to leverage impurity phases to mitigate volume expansion provides a unique design space

for the design of next-generation low-cost, and high performance electrodes. However, in the

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specific case of lead alloys, the ability to produce low-cost stationary storage applications from

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recycled lead materials provides a sustainable pathway to mitigate the leaching of toxic lead into

wastewater streams and the environment as the transition from combustion powered to electric
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powered vehicles evolves.

Supplementary Material

Supplementary material is available and contains additional information regarding recycling

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procedures and galvanostatic intermittent titration technique (GITT) as well as additional

characterization results. This material is available free of charge via the Internet.
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Acknowledgments

J.E. acknowledges support from a NSF graduate fellowship under grant 1445197.
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Notes

The authors declare no competing financial interest.

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 ed
References

[1] D.J. Payne, A.D. Ballantyne, J.P. Hallett, D.J. Riley, N. Shah, Lead acid battery recycling

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for the twenty-first century, R. Soc. Open Sci. 5 (2016).

http://dx.doi.org/10.1098/rsos.171368 (accessed May 2, 2019).

[2] T.W. Ellis, A.H. Mirza, The refining of secondary lead for use in advanced lead-acid

ev
batteries, J. Power Sources. 195 (2010) 4525–4529.

https://www.sciencedirect.com/science/article/pii/S0378775310000467 (accessed

r
September 3, 2019).

[3] er
Freedonia Focus, Lead: United States, 2018. www.freedoniafocusreports.com (accessed

September 3, 2019).
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[4] Freedonia Focus, Batteries: United States, 2018. www.freedoniafocusreports.com

(accessed September 3, 2019).

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[5] A Behind the Scenes Take on Lithium-ion Battery Prices | BloombergNEF, (n.d.).

https://about.bnef.com/blog/behind-scenes-take-lithium-ion-battery-prices/ (accessed
tn

September 3, 2019).

[6] W. Liu, L. Chen, J. Tian, Uncovering the Evolution of Lead In-Use Stocks in Lead-Acid
rin

Batteries and the Impact on Future Lead Metabolism in China, Environ. Sci. Technol. 50

(2016) 5412–5419.
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[7] U.S. Geological Survey, U.S. Geological Survey 2019, 2019.

https://www.usgs.gov/centers/nmic/mineral-commodity-summaries (accessed September

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6, 2019).

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This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 [8] L. Baggetto, P. Ganesh, R.P. Meisner, R.R. Unocic, J.-C. Jumas, C.A. Bridges, G.M.

ed
Veith, Characterization of sodium ion electrochemical reaction with tin anodes:

Experiment and theory, J. Power Sources. 234 (2013) 48–59.

iew
[9] B. Zhang, G. Rousse, D. Foix, R. Dugas, D.A.D. Corte, J.-M. Tarascon, Microsized Sn as

Advanced Anodes in Glyme-Based Electrolyte for Na-Ion Batteries, Adv. Mater. 28

(2016) 9824–9830. https://doi.org/10.1002/adma.201603212.

ev
[10] Z. Li, J. Ding, D. Mitlin, Tin and Tin Compounds for Sodium Ion Battery Anodes: Phase

Transformations and Performance, Acc. Chem. Res. 48 (2015) 1657–1665.

r
https://doi.org/10.1021/acs.accounts.5b00114.

[11] er
W. Liu, X. Chen, C. Zhang, H. Xu, X. Sun, Y. Zheng, Y. Yu, S. Li, Y. Huang, J. Li,
pe
Gassing in Sn-anode sodium-ion batteries and its remedy by metallurgically pre-alloying

Na, ACS Appl. Mater. Interfaces. 11 (2019) 23207–23212.

https://doi.org/doi/10.1021/acsami.9b05005.
ot

[12] H. Ying, W.-Q. Han, Metallic Sn-Based Anode Materials: Application in High-

Performance Lithium-Ion and Sodium-Ion Batteries, Adv. Sci. 4 (2017) 1700298.

tn

https://doi.org/10.1002/advs.201700298.
rin

[13] Y.-M. Lin, P.R. Abel, A. Gupta, J.B. Goodenough, A. Heller, C.B. Mullins, Sn−Cu

Nanocomposite Anodes for Rechargeable Sodium-Ion Batteries, ACS Appl. Mater.

Interfaces. 5 (2013) 8273–8277. https://doi.org/doi/pdf/10.1021/am4023994.

ep

[14] L.D. Ellis, B.N. Wilkes, T.D. Hatchard, M.N. Obrovac, In Situ XRD Study of Silicon,

Lead and Bismuth Negative Electrodes in Nonaqueous Sodium Cells, J. Electrochem. Soc.
Pr

161 (2014) 416–421.

17

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 [15] C. Wang, L. Wang, F. Li, F. Cheng, J. Chen, Bulk Bismuth as a High-Capacity and

ed
Ultralong Cycle-Life Anode for Sodium-Ion Batteries by Coupling with Glyme-Based

Electrolytes, Adv. Mater. 29 (2017) 1702212. https://doi.org/10.1002/adma.201702212.

iew
[16] J.-S. Bridel, S. Grugeon, S. Laruelle, J. Hassoun, P. Reale, B. Scrosati, J.-M. Tarascon,

Decomposition of ethylene carbonate on electrodeposited metal thin film anode, J. Power

Sources. 195 (2010) 2036–2043.

ev
[17] J. Sottmann, M. Herrmann, P. Vajeeston, Y. Hu, A. Ruud, C. Drathen, H. Emerich, H.

Fjellvåšg, D.S. Wragg, How Crystallite Size Controls the Reaction Path in Nonaqueous

r
Metal Ion Batteries: The Example of Sodium Bismuth Alloying, Chem. Mater. 28 (2016)

2750–2756. er
pe
[18] F. Yang, F. Yu, Z. Zhang, K. Zhang, Y. Lai, J. Li, Bismuth Nanoparticles Embedded in

Carbon Spheres as Anode Materials for Sodium/Lithium-Ion Batteries, Chem. - A Eur. J.

22 (2016) 2333–2338.
ot

[19] H. Hou, M. Jing, Y. Yang, Y. Zhang, W. Song, X. Yang, J. Chen, Q. Chen, X. Ji,

Antimony nanoparticles anchored on interconnected carbon nanofibers networks as

tn

advanced anode material for sodium-ion batteries, J. Power Sources. 284 (2015) 227–235.
rin

[20] Z. Li, X. Tan, P. Li, P. Kalisvaart, M.T. Janish, W.M. Mook, E.J. Luber, K.L. Jungjohann,

C.B. Carter, D. Mitlin, Coupling In Situ TEM and Ex Situ Analysis to Understand

Heterogeneous Sodiation of Antimony, Nano Lett. 15 (2015) 6339–6348.

ep

https://doi.org/10.1021/acs.nanolett.5b03373.

[21] M. He, K. Kravchyk, M. Walter, M. V. Kovalenko, Monodisperse Antimony Nanocrystals

Pr

for High-Rate Li-ion and Na-ion Battery Anodes: Nano versus Bulk, Nano Lett. 14 (2014)

18

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 1255–1262. https://doi.org/10.1021/nl404165c.

ed
[22] J. Qian, Y. Chen, L. Wu, Y. Cao, X. Ai, H. Yang, High capacity Na-storage and superior

cyclability of nanocomposite Sb/C anode for Na-ion batteries, Chem. Commun. 48 (2012)

iew
7070.

[23] A. Darwiche, C. Marino, M.T. Sougrati, B. Fraisse, L. Stievano, L. Monconduit, Better

Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: An

ev
Unexpected Electrochemical Mechanism, J. Am. Chem. Soc. 134 (2012) 20805–20811.

https://doi.org/10.1021/ja310347x.

r
[24] A. Darwiche, R. Dugas, B. Fraisse, L. Monconduit, Reinstating lead for high-loaded
er
efficient negative electrode for rechargeable sodium-ion battery, J. Power Sources. 304
pe
(2016) 1–8.

[25] S. Komaba, Y. Matsuura, T. Ishikawa, N. Yabuuchi, W. Murata, S. Kuze, Redox reaction

of Sn-polyacrylate electrodes in aprotic Na cell, Electrochem. Commun. 21 (2012) 65–68.

ot

[26] C. Kim, H. Kim, M.K. Sadan, M. Jeon, G.B. Cho, T.H. Nam, K.K. Cho, J.H. Ahn, H.J.
tn

Ahn, A high rate and long-cycle-life anode based on micrometer-sized Pb powder for

sodium-ion batteries, J. Alloys Compd. 886 (2021) 161240.

rin

https://doi.org/10.1016/J.JALLCOM.2021.161240.

[27] B. Pandit, B. Fraisse, L. Stievano, L. Monconduit, M.T. Sougrati, Carbon-coated FePO4

ep

nanoparticles as stable cathode for Na-ion batteries: A promising full cell with a Na15Pb4

anode, Electrochim. Acta. 409 (2022) 139997.

https://doi.org/10.1016/J.ELECTACTA.2022.139997.
Pr

19

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 [28] V. Ahuja, S. Singh, R. Vengarathody, P. Senguttuvan, Room-Temperature Synthesis and

ed
Stable Na-ion Storage Performance of Two-Dimensional Mixed Lead-Bismuth

Oxychloride, J. Phys. Chem. C. 125 (2021) 17622–17628.

iew
https://doi.org/10.1021/ACS.JPCC.1C04463/ASSET/IMAGES/LARGE/JP1C04463_0005

.JPEG.

[29] H. Zou, E. Gratz, D. Apelian, Y. Wang, A novel method to recycle mixed cathode

ev
materials for lithium ion batteries, Green Chem. 15 (2013) 1183.

[30] H. Wang, J.F. Whitacre, Direct Recycling of Aged LiMn2O4 Cathode Materials used in

r
Aqueous Lithium-ion Batteries: Processes and Sensitivities, Energy Technol. 6 (2018)

2429–2437. er
pe
[31] D.S. Kim, J.S. Sohn, C.K. Lee, J.H. Lee, K.S. Han, Y. Il Lee, Simultaneous separation and

renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable

batteries, J. Power Sources. 132 (2004) 145–149.

ot

[32] Y. Weng, S. Xu, G. Huang, C. Jiang, Synthesis and performance of

Li[(Ni1/3Co1/3Mn1/3)1−xMgx]O2 prepared from spent lithium ion batteries, J. Hazard.

tn

Mater. 246 (2013) 163–172.

rin

[33] T. Kasukabe, H. Nishihara, K. Kimura, T. Matsumoto, H. Kobayashi, M. Okai, T.

Kyotani, Beads-Milling of Waste Si Sawdust into High-Performance Nanoflakes for

Lithium-Ion Batteries, Sci. Rep. 7 (2017) 42734.

ep

[34] A.K. Naskar, Z. Bi, Y. Li, S.K. Akato, D. Saha, M. Chi, C.A. Bridges, M.P. Paranthaman,

Tailored recovery of carbons from waste tires for enhanced performance as anodes in
Pr

lithium-ion batteries, RSC Adv. 4 (2014) 38213.

20

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 [35] D. Soo Jung, M.-H. Ryou, Y. Joo Sung, S. Bin Park, J. Wook Choi, Recycling rice husks

ed
for high-capacity lithium battery anodes, PNAS. 110 (2013) 12229–12234.

[36] H.D. Jang, H. Kim, H. Chang, J. Kim, K.M. Roh, J.-H. Choi, B.-G. Cho, E. Park, H. Kim,

iew
J. Luo, J. Huang, Aerosol-Assisted Extraction of Silicon Nanoparticles from Wafer

Slicing Waste for Lithium Ion Batteries, Sci. Rep. 5 (2015) 9431.

[37] R.E. Ciez, J.F. Whitacre, Examining different recycling processes for lithium-ion

ev
batteries, Nat. Sustain. 2 (2019) 148–156.

r
[38] J.P. Hilger, Hardening process in ternary lead-antimony-tin alloys for battery grids, J.

Power Sources. 53 (1995) 45–51.

[39]
er
S. Feliu, E. Otero, J.A. Gonzalez, The effect of ageing on the anodic corrosion of Pb-Sb
pe
alloys, J. Power Sources. 3 (1978) 145–155.

[40] E. Rocca, J. Steinmetz, Passivation phenomenon of low antimony alloys in deep discharge

conditions of lead–acid batteries, J. Electroanal. Chem. 543 (2003) 153–160.

ot

[41] W.R. Osorio, D.M. Rosa, A. Garcia, The roles of cellular and dendritic microstructural
tn

morphologies on the corrosion resistance of Pb–Sb alloys for lead acid battery grids, J.

Power Sources. 175 (2008) 595–603.

rin

[42] H. Okamoto, Pb-Sb (Lead-Antimony), J. Phase Equilibria Diffus. 32 (2011) 567–567.

[43] B. Farbod, K. Cui, W.P. Kalisvaart, M. Kupsta, B. Zahiri, A. Kohandehghan, E.M.

ep

Lotfabad, Z. Li, E.J. Luber, D. Mitlin, Anodes for Sodium Ion Batteries Based on Tin–

Germanium–Antimony Alloys, ACS Nano. 8 (2014) 4415–4429.

Pr

https://doi.org/10.1021/nn4063598.

21

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153
 [44] J. Songster, A.D. Pelton, The Na-Sb (sodium-antimony) system, J. Phase Equilibria. 14

ed
(1993) 250–255.

[45] W. Plieth, Electrochemistry for Materials Science, 2008. https://doi.org/10.1016/B978-0-

iew
444-52792-9.X5001-5.

[46] M.N. Obrovac, L. Christensen, D.B. Le, J.R. Dahn, Alloy Design for Lithium-Ion Battery

Anodes, J. Electrochem. Soc. 154 (2007) A849. https://doi.org/10.1149/1.2752985.

ev
[47] S.Y. Sayed, W.P. Kalisvaart, E.J. Luber, B.C. Olsen, J.M. Buriak, Stabilizing Tin Anodes

r
in Sodium-Ion Batteries by Alloying with Silicon, ACS Appl. Energy Mater. 3 (2020)

9950–9962. https://doi.org/10.1021/acsaem.0c01641.

[48]
er
H. Li, L. Shi, W. Lu, X. Huang, L. Chen, Studies on Capacity Loss and Capacity Fading
pe
of Nanosized SnSb Alloy Anode for Li-Ion Batteries, J. Electrochem. Soc. 148 (2001)

A915. https://doi.org/10.1149/1.1383070.
ot
tn
rin
ep
Pr

22

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4124153